Photosensitive coloring composition, and color filter and image display device equipped with filter segments using the same

Abstract

To provide a photosensitive composition for a color filter that has high tinting power and high brightness, ensures compatibility between developability and solvent resistance, and can form a patterned pixel having good pattern adhesion and profiles, and a color filter formed therewith.SOLUTION: A photosensitive coloring composition contains a colorant (A), a binder resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), the colorant (A) including a yellow pigment (A1) and a red pigment (A2), the yellow pigment (A1) including the following (a) and (b) adducts, and the binder resin (B) including an alkali-soluble resin (B1) having an acid value of 90 mgKOH / g or more and selected from (III) and (IV). (a): a compound in the form of formula (I) or a tautomer thereof. (b): a compound of formula (II).SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a photosensitive coloring composition used in the manufacture of a color filter used in a color liquid crystal display device, a color solid-state imaging device, an organic EL display device, a quantum dot display device, electronic paper, etc., and to a color filter and an image display device having a filter segment formed using the same. [Background technology]

[0002] A color filter is formed by arranging two or more fine band-shaped filter segments with different hues on a transparent substrate such as a glass substrate in parallel (stripes) or crossing each other, or by arranging two or more fine filter segments with different hues in order in both the vertical and horizontal directions. The filter segments have small dimensions of several microns to several hundreds of microns, and are arranged in a predetermined order for each hue. Currently, the main method for manufacturing color filters is a pigment dispersion method that uses a pigment having excellent resistance to various factors such as light resistance and heat resistance as a coloring material. 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 film by drying, the coating film is exposed to light in a pattern corresponding to a filter segment of a certain color. Next, the unexposed parts of the coating film are removed by development, and then a treatment such as heating is performed as necessary. This results in a filter segment pattern of the first color. Then, the same operation is performed to form filter segment patterns of other colors, completing a color filter. In recent years, as mobile devices have become thinner and lighter, there has been a demand for thinner color filters. In addition, as brightness and color gamuts have increased, the color filters themselves have become highly luminous, and thinner filters are required to increase the aperture ratio of the filter segments and thereby increase brightness.

[0003] Patent Documents 1 to 5 disclose photosensitive coloring compositions containing a metal azo pigment including an adduct of a compound represented by formula (I) or a tautomeric form thereof and a compound represented by formula (II), and a red pigment. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2016-180100 A [Patent Document 2] WO2018-124087 publication [Patent Document 3] JP 2016-180100 A [Patent Document 4] JP 2017-171915 A [Patent Document 5] JP 2018-021204 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, when the pigment concentration is increased to make a thin film, conventional photosensitive coloring compositions have poor developability, which results in problems such as a long development process, a reverse tapered pattern shape, or the pattern itself not adhering well and peeling off.

[0006] The present invention aims to achieve the following objects. That is, an object of the present invention is to provide a photosensitive coloring composition for color filters, which has high coloring power and high brightness, and is compatible with developability and solvent resistance, and is capable of forming pixels of a pattern having good pattern adhesion and pattern shape, and a color filter formed using the same. [Means for solving the problem]

[0007] The present invention relates to a photosensitive coloring composition comprising a colorant (A), a binder resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), The colorant (A) contains a yellow pigment (A1) and a red pigment (A2), The yellow pigment (A1) contains an adduct of the following (a) and (b): The content of the colorant (A) is 40 to 60 mass% in 100 mass% of the nonvolatile content of the photosensitive coloring composition; The photosensitive coloring composition includes the binder resin (B) containing an alkali-soluble resin (B1) selected from the following (III) and (IV) having an acid value of 90 mgKOH / g or more.

[0008] (a) a compound of formula (I) or a tautomeric form thereof [ka]

[0009] [In formula (I), R 1 and R 2 are each independently OH, NH2, or NHR 5 and R 3 and R 4 are each independently =O or =NR 5 and R 5 is a hydrogen atom or an alkyl group, and Me is Ni 2+ , Zn 2+ , Cu 2+ , Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 , Co 2+ , and Co 3+ 2 / 3 are two or more divalent or trivalent metal ions selected from the following series: Cu based on 1 mole of the total of compounds (a) 2+ , Zn 2+ and Ni 2+ The total amount of ions is 95 to 100 mol %, and Al 3+ 2 / 3 , Fe 2+ , Fe 3+2 / 3 , Co 2+ , and Co 3+ The total amount of ions is 0 to 5 mol %, And the Cu 2+ , Zn 2+ and Ni 2+ Based on the total amount of ions, Ni 2+ The amount of ions is 10 to 95 mol %.

[0010] (b) A compound represented by formula (II) [ka]

[0011] [In formula (II), R 6 are each independently a hydrogen atom or an optionally substituted alkyl group. (III) A resin obtained by reacting a reaction product between an epoxy group in a copolymer of an epoxy group-containing monomer and another monomer and a carboxyl group of a carboxyl group-containing monomer with a polybasic acid anhydride. (IV) Resins which are reaction products of carboxyl groups in copolymers of carboxyl group-containing monomers and other monomers with epoxy groups in epoxy group-containing monomers.

[0012] The present invention also relates to the above photosensitive coloring composition, wherein the red pigment (A2) comprises one or more pigments selected from the group consisting of CI Pigment Red 177, CI Pigment Red 254, CI Pigment Red 291, and CI Pigment Red 296.

[0013] The present invention also relates to the above photosensitive coloring composition, wherein the content of the yellow pigment (A1) is 5 to 40 mass % in 100 mass % of the colorant (A).

[0014] The present invention also relates to the above photosensitive coloring composition, wherein the alkali-soluble resin (B1) has a weight average molecular weight of 2,000 to 6,000.

[0015] The present invention also relates to the above photosensitive coloring composition, wherein the content of the colorant (A) is 45 to 60 mass % in 100 mass % of the nonvolatile content of the photosensitive coloring composition.

[0016] The present invention also relates to the above photosensitive coloring composition, wherein the polymerizable compound (C) has a polymerizable compound (C1) containing an acid group.

[0017] The present invention also relates to a color filter comprising a substrate and a filter segment formed from the above-mentioned photosensitive coloring composition.

[0018] The present invention also relates to an image display device comprising the above color filter. Effect of the Invention

[0019] By using the photosensitive coloring composition of the present invention, it is possible to form a filter segment having high coloring power and high brightness, and having both developability and solvent resistance, and having good pattern adhesion and pattern shape. Therefore, by using the photosensitive coloring composition of the present invention, it is possible to obtain a high-quality color filter. [Brief description of the drawings]

[0020] [Figure 1] FIG. 1 is a schematic cross-sectional view of an image display device according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] The terms used in this specification are defined below. When "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" is written, it means "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide", respectively, unless otherwise specified. "CI" in this specification means Color Index (CI). Yellow pigment (A1) is also called metal azo pigment (A1).

[0022] <Coloring agent> The photosensitive coloring composition of the present invention contains a yellow pigment (A1) and a red pigment (A2) as colorants, and may contain dyes and other pigments as necessary. The photosensitive coloring composition of the present invention has high brightness and can achieve both developability and solvent resistance, even when the pigment concentration is high. Here, a high pigment concentration means that the pigment concentration is 40% by mass or more, preferably 45 to 60% by mass, based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. As the pigment, organic or inorganic pigments can be used alone or in combination of two or more kinds. The pigment is preferably a pigment having high color development and high heat resistance, particularly a pigment having high thermal decomposition resistance, and usually an organic pigment is used. Specific examples of organic pigments that can be used in the photosensitive coloring composition are shown below by color index number.

[0023] <Yellow pigment (A1), metal azo pigment (A1)> The yellow pigment (A1) of the present invention contains the following adducts (a) and (b). If necessary, it may contain other yellow pigments. The content of the yellow pigment (A1) is preferably 5 to 40 mass% in 100 mass% of the colorant (A).

[0024] (a) a compound of formula (I) or a tautomeric form thereof [ka]

[0025] [In formula (I), R 1 and R 2 are independently OH, NH 2 , or NHR 5 and R 3 and R 4 are each independently =O or =NR 5 It is. More preferably, in formula (I), R 1 and R 2 is OH and R 3 and R 4 is =O.

[0026] R 5 is hydrogen or alkyl, and Me is Ni 2+ , Zn 2+ , Cu 2+ , Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 , Co 2+ , and Co 3+ 2 / 3 are two or more divalent or trivalent metal ions selected from the following series: In formula (I), when Me is a trivalent metal ion, an additional anion is required to balance the charge. Examples of such anions include those represented by formula (Ia). Furthermore, in the case of the anion of formula (Ia), on average, two molecules of formula (Ia) are balanced by one molecule of formula (I) and two trivalent metal ions.

[0027] [ka] [In the formula, R 1 , R 2 , R 3 , and R 4 has the same meaning as in formula (I).

[0028] Cu based on 1 mole of the total of compounds (a) 2+, Zn 2+ and Ni 2+ The total amount of the ions is 95 to 100 mol %, preferably 98 to 100 mol %, and more preferably 99.9 to 100 mol %.

[0029] In addition, Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 , Co 2+ , and Co 3+ The total amount of ions is 0 to 5 mol %, preferably 0 to 2 mol %, and more preferably 0 to 0.1 mol %.

[0030] In addition, Cu 2+ , Zn 2+ and Ni 2+ Based on the total amount of ions, Ni 2+ The amount of ions is 10 to 95 mol %. In general, Ni in metallic azo pigments 2+ vs. Zn 2+ The molar ratio of these is 1:1 to 19:1, preferably 2:1 to 4:1, and more preferably 2.3:1 to 3:1. In general, Cu in metallic azo pigments 2+ vs. Zn 2+ The molar ratio of is 1:9 to 9:1, preferably 2:1 to 4:1, and more preferably 2.3:1 to 3:1.

[0031] (b) A compound represented by formula (II) [ka]

[0032] [In general formula (II), R 6 are each independently hydrogen or optionally substituted alkyl.

[0033] Preferably, in formula (II), R 6 is hydrogen or a C1-C4 alkyl group which may be mono- or polysubstituted with OH.6 is hydrogen.

[0034] Other yellow pigments include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, and the pigments described in JP-A-2012-226110. Preferred are CI Pigment Yellow 138, 139, 150, 185, 231, and 233, and the pigments described in JP-A-2012-226110.

[0035] <Red pigment (A2)> The photosensitive coloring composition of the present invention contains a red pigment (A2). Examples of the red pigment (A2) include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60 , 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 9, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 26 Examples of the pigments described in JP-A-2014-134712 and JP-A-2014-134712 include pigments described in Japanese Patent No. 6,368,844. Among these, from the viewpoints of heat resistance, light fastness, and transmittance of the filter segment, preferred are CI Pigment Red 48:1, 122, 177, 224, 242, 269, 254, 291, 295, 296, the pigments described in JP-A-2014-134712, and the pigments described in Japanese Patent No. 6,368,844, and more preferred are CI Pigment Red 177, 254, 291, 295, 296, the pigments described in JP-A-2014-134712, and the pigments described in Japanese Patent No. 6,368,844.

[0036] <Other pigments> In addition, the photosensitive coloring composition of the present invention may contain an orange pigment such as CI Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73 and / or a yellow pigment described below.

[0037] Examples of blue pigments include CI 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, and 79. Among these, from the viewpoints of heat resistance, light resistance, and transmittance of the filter segment, preferred are CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6, and more preferred is CI Pigment Blue 15:6.

[0038] Examples of inorganic pigments include titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, umber, synthetic iron black, etc. Inorganic pigments are used in combination with organic pigments to ensure good coatability, sensitivity, developability, etc. while maintaining a balance between saturation and brightness.

[0039] <Mixing pigments> When organic pigments such as yellow pigment (A1) and red pigment (A2) are used as colorants, it is preferable to mix them with other raw materials after fine processing. Examples of the method of fine processing include wet grinding, dry grinding, and dissolution precipitation. Among these, salt milling by a kneader method, which is a type of wet grinding, is preferable. The average primary particle size of the organic pigment after fine processing is preferably 10 to 80 nm, more preferably 15 to 70 nm. A moderate particle size improves dispersibility and the contrast ratio of the coating. The average primary particle size is the average value of about 20 particles arbitrarily selected from an enlarged image of a TEM (transmission electron microscope). When the particle has a vertical axis length and a horizontal axis length, the vertical axis length is used.

[0040] The salt milling process is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded while being heated using a batch or continuous kneader such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, or a planetary mixer, and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed during salt milling by utilizing the high hardness of the inorganic salt. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution.

[0041] Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate. Among these, sodium chloride (table salt) is preferred from the viewpoint of cost. The amount of the water-soluble inorganic salt used is preferably 50 to 2000 parts by mass, and more preferably 300 to 1000 parts by mass, per 100 parts by mass of the pigment, from the viewpoints of both treatment efficiency and production efficiency.

[0042] The water-soluble organic solvent moistens the pigment and the water-soluble inorganic salt. The water-soluble organic solvent is a compound that dissolves (is mixed) in water and does not substantially dissolve the water-soluble inorganic salt. The water-soluble organic solvent is preferably a high-boiling solvent having a boiling point of 120°C or more, in that it is less likely to volatilize due to the temperature rise during salt milling. Examples of the water-soluble organic solvent include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and liquid polypropylene glycol. The amount of the water-soluble organic solvent used is preferably 5 to 1000 parts by mass, more preferably 50 to 500 parts by mass, relative to 100 parts by mass of the pigment.

[0043] During the salt milling treatment, a resin can be added as necessary. Examples of the resin include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. The resin is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in a water-soluble organic solvent. The amount of the resin used is preferably 5 to 200 parts by mass relative to 100 parts by mass of the pigment. <dye> Examples of the dye include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. In addition, examples of the dye include dye derivatives and lake pigments obtained by converting dyes into lakes.

[0044] In addition, the dye may be an acid dye having an acidic group such as sulfonic acid or carboxylic acid, or in the case of a direct dye, an inorganic salt of an acid dye; a salt-forming compound of an acid dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound; or a salt-forming compound of a resin component having an amino group and an acid dye. A salt-forming compound of an acid dye and a compound having an onium salt group is also preferable because it has excellent fastness. In addition, the compound having an onium salt group is preferably a resin having a cationic group in the side chain.

[0045] Examples of the basic dye include salt-forming compounds with organic acids, perchloric acid, or metal salts thereof. Among the salt-forming compounds, salt-forming compounds of basic dyes are preferred because they have excellent resistance to various types of substances and are compatible with pigments.

[0046] The chemical structure of the dye may be, for example, an azo dye, a disazo dye, an azomethine dye (such as an indoaniline dye or an indophenol dye), a dipyrromethene dye, a quinone dye (such as a benzoquinone dye, a naphthoquinone dye, anthraquinone dye, or anthrapyridone dye), a carbonium dye (such as a diphenylmethane dye, a triphenylmethane dye, a xanthene dye, or an acridine dye), a quinoneimine dye (such as an oxazine dye), or a quinoneimine dye (such as an oxazine dye). dyes, thiazine dyes, etc.), azine dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, etc. Among these, from the viewpoint of color characteristics such as hue, color separation, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferred. Specific structures of dyes are described in "New Edition Dye Handbook" (edited by Organic Synthesis Chemistry Association; Maruzen, 1970), "Color Index" (The Society of Dyers and colourists), "Dye Handbook" (edited by Okawara et al.; Kodansha, 1986), and the like.

[0047] <Dye derivatives> The photosensitive coloring composition of the present invention can use a dye derivative as necessary. The dye derivative is a compound having an acidic group, a basic group, a neutral group, etc. in an organic dye residue. Examples of the dye derivative include compounds having an acidic substituent such as a sulfo group, a carboxy group, or a phosphoric acid group, as well as amine salts thereof, compounds having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal, and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group. Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

[0048] Specifically, diketopyrrolopyrrole dye derivatives are described in JP 2001-220520 A, WO 2009 / 081930 B, WO 2011 / 052617 B, WO 2012 / 102399 B, and JP 2017-156397 A; phthalocyanine dye derivatives are described in JP 2007-226161 A, WO 2016 / 163351 B, JP 2017-165820 B, and Japanese Patent No. 5753266 A; and anthraquinone dye derivatives are described in JP-A-63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009 / 025325 pamphlet; quinacridone dye derivatives are disclosed in JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383; dioxazine dye derivatives are disclosed in JP-A-2011-162662; thiazine indigo dye derivatives are disclosed in JP-A-2007-3147 85, triazine-based dye derivatives are disclosed in JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, and JP-A-2007-314681, benzoisoindole-based dye derivatives are disclosed in JP-A-2009-57478, quinophthalone-based dye derivatives are disclosed in JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, and JP-A-2007-314681. Examples of naphthol-based dye derivatives include those described in JP-A-2012-208329 and JP-A-2014-5439, examples of azo-based dye derivatives include those described in JP-A-2001-172520 and JP-A-2012-172092, examples of acidic substituents include those described in JP-A-2004-307854, and examples of basic substituents include those described in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, and JP-A-2005-213404. In these documents, the dye derivative may be referred to as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply as a compound, but the compound having a substituent such as an acidic group, a basic group, or a neutral group in the organic dye residue is synonymous with the dye derivative.

[0049] These dye derivatives can be used alone or in combination of two or more kinds.

[0050] The dye derivative is added in an amount of preferably 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, and even more preferably 5 to 50 parts by mass, per 100 parts by mass of the pigment.

[0051] By adding a dye derivative to a pigment and carrying out a pigmentation treatment such as acid pasting, acid slurry, dry milling, salt milling, or solvent salt milling, the dye derivative is adsorbed onto the pigment surface, and the primary particles of the pigment can be made finer than when the dye derivative is not added.

[0052] By adding a dye derivative to a pigment and carrying out a dispersion treatment such as wet dispersion using a two-roll roller, a three-roll roller, or beads, the dye derivative is adsorbed onto the pigment surface, the pigment surface has polarity, and adsorption of the resin-type dispersant is promoted, and compatibility with the pigment, the dye derivative, the resin-type dispersant, the solvent, and other additives is improved, and the dispersion stability and viscosity stability over time when the composition is made into a colored composition or a colored curable composition are improved. In addition, the improved compatibility provides excellent stability over time of the coating film when the colored curable composition is applied to a glass substrate, etc., and the stability and characteristics dependency of the pattern shape on the waiting time from application of the colored curable composition to exposure (PCD: Post Coating Delay) and the waiting time from exposure to heat treatment (PED: Post Exposure Delay) and the line width sensitivity stability are improved. In addition, by adsorbing and covering the pigment surface with the dye derivative and the resin-type dispersant, it is possible to suppress the aggregation of the pigment and the crystal precipitation due to sublimation when the coating film is heated and baked. Furthermore, the variation in development time and development residue are also suppressed.

[0053] <Resin-type dispersant> A known resin-type dispersant can be used in the photosensitive coloring composition of the present invention. The resin-type dispersant may be any dispersant that has a colorant affinity site that has the property of adsorbing to an added colorant and a site that is compatible with a colorant carrier, and that functions to adsorb to an added colorant and stabilize the dispersion in the colorant carrier. Specifically, urethane-based dispersants such as polyurethane, polycarboxylates such as polyacrylates, unsaturated polyamides, polycarboxylates, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylates, and modified products thereof. Examples of the dispersants that can be used include oil-based dispersants such as amides formed by the reaction of poly(lower alkylene imine) with a polyester having a free carboxyl group or salts thereof, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyester-based compounds, modified polyacrylate-based compounds, ethylene oxide / propylene oxide adducts, and phosphate-based compounds, and these can be used alone or in combination of two or more types.

[0054] Preferred examples of resin-type dispersants having an acidic functional group include resin-type dispersants having an aromatic carboxylic acid structure, which can be produced by known methods such as those described in WO2008 / 007776, JP2008-029901A, JP2009-155406A, JP2010-185934A, JP2011-157416A, JP2009-251481A, JP2007-23195A, and JP1996-143651A.

[0055] Preferred examples of resin-type dispersants having a basic functional group include nitrogen-atom-containing graft copolymers, and nitrogen-atom-containing acrylic block copolymers and urethane-based polymer dispersants having functional groups including tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc. in the side chains.

[0056] As disclosed in JP 2009-185277 A, a preferred example is the combined use of a resin-type dispersant having an aromatic carboxyl group and a vinyl resin having a tertiary amino group (having the function of a resin-type dispersant).

[0057] The resin type dispersant is preferably used in an amount of about 3 to 200% by mass based on the total amount of the colorant, and from the viewpoint of film-forming properties, more preferably about 5 to 100% by mass.

[0058] <Binder resin (B)> The photosensitive coloring composition of the present invention contains a binder resin (B). The binder resin (B) contains an alkali-soluble resin (B1) selected from the following (III) and (IV) having a carboxyl group and a polymerizable unsaturated group in the side chain and an acid value of 90 mgKOH / g or more. If necessary, it may contain an alkali-soluble resin having no ethylenically unsaturated double bond, a thermoplastic resin other than these, or a thermosetting compound. The binder resin (B) is a resin having a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm. The transmittance is preferably 95% or more. In terms of physical properties, the binder resin is preferably an alkali-soluble resin from the viewpoint of developability. The alkali-solubility is for imparting development solubility in the alkali development step during the production of a color filter, and an acidic group is required.

[0059] (III) A resin obtained by reacting a reaction product between an epoxy group in a copolymer of an epoxy group-containing monomer and another monomer and a carboxyl group in a carboxyl group-containing monomer with a polybasic acid anhydride. (IV) Resins which are reaction products of carboxyl groups in copolymers of carboxyl group-containing monomers and other monomers with epoxy groups in epoxy group-containing monomers.

[0060] (III) A resin obtained by reacting a polybasic acid anhydride with a reaction product of an epoxy group in a copolymer of an epoxy group-containing monomer and a carboxyl group of a carboxyl group-containing monomer is obtained by adding a carboxyl group of a carboxyl group-containing monomer, typically an unsaturated monobasic acid having an ethylenically unsaturated double bond, to a side-chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with another monomer.Then, the polybasic acid anhydride is reacted with the generated hydroxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[0061] Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with unsaturated monobasic acids.

[0062] The carboxyl group-containing monomer means an unsaturated bond monomer containing a carboxyl group, and an example of the monomer is an unsaturated monobasic acid. Examples of the unsaturated monobasic acid include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position.

[0063] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. If necessary, for example, to increase the number of carboxyl groups, a tricarboxylic acid anhydride such as trimellitic anhydride or a tetracarboxylic acid dianhydride such as pyromellitic dianhydride may be used to hydrolyze the remaining anhydride groups.

[0064] Examples of other monomers include the following: (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and ethoxypolyethylene glycol (meth)acrylate; Alternatively, examples of the monomer include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate and vinyl propionate.

[0065] Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide Examples of the polyimide include N-substituted maleimides such as imidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide and 9-maleimidoacridine, EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

[0066] (IV) A resin which is a reaction product between a carboxyl group in a copolymer of a carboxyl group-containing monomer and another monomer and an epoxy group of an epoxy group-containing monomer can be obtained by a method in which an ethylenically unsaturated monomer having a carboxyl group and another monomer are copolymerized to cause an addition reaction of an epoxy group-containing monomer with a part of the side chain carboxyl groups of a copolymer obtained by addition reaction of the monomer, thereby introducing an ethylenically unsaturated double bond and a carboxyl group. Examples of the carboxyl group-containing monomer, other monomer, and epoxy group-containing monomer are the same as those exemplified in (III).

[0067] The binder resin (B) is an alkali-soluble resin (B1) selected from the above (III) and (IV) having a carboxyl group and a polymerizable unsaturated group in the side chain and an acid value of 90 mgKOH / g or more, and may be, for example, a thermoplastic resin, a thermosetting resin, an active energy ray curable resin, etc., and two or more kinds may be used in combination. The active energy ray curable resin may be a thermoplastic resin or a thermosetting resin having an active energy ray reactive functional group.

[0068] The content of the binder resin is preferably 20 to 400 parts by mass, and more preferably 50 to 250 parts by mass, per 100 parts by mass of the colorant. When an appropriate amount is contained, a coating can be easily formed and good color characteristics can be easily obtained.

[0069] <Active energy ray-curable alkali-soluble resin> The active energy ray-curable alkali-soluble resin preferably has an ethylenically unsaturated double bond. The ethylenically unsaturated double bond can be obtained by the following production method other than the production method of the alkali-soluble resin (B1) selected from the above (III) and (IV). By curing with active energy rays, the resin is three-dimensionally crosslinked, increasing the crosslink density and improving chemical resistance.

[0070] <Method for producing active energy ray-curable alkali-soluble resin> Other than the alkali-soluble resin (B1) selected from the above (III) and (IV), the active energy ray-curable alkali-soluble resin can be obtained by a method in which an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group is reacted with a side chain hydroxyl group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another monomer.

[0071] Examples of the ethylenically unsaturated monomer having a hydroxyl group include hydroxyalkyl methacrylates such as 2-hydroxyethyl(meth)acrylate, 2- or 3-hydroxypropyl(meth)acrylate, 2-, 3- or 4-hydroxybutyl(meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. Other examples include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to hydroxyalkyl(meth)acrylates, and polyester mono(meth)acrylates obtained by addition of poly(γ-valerolactone), poly(ε-caprolactone, and / or poly(12-hydroxystearic acid). From the viewpoint of suppressing foreign matter in the coating, 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferred, and from the viewpoint of sensitivity, it is preferred to use a compound having 2 to 6 hydroxyl groups, with glycerol mono(meth)acrylate being even more preferred.

[0072] Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0073] Examples of 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, phosphate group-containing ethylenically unsaturated monomers, carboxyl group-containing ethylenically unsaturated monomers, and the like. Examples of N-substituted maleimides include cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-( 2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimide acridine and the like. Examples of the alkyleneoxy group-containing monomer include EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

[0074] As the carboxyl group-containing ethylenically unsaturated monomer, the monomers already explained can be used.

[0075] The phosphate group-containing ethylenically unsaturated monomer is, for example, a compound obtained by reacting the hydroxyl group of the above-mentioned hydroxyl group-containing ethylenically unsaturated monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

[0076] <Thermoplastic resin> Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. Examples of the alkali-soluble thermoplastic resin include resins having an acidic group such as a carboxyl group or a sulfonic group. Examples of the alkali-soluble thermoplastic resin include acrylic resins having an acidic group, α-olefin / maleic acid (anhydride) copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, and isobutylene / maleic acid (anhydride) copolymers. Among these, acrylic resins having an acidic group and styrene / styrene sulfonic acid copolymers are preferred in terms of improving developability, heat resistance, and transparency.

[0077] <Alkali-soluble resin having no ethylenically unsaturated double bond> The coloring composition of the present specification can contain an alkali-soluble resin having no ethylenically unsaturated double bond in order to adjust the degree of hardening of the coating.

[0078] The weight average molecular weight (Mw) of the alkali-soluble resin in the present invention is 1,000 to 40,000, preferably 1,500 to 20,000, more preferably 2,000 to 6,000, in order to impart alkali development solubility. The value of Mw / Mn is preferably 10 or less. If the weight average molecular weight (Mw) is less than 1,000, the adhesion to the substrate decreases, making it difficult to leave an exposed pattern. If it exceeds 40,000, the alkali development solubility decreases, residues are generated, and the pattern shape deteriorates. The acid value of the alkali-soluble resin in the present invention is 90 to 200 (KOH mg / g) in order to impart solubility in alkaline development, preferably 120 to 180, more preferably 140 to 170. If the acid value is less than 90, the solubility in alkaline development decreases, residues are generated, and the pattern shape deteriorates. If the acid value exceeds 200, the adhesion to the substrate decreases, making it difficult to leave an exposed pattern.

[0079] Each of the raw materials used in the synthesis of the binder resin can be used alone or in combination of two or more kinds.

[0080] <Thermosetting compounds> In the present invention, a thermosetting compound can be further included in combination with a thermoplastic resin as a binder resin. When a color filter is produced using the photosensitive coloring composition of the present invention, the thermosetting compound reacts during baking of the filter segment to increase the crosslink density of the coating film, thereby improving the heat resistance of the filter segment, suppressing pigment aggregation during baking of the filter segment, and improving the contrast ratio.

[0081] The thermosetting compound may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds, but the present invention is not limited thereto. In the photosensitive coloring composition of the present invention, epoxy compounds and oxetane compounds are preferably used.

[0082] <Polymerizable compound (C)> The photosensitive coloring composition of the present invention contains a polymerizable compound. The polymerizable compound includes a monomer or oligomer that is cured by ultraviolet light, heat, or the like to form a transparent resin.

[0083] Examples of the polymerizable compound include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, Examples of the acrylic acid esters and methacrylic acid esters include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid ester of methylolated melamine, epoxy (meth)acrylate, and urethane acrylate, as well as (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinyl formamide, and acrylonitrile.

[0084] (Polymerizable compound (C1) containing an acid group) The polymerizable compound preferably contains a polymerizable compound containing an acid group. Examples of the acid group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group. When the polymerizable compound contains a polymerizable compound containing an acid group, the alkaline developability is improved.

[0085] Examples of photopolymerizable monomers having an acid group include esters of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid with dicarboxylic acids; esters of polycarboxylic acids with monohydroxyalkyl (meth)acrylates; and the like. Specific examples include free carboxyl group-containing monoesters of monohydroxy oligoacrylates or monohydroxy oligomethacrylates, such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, with dicarboxylic acids, such as malonic acid, succinic acid, glutaric acid, and phthalic acid; and free carboxyl group-containing oligoesters of tricarboxylic acids, such as propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid, with monohydroxy monoacrylates or monohydroxy monomethacrylates, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

[0086] (Polymerizable compound having urethane bond) The polymerizable compound may contain a monomer having an ethylenically unsaturated bond and a urethane bond. Examples of the monomer include a polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and a polyfunctional urethane acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and further reacting the alcohol with a (meth)acrylate having a hydroxyl group.

[0087] Examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide modified penta(meth)acrylate, dipentaerythritol propylene oxide modified penta(meth)acrylate, dipentaerythritol caprolactone modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxy(meth)acrylate, and a hydroxyl group-containing polyol polyacrylate.

[0088] Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

[0089] The polymerizable compounds can be used alone or in combination of two or more kinds.

[0090] The blending amount of the polymerizable compound is preferably 1 to 50 mass %, more preferably 2 to 40 mass parts, based on 100 mass % of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is blended, the curability and developability are further improved.

[0091] <Photopolymerization initiator (D)> The photosensitive coloring composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator may be, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylamino)phenyl]-2-methyl-1-butanone. acetophenone compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzil dimethyl ketal; benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3',4,4'-tetra(t-butanone) benzophenone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, triazine-based compounds such as 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;Examples of suitable oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds. Among these, oxime ester compounds are preferred.

[0092] The photopolymerization initiators can be used alone or in combination of two or more kinds.

[0093] (Oxime ester compounds) In the oxime ester compound, the NO bond of the oxime is cleaved by absorbing ultraviolet light, generating iminyl radicals and alkyloxy radicals. These radicals further decompose to generate highly active radicals, so that 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 decrease, and the degree of curing of the coating film may decrease, but oxime ester compounds are preferably used because they have high quantum efficiency.

[0094] Examples of the oxime ester compound include oxime ester photopolymerization initiators described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, and the like.

[0095] The content of the photopolymerization initiator is preferably 2 to 50 parts by mass, and more preferably 2 to 30 parts by mass, based on 100 parts by mass of the colorant. When an appropriate amount is added, the photocurability and developability are further improved.

[0096] <Sensitizer> Furthermore, the photosensitive coloring composition of the present invention may contain a sensitizer. Examples of sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazinoporphyrazine derivatives. , phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenyl glyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like.

[0097] Among the above sensitizers, particularly suitable sensitizers include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, and 3,6-dibenzoyl-N-ethylcarbazole are used.

[0098] More specifically, examples of the sensitizers include, but are not limited to, those described in "Dye Handbook" edited by Makoto Okawara et al. (Kodansha, 1986), "Chemistry of Functional Dyes" edited by Makoto Okawara et al. (CMC, 1981), "Tokushu No Futoshi Zairyo" edited by Chuzaburo Ikemori et al., and "Tokushu No Futoshi Zairyo" (CMC, 1986). In addition, a sensitizer that absorbs light from the ultraviolet to near infrared region may also be contained.

[0099] The sensitizers can be used alone or in combination of two or more kinds.

[0100] The content of the sensitizer is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass, based on 100 parts by mass of the photopolymerization initiator. When an appropriate amount is contained, the curability and developability are further improved.

[0101] <Thiol-based chain transfer agents> The photosensitive coloring composition of the present invention preferably contains a thiol-based chain transfer agent as a chain transfer agent. By using thiol together with a photopolymerization initiator, the thiol acts as a chain transfer agent in the radical polymerization process after light irradiation, and generates a thiyl radical that is not easily inhibited by oxygen, so that the obtained coloring composition has high sensitivity.

[0102] Also preferred is a polyfunctional aliphatic thiol having two or more thiol groups bonded to an aliphatic group such as a methylene or ethylene group. More preferred is a polyfunctional aliphatic thiol having four or more thiol groups. By increasing the number of functional groups, the polymerization initiation function is improved, and curing can be achieved from the surface of the pattern to the vicinity of the substrate.

[0103] Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, ... Examples of the thiopropionate include taerythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, and the like. Preferred examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

[0104] The thiol chain transfer agents can be used alone or in combination of two or more kinds.

[0105] The content of the thiol chain transfer agent is preferably 0.1 to 10 mass%, more preferably 0.1 to 3 mass%, based on 100 mass% of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is contained, the photosensitivity and taper shape are improved, and wrinkles are less likely to occur on the coating surface.

[0106] <Polymerization inhibitor> The photosensitive coloring composition may contain a polymerization inhibitor, which can suppress photosensitivity due to diffracted light from a mask during exposure in a photolithography method, making it easier to obtain a pattern of a desired shape.

[0107] Examples of the polymerization inhibitor include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4-tert-butyl catechol, and 3,5-di-tert-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, and 2-n- alkyl resorcinol compounds such as butyl resorcinol, 4-n-butyl resorcinol, 2-tert-butyl resorcinol, and 4-tert-butyl resorcinol; alkyl hydroquinone compounds such as methyl hydroquinone, ethyl hydroquinone, propyl hydroquinone, tert-butyl hydroquinone, and 2,5-di-tert-butyl hydroquinone; phosphine compounds such as tributyl phosphine, trioctyl phosphine, tricyclohexyl phosphine, triphenyl phosphine, and tribenzyl phosphine; phosphine oxide compounds such as trioctyl phosphine oxide and triphenyl phosphine oxide; phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite; pyrogallol; and phloroglucine.

[0108] The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. Within this range, the effect of the polymerization inhibitor is increased, and the linearity of the taper, wrinkles in the coating film, pattern resolution, etc. are improved.

[0109] <Ultraviolet absorbing agent> The photosensitive coloring composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function, and examples of the ultraviolet absorber include benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, salicylic acid ester-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds.

[0110] The content of the ultraviolet absorber is preferably 5 to 70% by mass relative to 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. When an appropriate amount is contained, the resolution after development is further improved.

[0111] The total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is contained, the adhesion between the substrate and the coating is further improved, and good resolution can be obtained.

[0112] 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-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side and linear alkyl ester mixture, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300 reaction products, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t- Butyl-4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate. Other oligomer and polymer type compounds having a benzotriazole structure can also be used.

[0113] Triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. Examples of the compound include 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine. In addition, oligomer and polymer type compounds having a triazine structure can also be used.

[0114] Benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

[0115] Examples of the salicylate compounds include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, etc. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

[0116] <Antioxidants> The photosensitive coloring composition of the present invention can contain an antioxidant. The antioxidant prevents the photopolymerization initiator and thermosetting compound contained in the photosensitive coloring composition from being oxidized and yellowed by the thermal process during thermal curing or ITO annealing, and therefore can improve the transmittance of the coating film. In particular, when the colorant concentration of the coloring composition is high, the amount of the coating film crosslinking component is reduced, so that a highly sensitive crosslinking component is used or the amount of the photopolymerization initiator is increased, resulting in a phenomenon in which yellowing during the thermal process becomes stronger. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a high transmittance of the coating film can be obtained.

[0117] Examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In this specification, the antioxidant is preferably a compound that does not contain a halogen atom.

[0118] Among these, from the viewpoint of achieving both the transmittance and the sensitivity of the coating film, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0119] The antioxidants can be used alone or in combination of two or more kinds.

[0120] Furthermore, when the content of the antioxidant is 0.5 to 5.0% by mass relative to 100% by mass of the solid content of the colored composition, the transmittance, spectral characteristics, and sensitivity are excellent, which is more preferable.

[0121] <Leveling agent> In order to improve the coating property of the composition on a transparent substrate and the drying property of the colored coating, it is preferable to add a leveling agent to the photosensitive coloring composition of the present invention. As the leveling agent, various surfactants such as silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants can be used.

[0122] When the photosensitive coloring composition of the present invention contains a surfactant, the amount of the surfactant added is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0 mass %, based on the total solid content of the composition of the present invention. Within this range, the coloring composition has a good balance between the coatability, pattern adhesion, and transmittance. The photosensitive coloring composition of the present invention may contain only one type of surfactant, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0123] <Storage stabilizer> The coloring composition of the present invention can contain a storage stabilizer to stabilize the viscosity of the composition over time. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites. 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).

[0124] <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 improver, the reproducibility of fine lines is improved and the resolution is improved.

[0125] Examples of the adhesion improver include vinyl silanes such as vinyl trimethoxy silane and vinyl triethoxy silane, (meth)acrylic silanes such as 3-methacryloxypropyl methyl dimethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyl diethoxy silane, 3-methacryloxypropyl triethoxy silane and 3-acryloxypropyl trimethoxy silane, epoxy silanes such as 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyl methyl dimethoxy silane, 3-glycidoxypropyl trimethoxy silane, 3-glycidoxypropyl methyl diethoxy silane and 3-glycidoxypropyl triethoxy silane, N-2-(aminoethyl)-3-aminopropyl methyl dimethoxy silane and N-2-(aminoethyl)-3- Examples of the silane coupling agent include aminosilanes such as aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and hydrochloride salt of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureidos such as 3-ureidopropyltriethoxysilane, sulfides such as bis(triethoxysilylpropyl)tetrasulfide, and isocyanates such as 3-isocyanatepropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the colorant in the coloring composition. Within this range, the effect is large, and a good balance of adhesion, resolution, and sensitivity is achieved, which is more preferable.

[0126] <Method for producing photosensitive coloring composition> The photosensitive coloring composition included in the present invention can be produced by finely dispersing a colorant in a colorant carrier such as a dispersant or binder resin and / or a solvent, preferably together with a dispersion aid (dye derivative or surfactant), using various dispersing means such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). At this time, two or more types of colorants may be dispersed simultaneously in a colorant carrier, or may be mixed with those dispersed separately in a colorant carrier. When the solubility of a colorant such as a dye is high, specifically, when the solubility is high in the solvent used, and the colorant is dissolved by stirring and no foreign matter is confirmed, it is not necessary to produce the colorant by fine dispersion as described above.

[0127] In addition, when used as a photosensitive coloring composition (resist material) for color filters, it can be prepared as a solvent-developable or alkali-developable coloring composition. The solvent-developable or alkali-developable coloring composition can be prepared by mixing the colorant dispersion, the photopolymerizable monomer and / or the photopolymerization initiator, and, if necessary, a solvent, other dispersion aids, and additives. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

[0128] <Solvent> The coloring composition of the present invention contains a solvent to facilitate the formation of a colored film by coating the composition on a substrate such as glass so that the dry film thickness is 0.2 to 5 μm. The solvent is selected in consideration of the good coatability of the coloring composition, the solubility of each component of the coloring composition, and safety.

[0129] As the solvent, any solvent commonly used in the relevant field can be used, and they are used alone or in combination as appropriate according to the coating conditions (speed, drying conditions, etc.) taking into consideration performance such as boiling point, SP value, evaporation rate, and viscosity.

[0130] Examples of the solvent to be used include ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO- or -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

[0131] Of the above solvents, from the viewpoint of coatability and drying property, it is preferable to include an organic solvent having a boiling point at 1 atm of 120° C. or more and 180° C. or less. 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, etc. are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are more preferred.

[0132] <Removal of large particles> The photosensitive coloring composition of the present invention is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of centrifugation at a gravitational acceleration of 3000 to 25000 G, filtration with a sintered filter or a membrane filter, etc. In this way, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, the particles are 0.3 μm or less.

[0133] <Color filters> Next, the color filter of the present invention will be described. The color filter of the present invention comprises a red filter segment, a green filter segment, and a blue filter segment, and may further comprise a magenta filter segment, a cyan filter segment, and a yellow filter segment.

[0134] <Manufacturing method for color filters> It is preferable to form a color filter by first forming a black matrix on a substrate and then forming filter segments. It is also possible to form a thin film transistor (TFT) on the substrate before forming the black matrix. Examples of the black matrix include a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, and a resin film with a light-shielding agent dispersed therein.

[0135] The filter segments can be formed by, for example, a printing method, an electrodeposition method, a transfer method, an ink-jet method, a photolithography method, or the like. The printing method is excellent in terms of low cost and mass productivity as a method for producing color filters, since a pattern can be formed simply by repeating printing and drying of a photosensitive coloring composition prepared as a printing ink. Furthermore, the development of printing technology has made it possible to print fine patterns with high dimensional accuracy and smoothness. In order to perform printing, it is preferable to have a composition that does not cause the ink to dry or solidify on the printing plate or blanket. In addition, control of the fluidity of the ink on the printing machine is also important, and the ink viscosity can be adjusted by using a dispersant or an extender pigment.

[0136] In the electrodeposition method, a transparent conductive film is formed on a transparent substrate, and filter segments of each color are electrodeposited on the transparent conductive film by electrophoresis of colloidal particles to produce a color filter. In the transfer method, filter segments are formed on the release-treated surface of a release sheet, and then the filter segments are transferred to a transparent substrate to produce a color filter.

[0137] In the photolithography method, for example, a photosensitive coloring composition containing a colorant of a certain color tone is applied onto a transparent substrate so that the dry film thickness is about 0.2 to 5 μm to form a film. The obtained film (hereinafter referred to as the first film) is exposed (irradiated with light) through a mask having a predetermined pattern. Then, the film is developed by immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like, and the uncured parts are removed to obtain a desired pattern. This process can be similarly carried out using a photosensitive coloring composition containing a colorant of another color tone to produce a color filter having filter segments of each color. In addition, a second film (oxygen barrier film) can be formed on the first film before exposure using polyvinyl alcohol or a water-soluble acrylic resin. This prevents the first film from coming into contact with oxygen, and thus the exposure sensitivity is further improved. In addition, the color filter can be heated to cure the uncured polymerizable compound in the filter segment. The photolithography method is preferable because it can produce a color filter with higher accuracy than the printing method.

[0138] Examples of the coating device include a spray coater, a spin coater, a slit coater, and a roll coater. A drying step can be carried out during coating. Examples of the drying device include a hot air oven and an infrared heater.

[0139] The developer may be an alkaline developer, for example, an inorganic alkali such as sodium carbonate or sodium hydroxide, or an organic alkali such as dimethylbenzylamine or triethanolamine. A defoaming agent or a surfactant may be added to the developer.

[0140] The color filter of the present invention is laminated to an opposing substrate using a sealant, liquid crystal is injected through an injection port provided in the sealing part, the injection port is sealed, and a polarizing film or a retardation film is laminated to the outside of the substrate as necessary, to produce a color liquid crystal display device. This color liquid crystal display device can be used in liquid crystal display modes that use color filters such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertically aligned (VA), and optically convencive bend (OCB).

[0141] The color filter in this specification can be used for image display devices such as solid-state imaging devices, organic EL display devices, quantum dot display devices, electronic paper, and head-mounted displays, in addition to liquid crystal display devices.

[0142] <Image display device> An image display device equipped with the color filter of the present invention will be described. The image display device of the present invention comprises the color filter of the present invention and a light source. Examples of light sources include cold cathode fluorescent lamps (CCFL) and white LEDs, but in the present invention, it is preferable to use a white LED because it broadens the red reproduction range. Fig. 1 is a schematic cross-sectional view of an image display device 10 equipped with the color filter of the present invention. The device 10 shown in Fig. 1 comprises a pair of transparent substrates 11 and 21 arranged to face each other at a distance, with liquid crystal LC sealed between them.

[0143] The liquid crystal LC is aligned according to a driving mode such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane switching), VA (Vertical Alignment), OCB (Optically Compensated Bifefringence), etc. A TFT (Thin Film Transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. In addition, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0144] On the other hand, a color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. Red, green and blue filter segments constituting the color filter 22 are separated by a black matrix (not shown).

[0145] A transparent protective film (not shown) is formed as necessary to cover the color filter 22, and a transparent electrode layer 23 made of, for example, ITO is formed on top of the transparent protective film. An alignment layer 24 is provided to cover the transparent electrode layer 23.

[0146] In addition, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Below the polarizing plate 25, a backlight unit 30 is provided.

[0147] The white LED light source may be one in which a fluorescent filter is formed on the surface of a blue LED, or one in which a fluorescent material is contained in the resin package of a blue LED, and has a wavelength (λ3) in the range of 430 nm to 485 nm at which the emission intensity is maximized, a wavelength (λ4) in the range of 530 nm to 580 nm at which the emission intensity is maximized, and a wavelength (λ5) in the range of 600 nm to 650 nm at which the emission intensity is maximized, and the ratio (I4 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less. In particular, a white LED light source (LED1) having spectral characteristics in which the ratio (I5 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 is 0.1 or more and 1.3 or less, or a white LED light source (LED2) having a wavelength (λ1) at which the emission intensity is maximum within the range of 430 nm to 485 nm, a peak wavelength (λ2) of the second emission intensity within the range of 530 nm to 580 nm, and a ratio (I2 / I1) of the emission intensity I1 at wavelength λ1 to the emission intensity I2 at wavelength λ2 is 0.2 or more and 0.7 or less is preferred.

[0148] Specific examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.).

[0149] Specific examples of the LED 2 include NSSW440 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D (manufactured by Nichia Chemical Industries, Ltd.). EXAMPLES

[0150] The present invention will be described below with reference to examples. In the examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

[0151] Prior to the examples, the methods for measuring and calculating the average molecular weight of a resin and the acid value of a resin will be described.

[0152] (Average molecular weight of resin) The number average molecular weight (Mn) and mass average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was an HLC-8220GPC (manufactured by Tosoh Corporation), with two separation columns connected in series, and both packings were "TSK-GEL SUPER HZM-N" connected in series. The oven temperature was 40°C, THF solution was used as the 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 20 microliters were injected. All molecular weights are polystyrene equivalent values.

[0153] (Acid value of resin) 80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of the resin solution, and the solution was stirred to dissolve uniformly. The solution was titrated using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) with a 0.1 mol / L KOH aqueous solution as the titrant, and the acid value (mgKOH / g) of the resin solution was measured. The acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

[0154] <Production of resin-type dispersant solution 1> In the first stage synthesis, 90 parts of methyl methacrylate, 60 parts of ethyl acrylate, 40 parts of t-butyl acrylate, 10 parts of methacrylic acid, and 40 parts of PGMAC (propylene glycol monomethyl ether acetate) were charged into a reaction vessel equipped with a gas inlet tube, a condenser, an agitator, and a thermometer, and the atmosphere was replaced with nitrogen gas. The inside of the reaction vessel was heated to 80°C, and 12 parts of 3-mercapto-1,2-propanediol was added, and then 0.2 parts of 2,2'-azobisisobutyronitrile were added in 20 portions every 30 minutes, and the reaction was continued for 12 hours at 80°C, and it was confirmed that 95% had reacted by measuring the non-volatile content. Next, in the second stage synthesis, 18 parts of pyromellitic anhydride, 190 parts of PGMAC, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was continued for 7 hours at 120°C. The reaction was terminated when it was confirmed by titration that 98% or more of the acid anhydride had been half-esterified. In this way, a resin-type dispersant solution with an acid value of 42 mgKOH / g per non-volatile content and a weight average molecular weight of 9,800 was obtained. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content, and PGMAC was added so that the non-volatile content became 40% by mass, thereby obtaining a resin-type dispersant solution 1.

[0155] (Yellow colorant (Y-1)) The azobarbituric acid precursor was prepared according to the synthesis method described in JP 2017-171915 A. (Instruction 1) 46.2 g of diazobarbituric acid and 38.4 g of barbituric acid were introduced into 1100 g of distilled water at 85° C. The pH was then adjusted to about pH 5 with an aqueous potassium hydroxide solution and stirring was continued for 90 minutes.

[0156] Azobarbituric acid (0.3 mol) prepared in instruction 1 was mixed with 1500 g of distilled water at 82 ° C. Then 10 g of 30% strength hydrochloric acid was added dropwise to adjust the pH to 2-2.5. After that, 79.4 g of melamine (0. 63 mol) was introduced. Then 0.3 mol of about 25% strength nickel chloride solution was added dropwise. After 3 hours at 82 ° C, the pH was adjusted to about 5.5 with KOH. This was followed by dilution with about 100 g of distilled water at 90 ° C. Then 21 g of 30% strength hydrochloric acid was added dropwise and the temperature was kept at 90 ° C for 12 hours. After that, the pH was adjusted to about 5 with aqueous potassium hydroxide solution. The pigment was then isolated on a suction filter, washed, dried at 80 ° C in a vacuum drying cabinet and ground in a standard laboratory mill for 2 minutes. (Yellow colorant (Y-1) = adduct of nickel azobarbituric acid and melamine).

[0157] (Yellow colorant (Y-2)) Yellow colorant (Y-2) was obtained in the same manner as for yellow colorant (Y-1), except that "0.3 moles of 25% strength nickel chloride solution" in the preparation example for yellow colorant (Y-1) was replaced by "0.225 moles of a mixed solution of 25% strength nickel chloride + 0.075 moles of a 25% strength copper(II) chloride solution". (Yellow colorant (Y-2) = melamine adduct of copper / nickel azobarbituric acid, a hybrid compound with 25 mole % copper and 75 mole % nickel components)

[0158] (Yellow colorant (Y-3)) Yellow colorant (Y-3) was obtained in the same manner as for yellow colorant (Y-2), except that the "0.3 moles of 25% strength nickel chloride solution" in the preparation example for yellow colorant (Y-1) was replaced by "a mixed solution of 0.225 moles of 25% strength nickel chloride + 0.075 moles of 25% strength zinc chloride". (Yellow colorant (Y-3) = melamine adduct of zinc / nickel azobarbituric acid, a hybrid compound with the components 25 mole % Zn and 75 mole % Nickel).

[0159] (Yellow colorant (Y-4)) Yellow colorant (Y-4) was obtained in the same manner as for yellow colorant (Y-2), except that the "0.3 moles of 25% strength nickel chloride solution" in the preparation example for yellow colorant (Y-1) was replaced by "a mixed solution of 0.150 moles of 25% strength nickel chloride + 0.150 moles of 25% strength zinc chloride". (Yellow colorant (Y-4) = melamine adduct of zinc / nickel azobarbituric acid, a hybrid compound with the components 50 mole % Zn and 50 mole % Nickel).

[0160] (Yellow colorant (Y-5)) Yellow dye (Y-5) was obtained in the same manner as for yellow dye (Y-2), except that the "0.3 moles of 25% strength nickel chloride solution" in the preparation example for yellow dye (Y-1) was replaced by "a mixed solution of 0.075 moles of 25% strength nickel chloride + 0.225 moles of 25% strength zinc chloride". (Yellow dye (Y-5) = melamine adduct of zinc / nickel azobarbituric acid, a hybrid compound with the components 75 mole % Zn and 25 mole % Nickel).

[0161] (Yellow finely processed pigment (PY-1)) 100 parts of yellow colorant (Y-1), 10 parts of dye derivative (PD-1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 8 hours at 70° C. This mixture was poured into 2000 parts of warm water, heated to about 80° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, which was filtered and washed repeatedly with water to remove salt and solvent, and then dried at 80° C. for 24 hours to obtain a yellow finely divided pigment (PY-1).

[0162] (Yellow finely processed pigment (PY-2)) A yellow finely divided pigment (PY-2) was obtained in the same manner as in the production of the yellow finely divided pigment (PY-1), except that the yellow colorant (Y-1) was changed to the yellow colorant (Y-2).

[0163] (Yellow finely processed pigment (PY-3)) A yellow finely divided pigment (PY-3) was obtained in the same manner as in the production of the yellow finely divided pigment (PY-1), except that the yellow colorant (Y-1) was changed to the yellow colorant (Y-3).

[0164] (Yellow finely processed pigment (PY-4)) A yellow finely divided pigment (PY-4) was obtained in the same manner as in the production of the yellow finely divided pigment (PY-1), except that the yellow colorant (Y-1) was changed to the yellow colorant (Y-4).

[0165] (Yellow finely processed pigment (PY-5)) A yellow finely divided pigment (PY-5) was obtained in the same manner as in the production of the yellow finely divided pigment (PY-1), except that the yellow colorant (Y-1) was changed to the yellow colorant (Y-5).

[0166] (Red finely processed pigment (PR-1)) A red finely-processed pigment (PR-1) was obtained in the same manner as in the production of the yellow finely-processed pigment (PY-1), except that the yellow colorant (Y-1) was changed to CI Pigment Red 177 (PR177) ("Chromophthal Red A2B" manufactured by BASF Japan Ltd.) and the dye derivative (PD-1) was changed to the dye derivative (PD-2).

[0167] (Red finely processed pigment (PR-2)) A red finely-processed pigment (PR-2) was obtained in the same manner as in the production of the yellow finely-processed pigment (PY-1), except that the yellow colorant (Y-1) was changed to CI Pigment Red 254 (PR254) (BASF's "Irgaphor Red B-CF") and the dye derivative (PD-1) was changed to the dye derivative (PD-3).

[0168] A red fine pigment (PR-3) was obtained in the same manner as in the production of the yellow fine pigment (PY-1), except that the yellow colorant (Y-1) was a pigment represented by the following chemical formula (1) prepared in accordance with the examples of JP-A-2017-138417.

[0169] Chemical formula (1) [ka]

[0170] A red fine pigment (PR-4) was obtained in the same manner as in the production of the yellow fine pigment (PY-1), except that the yellow colorant (Y-1) was a pigment represented by the chemical formula (1) prepared in accordance with Example 22 of Japanese Patent No. 6368844.

[0171] (Blue finely processed pigment (PB-1) A blue finely divided pigment (PB-1) was obtained in the same manner as in the production of the yellow finely divided pigment (PY-1), except that the yellow colorant (Y-1) was changed to CI Pigment Blue 15:6 (PB15:6) ("Lionol Blue ES" manufactured by Toyo Color Co., Ltd.) and the dye derivative (PD-1) was changed to the dye derivative (PD-4).

[0172] <Method of manufacturing pigment dispersion> (Pigment Dispersion (DY-1)) The mixture below was stirred and mixed until homogeneous, and then dispersed in an Eiger mill (Eiger Japan, "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm for 5 hours. The mixture was then filtered through a 5.0 μm filter to produce a yellow pigment dispersion (DY-1). Yellow finely processed pigment (PY-1): 11.9 parts Dye derivative (PD-1): 2.1 parts Resin-type dispersant solution 1: 15.0 parts PGMAC: 71.0 copies

[0173] (Pigment Dispersion (DY-2~6, DR-1~8, DB-1)) The following pigment dispersions (DY-2 to 6, DR-1 to 8, DB-1) were prepared in the same manner as pigment dispersion (DY-1), except that the types and blending amounts (parts by mass) of the finely divided pigment, dye derivative, resin-type dispersant solution, and solvent were changed to those shown in Table 1.

[0174] [Table 1]

[0175] The dye derivatives in Table 1 are shown in Table 2.

[0176] [Table 2]

[0177] The abbreviations in Table 2 are as follows: Me: Methyl group Et: Ethyl group

[0178] <Method for producing alkali-soluble resin solution> (Alkali-soluble resin solution (B-1)) A separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer was charged with 350 parts of PGMAC, heated to 80°C, and the flask was replaced with nitrogen. From the dropping tube, a mixture of 6.4 parts of tricyclodecane-based monomethacrylate (Hitachi Chemical Co., Ltd. FA-513M), 6.4 parts of benzyl methacrylate, 31.6 parts of glycidyl methacrylate, 12.8 parts of methyl methacrylate, and 8.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, and then a solution of 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of PGMAC was added, and the reaction was continued at 100°C for 1 hour. Next, the inside of the container was replaced with air, and 16.0 parts of acrylic acid (100 mol% of glycidyl groups), 0.5 parts of N,N-dimethylbenzylamine, and 0.1 parts of hydroquinone were added to the container, and the reaction was continued for 6 hours at 120 ° C., and the reaction was terminated when the non-volatile acid value reached 0.5 mg KOH / g, to obtain an acrylic resin solution. Furthermore, 16.9 parts of succinic anhydride were added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAC was added to the resin solution previously synthesized so that the non-volatile content was 20 mass % to prepare an alkali-soluble resin solution (B-1) that is an active energy ray curable resin. The weight average molecular weight (Mw) of the alkali-soluble resin solution (B-1) was 5,500, and the non-volatile acid value was 95.0 mg KOH / g.

[0179] (Alkali-soluble resin solutions (B-2 to 7, 12)) The following alkali-soluble resin solutions (B-2 to 7, 12) were prepared in the same manner as the alkali-soluble resin solution (B-1), except that the types and blending amounts (parts by mass) of the epoxy group-containing monomer, other monomers, polymerization initiator, carboxyl group-containing monomer, and polybasic acid anhydride were changed to those shown in Table 3.

[0180] [Table 3]

[0181] (Alkali-soluble resin solution (B-8)) A separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer was charged with 350 parts of PGMAC, heated to 80°C, and the flask was replaced with nitrogen. From the dropping tube, a mixture of 6.2 parts of tricyclodecane-skeleton monomethacrylate (Hitachi Chemical Co., Ltd. FA-513M), 6.2 parts of benzyl methacrylate, 33.7 parts of methacrylic acid, 12.4 parts of methyl methacrylate, and 8.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, and then a solution of 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of PGMAC was added, and the reaction was continued at 100°C for 1 hour. Next, the inside of the container was replaced with air, and 31.6 parts of glycidyl methacrylate, 0.5 parts of N,N-dimethylbenzylamine, and 0.1 parts of hydroquinone were added to the container, and the reaction was continued at 120 ° C for 6 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C for 20 minutes to measure the non-volatile content, and PGMAC was added to the resin solution previously synthesized so that the non-volatile content was 20 mass % to prepare an alkali-soluble resin solution (B-8) that is an active energy ray curable resin. The weight average molecular weight (Mw) of the alkali-soluble resin solution (B-8) was 5,500, and the non-volatile acid value was 95.0 mg KOH / g.

[0182] (Alkali-soluble resin solution (B-9, 10)) The following alkali-soluble resin solutions (B-9, 10) were prepared in the same manner as the alkali-soluble resin solution (B-8), except that the types and amounts (parts by mass) of the carboxyl group-containing monomer, other monomers, polymerization initiator, and epoxy group-containing monomer were changed to those shown in Table 4.

[0183] [Table 4]

[0184] (Alkali-soluble resin solution (B-11)) A separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer was charged with 350 parts of PGMAC, and the temperature was raised to 80°C. After replacing the inside of the reaction vessel with nitrogen, a mixture of 40.0 parts of n-butyl methacrylate, 5.0 parts of 2-hydroxyethyl methacrylate, 15.0 parts of methacrylic acid, 30.0 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), and 8.0 parts of azobisisobutyronitrile was dropped over 2 hours from the dropping tube. After the dropwise addition was completed, the reaction was continued for another 3 hours, and a solution of 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of PGMAC was added, and the reaction was continued for another 1 hour at 100°C to obtain an acrylic resin solution. After cooling to room temperature, about 2 g of the resin solution was sampled and dried at 180°C for 20 minutes to measure the non-volatile content, and PGMAC was added to the previously synthesized resin solution so that the non-volatile content was 20 mass%, to prepare an alkali-soluble resin solution (B-11). The weight average molecular weight (Mw) of the alkali-soluble resin solution (B-11) was 5,500, and the acid value of the non-volatile content was 95.0 mgKOH / g.

[0185] (Polymerizable compound (C-6)) In a separable 4-neck flask equipped with a thermometer, a cooling tube, an air inlet tube, a dropping tube and a stirrer, 400 parts of dipentaerythritol pentaacrylate, 400 parts of PGMAC, 1.0 parts of N,N-dimethylbenzylamine and 1.0 parts of 4-methoxyphenol were charged, and the temperature was raised to 70°C. A mixture of 64 parts of hexamethylene diisocyanate and 64 parts of PGMAC was dropped from the dropping tube over 1 hour. After dropping, the mixture was reacted for another 7 hours, and it was confirmed by IR analysis that no isocyanate group was present in the reaction product. After cooling to room temperature, 35.1 parts of mercaptopropionic acid and 35.1 parts of PGMAC were charged and reacted at a temperature of 50 to 60°C for 6 hours to obtain a polymerizable compound (C-6).

[0186] <Method for producing photosensitive coloring composition for color filters> [Example 1] (Photosensitive red composition (RR-1)) The following mixture was stirred and mixed to be homogeneous, and then filtered through a 1.0 μm filter to prepare a photosensitive coloring composition for color filters (RR-1). Pigment dispersion (DY-2): 10.71 parts Pigment dispersion (DR-1): 21.43 parts Pigment dispersion (DR-3): 21.43 parts Alkali-soluble resin solution (B-1): 12.80 parts Polymerizable compound (C-1): 1.50 parts Photopolymerization initiator (D-1): 0.15 parts Chain transfer agent (E-1): 0.08 parts PGMAC: 31.95 copies

[0187] [Examples 2 to 57, Comparative Examples 1 to 4] (Photosensitive coloring composition (RR-2~61) The following photosensitive coloring compositions for color filters (RR-2 to RR-61) were prepared in the same manner as the photosensitive red composition (RR-1), except that the pigment dispersion, alkali-soluble resin solution, polymerizable compound, photopolymerization initiator, chain transfer agent, ultraviolet absorber, and solvent were changed to the types and blending amounts (parts by mass) shown in Tables 5, 6, and 7.

[0188] [Table 5]

[0189] [Table 6]

[0190] [Table 7]

[0191] The abbreviations in Tables 5 to 7 are as follows: Polymerizable compound (C-1): "Aronix M-402" (dipentaerythritol penta- and hexaacrylate) manufactured by Toagosei Co., Ltd. Polymerizable compound (C-2): "Aronix M-309" (trimethylolpropane triacrylate) manufactured by Toagosei Co., Ltd. Polymerizable compound (C-3): "A-DCP" (tricyclodecane dimethanol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. Polymerizable compound (C-4): "Aronix M-510" (polybasic acid modified acrylic oligomer) manufactured by Toagosei Co., Ltd. Polymerizable compound (C-5): "Aronix M-520" (polybasic acid modified acrylic oligomer) manufactured by Toagosei Co., Ltd. Polymerizable compound (C-6): As described above Photopolymerization initiator (D-1): "Irgacure OXE02" (1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime)) manufactured by BASF Japan Ltd. Photopolymerization initiator (D-2): ADEKA Arcles NCI-831E Photopolymerization initiator (D-3): a compound represented by the following structure

[0192] [ka]

[0193] Photopolymerization initiator (D-4): "Irgacure OXE01" (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)]) manufactured by BASF Japan Ltd. Photopolymerization initiator (D-5): Nikko Chemtech "TR-PBG-305" Photopolymerization initiator (D-6): "Omnirad369E" (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone) manufactured by IGM Resins Photopolymerization initiator (D-7): "Omnirad907" (2-[4-(methylthio)benzoyl]-2-(4-morpholinyl)propane) manufactured by IGM Resins Chain transfer agent (E-1): Pentaerythritol tetrakis(3-mercaptopropionate) UV absorber (F-1): BASF Japan "TINUVIN326"

[0194] <Evaluation of photosensitive coloring composition for color filters> The photosensitive coloring compositions obtained in the Examples and Comparative Examples were evaluated for developability, film thickness, brightness, development speed, pattern adhesion, pattern shape, and chemical resistance by the following methods. The results are shown in Tables 8 to 10.

[0195] <Developability> The photosensitive coloring composition obtained was applied to a glass substrate of 100 mm length x 100 mm width, 0.7 mm thickness by a spin coater at a rotation speed that resulted in a film thickness of 2.0 μm after drying, and the substrate was dried at 90° C. for 90 seconds to remove the solvent, to obtain a coated substrate. Then, the substrate was spray-developed with an alkaline developer consisting of a 0.2% by mass aqueous solution of sodium carbonate, and the time until the coating film was completely dissolved was taken as the development dissolution time, which was evaluated according to the following criteria. .DELTA.: The development dissolution time was less than 20 seconds, and the developability was extremely good. ◯: The developing dissolution time was 20 seconds or more and less than 40 seconds, and the developing property was good. △: The development dissolution time was 40 seconds or more and less than 60 seconds, and the developability was practical. ×: The development dissolution time was 60 seconds or more, and the developability was not practical.

[0196] <Formation of filter segments> A black matrix was patterned on a glass substrate measuring 100 mm long x 100 mm wide and 0.7 mm thick. The resulting photosensitive coloring composition was then applied to the glass substrate using a spin coater at a rotation speed such that, after baking, x in the XYZ color system would be 0.676 when a C light source was used as a backlight, and the composition was dried at 90°C for 90 seconds to remove the solvent, yielding a coated substrate. The coating was then irradiated with 100 mJ / cm2 of light using an ultra-high pressure mercury lamp through a mask having a stripe pattern with a width of 10 to 50 μm and a pattern of 400 μm x 400 μm. 2 The coated substrate was irradiated with ultraviolet light of 1000 nm. The uncured portions were then removed by spray development using an alkaline developer consisting of a 0.2% by mass aqueous solution of sodium carbonate, to form the desired pattern. The coated substrate was then heated in an oven at 230°C for 20 minutes to form filter segments. The transmission spectrum was measured using a microspectrophotometer (OSP-SP100 manufactured by Olympus Optical Co., Ltd.) to calculate x.

[0197] <Film thickness> The film thickness of the patterned portion of the obtained filter segment, which was 400 μm×400 μm, was measured using Dektak 3030 (manufactured by Japan Vacuum Engineering Co., Ltd.) The evaluation was performed according to the following criteria. ◎: Less than 2.2 μm, extremely good film thickness. ◯: 2.2 μm or more and less than 2.6 μm, good film thickness. △: 2.6 μm or more and less than 3.0 μm, a practical film thickness. ×: 3.0 μm or more, a film thickness that is not practical.

[0198] <lightness> The transmission spectrum of the 400μm×400μm pattern of the obtained filter segment was measured using a microspectrophotometer (OSP-SP100 manufactured by Olympus Optical Co., Ltd.), and the Y value (brightness) in the XYZ color system was calculated when a C light source was used as the backlight. Evaluation was performed according to the following criteria. ◎: 16.0pts or more, extremely good brightness. ○: 15.5 pts or more and less than 16.0 pts, good brightness. △: 15.0 pts or more and less than 15.5 pts, practical lightness. ×: Less than 15.0 pts, impractical brightness

[0199] <Pattern adhesion> The obtained filter segments were checked for the presence or absence of loss of the 10 μm to 50 μm pattern in transmission mode using an optical microscope (Nikon ECLIPSE LV100POL Model). The pattern adhesion was evaluated according to the following criteria, based on how fine the pattern remained on the glass substrate. ◎: All patterns of 10 μm or more remain, and the pattern adhesion is extremely good. ◯: All patterns of 30 μm or more remain, and the pattern adhesion is good. △: All patterns of 50 μm or more remain, and the pattern adhesion is sufficient for practical use. ×: Pattern adhesion of 50 μm or more was lost in some places, making the pattern adhesion impractical.

[0200] <Pattern cross-sectional shape> The cross-sectional shape of the pattern of the obtained filter segment was confirmed by a scanning electron microscope (Hitachi High-Tech Corporation's "S-3000H") The evaluation was performed by taking SEM images of a 50 μm-wide stripe pattern and evaluating them as follows. ◎: Taper angle is 60° or more and less than 70°, and the cross-sectional shape is extremely good ○: Good cross-sectional shape with taper angle of 50° or more and less than 60°, or 70° or more and less than 80°. △: A cross-sectional shape with a taper angle of 30° or more and less than 50°, or 80° or more and less than 90° that is practical. ×: The taper angle is 90° or more, there is a reverse taper, and the cross-sectional shape is not practical.

[0201] <Chemical resistance> The chromaticity ([L*(1), a*(1), b*(1)]) of the obtained filter segment pattern with 400 μm×400 μm under Illuminant C was measured using a microspectrophotometer (Olympus Optical Co., Ltd., OSP-SP100). After that, the filter segment was immersed in N-methylpyrrolidone for 30 minutes, washed with ion-exchanged water, and air-dried. Next, the chromaticity ([L*(2), a*(2), b*(2)]) of the 400 μm×400 μm pattern under Illuminant C was measured, and the color difference ΔE*a*b* was calculated using the following formula. ΔE*a*b* = {(L*(2)-L*(1)) 2 +(b*(2)-b*(1)) 2 +(a*(2)-a*(1)) 2} 0.5 The evaluation criteria are as follows: ◎: ΔE*a*b* is less than 1.0, showing extremely good chemical resistance. ○: ΔE*a*b* is 1.0 or more and less than 2.0, showing good chemical resistance. △: ΔE*a*b* is 2.0 or more and less than 3.0, indicating practical chemical resistance. ×: ΔE*a*b* is 3.0 or more, and the chemical resistance is not suitable for practical use.

[0202] [Table 8]

[0203] [Table 9]

[0204] [Table 10]

[0205] As shown in Tables 8 to 10, the photosensitive coloring compositions (Examples 1 to 57) containing the colorant (A), binder resin (B), polymerizable compound (C), and photopolymerization initiator (D) of the present invention, in which the colorant (A) contains a metal azo pigment (A1) containing a compound represented by formula (I) or its tautomer and formula (II), and a red pigment (A2), and the binder resin (B) has a carboxyl group and a polymerizable unsaturated group in the side chain, and has an acid value of 90 mgKOH / g or more, and contains an alkali-soluble resin (B1) selected from formulas (III) and (IV) were thin and had high brightness, and had both developability and solvent resistance, and had good pattern adhesion and pattern shape. On the other hand, Comparative Example 2, which did not use a metal azo pigment containing a compound represented by formula (I) or its tautomer and formula (II), had poor film thickness, Comparative Example 3, which used only an alkali-soluble resin having no polymerizable group in the side chain, had poor chemical resistance, and Comparative Example 4, which used an alkali-soluble resin with an acid value of less than 90 mgKOH / g, had poor developability. Among them, Examples 1 to 23, 26, 27, 29 to 31, 33, 34, 36, 38, 39, 41 to 57, which used alkali-soluble resins (B-1 to 5, 8, 9) with weight average molecular weights of 2000 to 6000, and Examples 43 to 47, which used polymerizable compounds (C4 to 6) containing acid groups, had excellent developability. [Explanation of symbols]

[0206] 10 Image display device 11 Transparent substrate 12 TFT array 13 Transparent electrode layer 14 Alignment layer 15 Polarizing plate 21 Transparent substrate 22 Color Filter 23 Transparent electrode layer 24 Alignment layer 25 Polarizing Plate 30 Backlight unit 31 White LED light source LC Liquid Crystal

Claims

1. A photosensitive coloring composition comprising a colorant (A), a binder resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), The colorant (A) contains a yellow pigment (A1) and a red pigment (A2), The yellow pigment (A1) contains an adduct of the following (a) and (b): The content of the colorant (A) is 40 to 60 mass% in 100 mass% of the nonvolatile content of the photosensitive coloring composition; The photosensitive coloring composition, wherein the binder resin (B) contains an alkali-soluble resin (B1) selected from the following (III) and (IV) having an acid value of 90 mgKOH / g or more: (a) a compound of formula (I) or a tautomeric form thereof 【Chemistry 1】 [In formula (I), R １ and R ２ is OH, R ３ and R ４ is =O, Me is Ni ２＋ , Zn ２＋ , Cu ２＋ are two or more divalent metal ions selected from the following series: Cu based on 1 mole of the total of the compounds (a) ２＋ , Zn ２＋ and Ni ２＋ the total amount of ions is 95 to 100 mol %, And the Cu ２＋ , Zn ２＋ and Ni ２＋ Based on the total amount of ions, Ni ２＋ The amount of ions is 10 to 95 mol %. (b) a compound represented by formula (II) 【Chemistry 2】 [In formula (II), R ６ is a hydrogen atom. (III) A resin obtained by reacting a reaction product between an epoxy group in a copolymer of an epoxy group-containing monomer and another monomer and a carboxyl group of a carboxyl group-containing monomer with a polybasic acid anhydride. (IV) A resin which is a reaction product between a carboxyl group in a copolymer of a carboxyl group-containing monomer and other monomers and an epoxy group in an epoxy group-containing monomer.

2. 2. The photosensitive coloring composition according to claim 1, wherein the red pigment (A2) comprises one or more pigments selected from the group consisting of C.I. Pigment Red 177, C.I. Pigment Red 254, C.I. Pigment Red 291, and C.I. Pigment Red 296.

3. The photosensitive coloring composition according to claim 1 or 2, wherein the content of the yellow pigment (A1) is 5 to 40 mass% in 100 mass% of the colorant (A).

4. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the weight average molecular weight of the alkali-soluble resin (B1) is 2000 to 6000.

5. The photosensitive coloring composition according to any one of claims 1 to 4, wherein the content of the colorant (A) is 45 to 60 mass% in 100 mass% of the nonvolatile content of the photosensitive coloring composition.

6. The photosensitive coloring composition according to any one of claims 1 to 5, wherein the polymerizable compound (C) has a polymerizable compound (C1) containing an acid group.

7. A color filter comprising a substrate and a filter segment formed from the photosensitive coloring composition according to any one of claims 1 to 6.

8. An image display device comprising the color filter according to claim 7.

Images