Photosensitive colored composition and method for manufacturing the same, and color filter, color liquid crystal display device, solid-state image sensor

Abstract

The present invention aims to provide a photosensitive coloring composition in which the pigment concentration is increased within a range that satisfies the necessary characteristics of the photosensitive coloring composition, and furthermore, the film formed after the heating step following the coating, exposure, and development of the photosensitive coloring composition becomes thinner, and the colorant concentration in the thin film becomes even higher. [Solution] The above problem is solved by a photosensitive colored composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), wherein the resin (B) comprises at least one of a dispersion resin (B1) or a binder resin (B2), and either of these contains 30 to 70% by mass of structural units having a t-butyl group (b1) or a blocked isocyanate group (b2) in the total resin.

Description

[Technical Field]

[0001] This invention relates to a photosensitive colored composition used in the manufacture of color filters used in color liquid crystal display devices, solid-state image sensors, etc., a method for manufacturing the same, and a color filter using the same. [Background technology]

[0002] Color filters, which make up color liquid crystal display devices (LCDs) and solid-state image sensors, are manufactured by applying a coating solution (coloring composition) to a transparent substrate and drying it to form a coating film with a thickness of approximately 0.3 to 3 μm.

[0003] As a method for manufacturing color filters used in color liquid crystal displays and solid-state image sensors, for example, the most widely adopted method involves coating a pigment-dispersed photosensitive colored composition onto a substrate, removing the solvent by drying, exposing the dried coating to a desired pattern shape (irradiation), removing the unexposed areas by development, and applying treatments such as heating as necessary to obtain each RGB color pixel. In particular, color filters used in solid-state image sensors and the like are in high demand for thinner films. Consequently, the photosensitive colored composition used as the material for these color filters needs to have a higher pigment concentration. As disclosed in Patent Document 1, a method is available in which the film is thinned by a post-bake process to increase the pigment concentration within the film. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] WO2024 / 128043 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] The present invention aims to provide a photosensitive coloring composition in which the pigment concentration is increased within a range that satisfies the necessary characteristics of the photosensitive coloring composition, and furthermore, the film formed after the heating step following the coating, exposure, and development of the photosensitive coloring composition becomes thinner, and the colorant concentration in the thin film becomes even higher. [Means for solving the problem]

[0006] In other words, the present invention relates to a photosensitive colored composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), wherein the resin (B) comprises a dispersion resin (B1) and / or a binder resin (B2), and either the dispersion resin (B1) or the binder resin (B2) contained in the resin (B) comprises a structural unit having a t-butyl group (b1) and / or a structural unit having a blocked isocyanate group (b2), and the total amount of the structural unit having a t-butyl group (b1) and the structural unit having a blocked isocyanate group (b2) is 30 to 70% by mass of 100% by mass of the resin (B).

[0007] In other words, the present invention relates to the photosensitive colored composition characterized in that the content of the constituent unit (b3) having a cyclic structure is 0 to 10% by mass of the binder resin (B2) in 100% by mass.

[0008] In other words, the present invention relates to the photosensitive coloring composition characterized in that the resin (B) further comprises a resin (B3) having an epoxy group.

[0009] In other words, the present invention relates to a photosensitive resin composition in which the content of each solid component in 100% by mass of the total solid content of the photosensitive colored composition is as follows. Coloring agent (A): 40% by mass or more and less than 65% by mass Resin (B): 10% by mass or more and less than 50% by mass Polymerizable compound (C): 5% by mass or more and less than 25% by mass Photopolymerization initiator (D): 1% by mass or more and less than 5% by mass

[0010] That is, the present invention relates to a color filter having a filter segment formed from the photosensitive coloring composition.

[0011] That is, the present invention relates to a solid-state imaging device including the color filter.

[0012] That is, the present invention relates to a liquid crystal display device including the color filter.

[0013] That is, the present invention relates to a method for manufacturing a color filter including the steps of: applying the photosensitive resin composition onto a substrate to form a coating film; exposing and developing the coating film to form a pattern; heat-treating the pattern at 240 to 300°C.

Advantages of the Invention

[0014] According to the present invention, a photosensitive coloring composition having high developability, coating properties, and viscosity stability can be provided. By using the photosensitive coloring composition of the present invention, when used as a color filter, it can be made thinner, resulting in a higher pigment concentration and thus a high-quality color filter, color liquid crystal display device, solid-state imaging device, etc. with high coloring power can be provided.

Brief Description of the Drawings

[0015] [Figure 1] FIG. 1 is a schematic cross-sectional view of an image display device. [Figure 2] FIG. 2 is a schematic cross-sectional view of an infrared sensor.

Embodiments for Carrying Out the Invention

[0016] Hereinafter, each constituent component of the photosensitive coloring composition of the present invention will be described. In this invention, when "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamide" are used, unless otherwise specified, they represent "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or methacrylamide," respectively. Furthermore, "CI" as used herein refers to Color Index (CI).

[0017] <Photosensitive coloring composition> The photosensitive colored composition of the present invention is a photosensitive colored composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), wherein the resin (B) comprises a dispersion resin (B1) and / or a binder resin (B2), and either the dispersion resin (B1) or the binder resin (B2) contained in the resin (B) comprises a structural unit having a t-butyl group (b1) and / or a structural unit having a blocked isocyanate group (b2), and the total amount of the structural unit having a t-butyl group (b1) and the structural unit having a blocked isocyanate group (b2) is 30 to 70% by mass of 100% by mass of the resin (B).

[0018] <Coloring agent (A)> In the present invention, in order to maintain the viscosity stability and photolithographic properties of the photosensitive coloring composition, and for the coating film thinned as a result of thermal decomposition and thermal shrinkage of the components of the photosensitive coloring composition by post-baking to exhibit sufficient coloring power, it is preferable that the colorant (A) is contained in an amount of 40% by mass or more and less than 65% by mass of 100 parts by mass of the total solids. The photosensitive colored composition of the present invention can be used as a colorant (A) by using the following pigments or dyes individually or by mixing two or more in any ratio as needed.

[0019] For example, red pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 57:1, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 2 Examples include, but are not limited to, azo pigments described in Japanese Patent Publication No. 2014-112527, azo pigments described in Japanese Patent Publication No. 2013-161026, or diketopyrrolopyrrole pigments described in Japanese Patent Publication No. 2011-523433.

[0020] Among these, CI Pigment Red 254 and CI Pigment Red 177 are preferred in terms of their high transmittance.

[0021] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, and 73, but the range is not limited to these. Among these, CI Pigment Orange 71 is preferred for reproducing the color gamut of the color filter. For example, yellow pigments include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73 ,74,75,81,83,87,93,94,95,97,100,101,104,105,108,109,110,111,116,117,119,120,126,127,127:1,128,129,133,134,136,138,139,142,147,148,150 Examples include, but are not limited to, quinophthalone compounds described in Japanese Patent Publication No. 2012-226110, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, 231, 233, and quinophthalone compounds described in Japanese Patent Publication No. 2012-226110. Among these, CI Pigment Yellow 138, 139, 150, 185 and the quinophthalone compounds described in Japanese Patent Publication No. 2012-226110 are preferred for reproducing the color gamut of the color filter.

[0022] Examples of green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, 62, and 63. Among these, CI Pigment Green 7, 36, 58, 59, 62, and 63 are preferred from the viewpoint of brightness and coloring power. In addition, zinc phthalocyanine pigments described in Japanese Patent Publication No. 2008-19383, Japanese Patent Publication No. 2007-320986, Japanese Patent Publication No. 2004-70342, etc., and aluminum phthalocyanine pigments described in Japanese Patent Publication No. 2004-333817, Japanese Patent Publication No. 2012-247588, etc. can be used. For blue pigments, for example, CIPigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 80, etc. can be used. For purple pigments, for example, CIPigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, etc. can be used. For black pigments, for example, carbon black, aniline black, anthraquinone-based black pigments, perylene-based black pigments, specifically CI Pigment Black 1, 6, 7, 12, 20, 31, etc. can be used. Additionally, metal lake pigments of rhodamine-based dyes such as CI Pigment Red 81, 81:1, 81:2, 81:3, 81:4, and 81:5 can be used in combination.

[0023] In addition, examples of inorganic pigments include metal oxide powders such as silicon dioxide, zirconia oxide, barium sulfate, zinc oxide, lead sulfate, lead yellow, zinc yellow, red iron(III) oxide, cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, titanium dioxide, and iron tetroxide, as well as metal sulfide powders and metal powders.

[0024] Furthermore, any of the following dyes can be used: acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. Derivatives of these dyes, or even lake pigments (dyes prepared by lake formation), are also acceptable.

[0025] Furthermore, in the case of acidic dyes having acidic groups such as sulfonic acid or carboxylic acid, or in the form of direct dyes, it is preferable to use inorganic salts of the acidic dye, or salt compounds formed by combining the acidic dye with nitrogen-containing compounds such as quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, or primary amine compounds, or to use them as salt compounds by chlorinating them using resin components having these functional groups, or to use them as sulfonamide compounds by sulfonamide formation, as this results in a colored composition with excellent durability. Furthermore, salt-forming compounds of acid dyes and compounds containing an onium base are also preferred due to their excellent fastness, and more preferably, the compound containing the onium base is a resin having a cationic group in its side chain.

[0026] In the case of basic dyes, they can be used after being chlorinated using organic acids, perchloric acid, or their metal salts. Among these, salt compounds of basic dyes are preferred because they have excellent resistance and compatibility with pigments. Furthermore, it is even more preferable to use salt compounds obtained by saturating a basic dye with an organic sulfonic acid, organic sulfuric acid, a fluorine group-containing phosphorus anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or an acid dye, which act as a counter ion.

[0027] Furthermore, if the pigment skeleton has polymerizable unsaturated groups, it can be used to produce a dye with excellent resistance, which is preferable.

[0028] Examples of dye chemical structures include azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), and azine. Examples of pigment structures derived from dyes selected from the following: polymethine dyes (oxonol dyes, merocyanine dyes, allylidene 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, and metal complex dyes thereof.

[0029] Among these pigment structures, from the viewpoint of color characteristics such as hue, color separation, and color unevenness, pigment structures derived from pigments selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and pigment structures derived from pigments selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, and phthalocyanine dyes are more preferred. Specific pigment compounds that can form pigment structures are described in "New Edition Dye Handbook" (edited by the Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and colourists), and "Pigment Handbook" (edited by Okawara et al.; Kodansha, 1986), among others.

[0030] <Pigment miniaturization> The method for micronizing the pigment used in the photosensitive colored composition of the present invention is not particularly limited. For example, wet grinding, dry grinding, or dissolution extraction methods can all be used. As exemplified in the present invention, micronization can be performed by salt milling using a kneader method, which is a type of wet grinding. The average primary particle size of the pigment, as determined by TEM (transmission electron microscope), is preferably in the range of 10 to 80 nm. If it is smaller than 10 nm, dispersion in the organic solvent becomes difficult, and if it is larger than 80 nm, a sufficient contrast ratio may not be obtained. For these reasons, a more preferable average primary particle size is in the range of 15 to 70 nm.

[0031] Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt, and water-soluble organic solvent is mechanically kneaded while heated using batch or continuous kneading machines such as kneaders, two-roll mills, three-roll mills, ball mills, attritors, sand mills, and planetary mixers, and then washed with water to remove the water-soluble inorganic salt and water-soluble organic solvent. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain pigments with a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

[0032] As water-soluble inorganic salts, sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc., can be used, but from a cost standpoint, sodium chloride (table salt) is preferred. From the perspective of both processing efficiency and production efficiency, it is preferable to use 50 to 2000 parts by mass of water-soluble inorganic salt per 100 parts by mass of pigment, and most preferably 300 to 1000 parts by mass.

[0033] The water-soluble organic solvent serves to wet the pigment and the water-soluble inorganic salt. It is not particularly limited as long as it dissolves (miscible) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent is prone to evaporation, a high-boiling-point solvent with a boiling point of 120°C or higher is preferred from a safety standpoint. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by mass, and most preferably 50 to 500 parts by mass, per 100 parts by mass of pigment.

[0034] When the pigment is subjected to salt milling, a resin may be added as needed. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc., can be used. The resin used is preferably solid at room temperature, insoluble in water, and more preferably partially soluble in the above organic solvent. The amount of resin used is preferably in the range of 5 to 200 parts by mass per 100 parts by mass of pigment.

[0035] <Metal Removal> If specific metal elements are present in large quantities as impurities other than the pigment components in the colored composition, it can impair the dispersion stability over time, and may also reduce heat resistance or sensitivity. Furthermore, color filters made using such compositions may develop foreign matter, which can easily lead to a decrease in brightness. It is preferable that the total content of Li, Na, K, Mg, Ca, Fe, Al, and Cr (hereinafter also referred to as specific metal elements) in the photosensitive colored composition is 500 ppm by mass or less.

[0036] The total amount of specific metal elements contained in the photosensitive colored composition is more preferably 300 ppm by mass or less, and particularly preferably 200 ppm by mass or less. Furthermore, while there is no particular lower limit to the total amount of specific metal elements, it is preferably 1 ppm by mass or more, and more preferably 5 ppm by mass or more. Within the above range, a photosensitive colored composition can be obtained that suppresses costs, has excellent storage stability, and can form a color filter with minimal generation of foreign matter and reduction in brightness.

[0037] The amount of each specific metal element contained in the photosensitive coloring composition is preferably 100 ppm by mass or less, and more preferably 50 ppm by mass or less.

[0038] Furthermore, it is preferable that the metals that make up the pigment, such as Ni, Zn, Cu, Al, Fe, Fe, Co, and Co, contain fewer impurities that do not function effectively, and these can be removed in the same way as specific metal elements by the following methods. In addition, it is preferable that the concentrations of Mn, Cs, Ti, Co, Si, Pd, etc., that have been introduced due to materials used in the manufacturing process of the various raw materials of the photosensitive colored composition (for example, catalysts) be low.

[0039] Methods for removing colorants (A) or metals introduced from equipment during the manufacturing process include washing with water as described in Japanese Patent Publication No. 2010-83997, Japanese Patent Publication No. 2018-36521, Japanese Patent Publication No. Hei 7-198928, Japanese Patent Publication No. Hei 8-333521, Japanese Patent Publication No. 2009-7432, etc., and methods for removing magnetic foreign matter using a magnet as described in Japanese Patent Publication No. 2011-48736, and one or more of these methods may be used as appropriate.

[0040] The content of specific metal elements can be measured by inductively coupled plasma atomic emission spectroscopy (ICP).

[0041] <Dye derivative (a)> In the present invention, in addition to the dispersion resin (B1), a dye derivative may be used as needed to disperse the pigment, which is a coloring agent. Specifically, known dye derivatives having acidic groups, basic groups, neutral groups, etc., in the organic dye residues can be used. Examples include compounds having acidic substituents such as sulfo groups, carboxyl groups, and phosphate groups, and their amine salts; compounds having basic substituents such as sulfonamide groups or tertiary amino groups at the terminal; and compounds having neutral substituents such as phenyl groups or phthalimidoalkyl groups. Since the resin-type dispersant used in combination has acidic groups, dye derivatives having basic groups are preferred. Examples of organic pigments in organic pigment residues include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiaidine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, surene pigments, metal complex pigments, azo pigments such as azo, disazo, and polyazo, and so on.

[0042] Specifically, diketopyrrolopyrrole dye derivatives include Japanese Patent Publication No. 2001-220520, WO2009 / 081930, WO2011 / 052617, WO2012 / 102399, and Japanese Patent Publication No. 2017-156397; phthalocyanine dye derivatives include Japanese Patent Publication No. 2007-226161, WO2016 / 163351, Japanese Patent Publication No. 2017-165820, and Japanese Patent No. 5753266; and anthraquinone dye derivatives include Japanese Patent Publication No. Japanese Patent Publication No. 63-264674, Japanese Patent Publication No. 09-272812, Japanese Patent Publication No. 10-245501, Japanese Patent Publication No. 10-265697, Japanese Patent Publication No. 2007-079094, Pamphlet WO2009 / 025325, as quinacridone-based dye derivatives, Japanese Patent Publication No. 48-54128, Japanese Patent Publication No. 03-9961, Japanese Patent Publication No. 2000-273383, as dioxazine-based dye derivatives, Japanese Patent Publication No. 2011-162662, as thiaidine-indigo-based dye derivatives, Japanese Patent Publication No. 2007-314785 Publications: Triazine-based dye derivatives include Japanese Patent Publication No. 61-246261, Japanese Patent Publication No. 11-199796, Japanese Patent Publication No. 2003-165922, Japanese Patent Publication No. 2003-168208, Japanese Patent Publication No. 2004-217842, Japanese Patent Publication No. 2007-314681; Benzoisoindole-based dye derivatives include Japanese Patent Publication No. 2009-57478; Quinophthalone-based dye derivatives include Japanese Patent Publication No. 2003-167112, Japanese Patent Publication No. 2006-291194, Japanese Patent Publication No. 2008-31281, Japanese Patent Publication No. 2012-2 Examples of known dye derivatives include those described in Japanese Patent Publication No. 26110, Japanese Patent Publication No. 2012-208329 and Japanese Patent Publication No. 2014-5439 as naphthol-based dye derivatives, Japanese Patent Publication No. 2001-172520 and Japanese Patent Publication No. 2012-172092 as azo-based dye derivatives, Japanese Patent Publication No. 2004-307854 as acidic substituents, and Japanese Patent Publication No. 2002-201377, Japanese Patent Publication No. 2003-171594, Japanese Patent Publication No. 2005-181383 and Japanese Patent Publication No. 2005-213404 as basic substituents.In these documents, dye derivatives may be described as derivatives, pigment derivatives, dispersants, pigment dispersants, or simply compounds. However, compounds having substituents such as acidic groups, basic groups, or neutral groups on the aforementioned organic dye residues are synonymous with dye derivatives.

[0043] These dye derivatives (a) can be used individually or in combination of two or more types.

[0044] The pigment derivative (a) is preferably added in an amount of 1 to 30 parts by mass, more preferably in an amount of 3 to 25 parts by mass, and even more preferably in an amount of 5 to 20 parts by mass, per 100 parts by mass of pigment. Furthermore, in the present invention, when a dye derivative (a) is used, the content of the colorant (A) in the photosensitive colored composition is calculated including the dye derivative (a).

[0045] By adding a pigment derivative (a) to a pigment and performing pigmentation treatments such as acid pasting, acid slurry, dry milling, salt milling, and solvent-salt milling, the pigment derivative (a) is adsorbed onto the pigment surface, and the primary particles of the pigment can be made finer compared to when the pigment derivative (a) is not added.

[0046] By adding a dye derivative (a) to the pigment and performing dispersion treatments such as wet dispersion using two-roll, three-roll, or beads, the dye derivative is adsorbed onto the pigment surface, giving the pigment surface polarity and promoting the adsorption of resin-type dispersants. This improves compatibility with the pigment, dye derivative, resin-type dispersant, solvent, and other additives, resulting in improved dispersion stability and viscosity stability over time when used in colored compositions and colored curable compositions. Furthermore, the improved compatibility leads to excellent film stability over time when the colored curable composition is coated onto a glass substrate, resulting in good stability and property dependence of pattern shape, etc., on the waiting time from coating to exposure (PCD: Post Coating Delay) and the waiting time from exposure to heat treatment (PED: Post Exposure Delay), as well as good line width sensitivity stability. In addition, the adsorption and coating of the pigment surface with the dye derivative and resin-type dispersant suppresses pigment aggregation and crystal precipitation due to sublimation when the coating film is heated and fired. Furthermore, variations in development time and development residue are also suppressed.

[0047] <Resin (B)> The resin (B) in the present invention comprises at least one of a dispersion resin (B1) and / or a binder resin (B2), wherein either the dispersion resin (B1) or the binder resin (B2) comprises at least one of a structural unit having a t-butyl group (b1) and a structural unit having a blocked isocyanate group (b2), and the total content of the structural unit having a t-butyl group (b1) and the structural unit having a blocked isocyanate group (b2) is 30 to 70% by mass of 100% by mass of resin (B). This range is preferable because it has the effect of thinning the film due to thermal shrinkage caused by the thermal decomposition of the t-butyl group and the blocked isocyanate group, thereby increasing the concentration of the colorant in the film, while also being well-balanced with other resin properties (dispersion stability, photolithography properties, etc.). More preferably, it is 40 to 60% by mass.

[0048] Furthermore, the resin (B) used in the present invention is 100% by mass of the total solid content of the photosensitive colored composition. It is preferable that the content be in the range of 10% by mass or more and less than 50% by mass of the total.

[0049] Furthermore, in the binder resin (B2) of the present invention, it is preferable to have fewer constituent units (b3) having an annular structure. Specifically, it is preferable that the content of constituent units (b3) having an annular structure is 0 to 10% by mass of 100% by mass of the binder resin (B2). This is because the annular structure acts as a steric hindrance, which inhibits thermal shrinkage due to post-baking.

[0050] Furthermore, in the resin (B) of the present invention, either the dispersion resin (B1) or the binder resin (B2) may be present in the resin (B), but from the viewpoint of dispersion stability and photolithographic properties, it is preferable that the dispersion resin (B1) be 20 to 80% by mass and the binder resin (B2) be 10 to 70% by mass of 100% by mass of the resin (B).

[0051] (Structural unit containing a t-butyl group (b1)) Examples of structural units (b1) having a t-butyl group include t-butyl (meth)acrylate.

[0052] (Structural unit having a blocked isocyanate group (b2)) The structural unit (b2) having a blocked isocyanate group is a reaction product of an isocyanate group-containing monomer and a blocking agent. For the blocking reaction, it is preferable to use an organometallic salt such as zinc or lead, or a tertiary amine, as a catalyst. The reaction temperature is generally around -20 to 150°C, and preferably 0 to 100°C. A solvent may be used during the reaction as needed. Examples of the structural unit (b2) having a blocked isocyanate group include those derived from compounds represented by the following general formula (1).

[0053] General formula (1) [ka]

[0054] In the above general formula (1), R 1 R represents a hydrogen atom or a methyl group. 2is -CO-, -COOR 3 - (where R 3 is an alkylene group having 1 to 6 carbon atoms) or -COO-R 4 O-CONH-R 5 - (where R 4 is an alkylene group having 2 to 6 carbon atoms, and R 5 is an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms which may have a substituent). R 2 is preferably -COOR 3 -, where R 3 is preferably an alkylene group having 1 to 4 carbon atoms.

[0055] Examples of the compound represented by the general formula (1) include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, methacryloyl isocyanate, and the like. Further, an equimolar (1 mol:1 mol) reaction product of 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound can also be used. As the alkyl group of the 2-hydroxyalkyl (meth)acrylate, an ethyl group or an n-propyl group is preferable, and an ethyl group is more preferable. Examples of the diisocyanate compound include hexamethylene diisocyanate, 2,4- (or 2,6-) tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate (IPDI), m- (or p-)xylene diisocyanate, 1,3- (or 1,4-) bis(isocyanatomethyl)cyclohexane, lysine diisocyanate, and the like.

[0056] Among these, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, and methacryloyl isocyanate are preferred, with 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate being more preferred.

[0057] Blocking agents include, for example, lactam-based compounds such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; alcohol-based compounds such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, and cyclohexanol; phenol-based compounds such as phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrene-based compounds such as methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, thymol, p-naphthol, p-nitrophenol, and p-chlorophenol; and active methylene-based compounds such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone. Mercaptans such as butyl mercaptan, thiophenol, and tert-dodecyl mercaptan; Amine compounds such as diphenylamine, phenylnaphthylamine, aniline, and carbazole; acid amide compounds such as acetanilide, acetanisidide, acetic acid amide, and benzamide; Acid imides such as succinimide and maleimide; Imidazole derivatives such as imidazole, 2-methylimidazole, and 2-ethylimidazole; Pyrazoles such as pyrazoles and 3,5-dimethylpyrazole; Urea compounds such as urea, thiourea, and ethyleneurea; Carbamidates such as phenyl N-phenylcarbamate and 2-oxazolidone; imines such as ethyleneimine and polyethyleneimine; Oxime compounds such as formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, and cyclohexanone oxime; Examples include sodium bisulfite, potassium bisulfite, and other bisulfite-based salts.

[0058] In this invention, the blocked isocyanate groups are regenerated by heating, which dissociates the blocking agent. These isocyanate groups react with reactive functional groups, such as acid groups, or optionally hydroxyl groups, amino groups, etc., to form a cured product with high crosslink density.

[0059] In this specification, the dissociation temperature of the blocking agent is preferably 80 to 150°C.

[0060] As the structural unit (b2) having a blocked isocyanate group used in the photosensitive colored composition of the present invention, a blocked isocyanate group-containing (meth)acrylate is preferred. Furthermore, as the blocked isocyanate group-containing (meth)acrylate, it is preferable to use one in which the dissociation rate of the blocked isocyanate group after heat treatment at 100°C for 30 minutes is preferably 5 to 99% by mass, more preferably 8 to 97% by mass, and most preferably 10 to 95% by mass. The dissociation rate of the blocked isocyanate group in the blocked isocyanate group-containing (meth)acrylate is determined by preparing an n-octanol solution with a concentration of 20% by mass of the blocked isocyanate group-containing (meth)acrylate, adding 1% by mass of dibutylsulfur laurate and 3% by mass of phenothiazine (polymerization inhibitor) to the solution, and then heating it at 100°C for 30 minutes. The mass reduction rate of the blocked isocyanate group-containing (meth)acrylate is then measured by HPLC analysis. Using a blocked isocyanate group-containing (meth)acrylate with a dissociation rate within the above range ensures sufficient stability of the copolymer during synthesis, allows for a sufficiently lower baking temperature during cured coating film preparation, and ensures sufficient solvent resistance of the cured coating film. Examples of blocking agents for (meth)acrylates containing blocked isocyanate groups having such a dissociation rate include γ-butyrolactam, 1-methoxy-2-propanol, 2,6-dimethylphenol, diisopropylamine, methyl ethyl ketoxime, 3,5-dimethylpyrazole, and diethyl malonate. Among these blocking agents, diethyl malonate, 3,5-dimethylpyrazole, and methyl ethyl ketoxime are more preferred from the viewpoint of low-temperature curability.

[0061] Furthermore, as the structural unit (b2) having a blocked isocyanate group used in the photosensitive colored composition of the present invention, it is preferable to use a blocked isocyanate group-containing (meth)acrylate in which the dissociation temperature of the blocked isocyanate group is 80°C or higher. Using a blocked isocyanate group-containing (meth)acrylate with a dissociation temperature of 80°C or higher ensures sufficient stability of the copolymer during synthesis and reduces unintended crosslinking reactions during the modification reaction described later. On the other hand, if the dissociation temperature of the blocked isocyanate group is 150°C or lower, the baking temperature can be sufficiently lowered and sufficient solvent resistance of the cured coating film can be ensured. The dissociation temperature of the blocked isocyanate group in a blocked isocyanate group-containing (meth)acrylate is determined by preparing an n-octanol solution with a concentration of 20% by mass of the blocked isocyanate group-containing (meth)acrylate, adding 1% by mass of dibutylsus laurate and 3% by mass of phenothiazine (polymerization inhibitor) to the solution, heating it at a predetermined temperature, and measuring the mass loss rate of the blocked isocyanate group-containing (meth)acrylate after 30 minutes by HPLC analysis. The temperature at which the mass loss rate is 80% by mass or more is defined as the dissociation temperature of the blocked isocyanate group.

[0062] Examples of the aforementioned blocked isocyanate group-containing (meth)acrylates include methacrylates such as Karenz (registered trademark) MOI-DEM shown in formula (2) below (reaction product of methacroyloxyethyl isocyanate and diethyl malonate, manufactured by Showa Denko Corporation, dissociation temperature of blocked isocyanate group: 90°C, dissociation rate: 90% by mass), Karenz MOI-BP shown in formula (3) below (reaction product of methacroyloxyethyl isocyanate and 3,5-dimethylpyrazole, manufactured by Showa Denko Corporation, dissociation temperature of blocked isocyanate group: 110°C, dissociation rate: 70% by mass), and Karenz MOI-BM shown in formula (4) below (reaction product of methacroyloxyethyl isocyanate and methyl ethyl ketoxime, manufactured by Showa Denko Corporation, dissociation temperature of blocked isocyanate group: 130°C, dissociation rate: 18% by mass), and corresponding acrylates. These blocked isocyanate group-containing (meth)acrylates may be used individually or in combination of two or more types.

[0063] [ka]

[0064] [ka]

[0065] (Constituent unit having a ring structure (b3)) Examples of constituent units (b3) having a cyclic structure include benzyl (meth)acrylate, styrene, dicyclopentanyl (meth)acrylate, and dicyclopentenyl (meth)acrylate. <Dispersion resin (B1)> The photosensitive colored composition of the present invention may use a dispersion resin (B1) to effectively disperse the colorant. The dispersion resin (B1) is synonymous with a resin-type dispersant and has a colorant affinity site that has the property of adsorbing to the colorant and a site that is compatible with solvents and the binder resin (B2) described later, and it is sufficient if it works to stabilize the dispersion of the colorant by adsorbing to the colorant. Specifically, this includes urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial)amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and These modified products, oily dispersants such as amides and their salts formed by the reaction of poly(lower alkyleneimines) with polyesters having free carboxyl groups, 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, modified polyacrylate-based, ethylene oxide / propylene oxide adduct compounds, and phosphate ester-based compounds can be used, and these can be used individually or in combination of two or more. Furthermore, examples of polymeric dispersants having basic functional groups include nitrogen atom-containing graft copolymers, nitrogen atom-containing acrylic block copolymers and urethane polymeric dispersants having functional groups in their side chains that include tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc. These can be used individually or in combination of two or more. The dispersion resin (B1) of the present invention may have structural units (b1) having a t-butyl group or structural units (b2) having a blocked isocyanate group.

[0066] Commercially available dispersion resins (B1) include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, and 2150, all manufactured by BIC Chemi Japan. , 2155, 2163, 2164 or Anti-Terra-U, 203, 204 or BYK-P104, P104S, 220S, LPN6919, LPN21116, LPN21324 or Lactimon, Lactimon-WS or Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, manufactured by Lubrizol Japan Co., Ltd. 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., as well as BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080 Examples include 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., as well as Ajispa-PA111, PB711, PB821, PB822, PB824 manufactured by Ajinomoto Fine Techno Co., Ltd.

[0067] <Binder resin (B2)> As described above, the photosensitive colored composition of the present invention contains at least one type of resin (B) as the resin (B), which is either a dispersion resin (B1) or a binder resin (B2). The binder resin (B2) is preferably a resin with a transmittance of 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm. The binder resin can be classified by its main curing method into thermoplastic resins, thermosetting resins, active energy ray curable resins having ethylenically unsaturated double bonds, etc. The active energy ray curable resin may be a thermoplastic resin or one that also has thermosetting function, and from the viewpoint of developability, it is preferable that it be an alkali-soluble resin. It may also contain a thermoplastic resin that is not active energy ray curable, and it is also preferable that this is alkali-soluble. These can be used individually or in mixtures of two or more types. The binder resin (B2) of the present invention may have structural units (b1) having a t-butyl group or structural units (b2) having a blocked isocyanate group. The binder resin (B2) of the present invention may also have structural units (b3) having a cyclic structure.

[0068] <Thermoplastic resin> Examples of thermoplastic resins that can be used as binder resin (B2) 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, cyclic rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. Thermoplastic resins are preferably alkali-soluble, and examples include resins having acidic groups such as carboxyl groups and sulfone groups. Specifically, examples of resins include acrylic resins having acidic groups, α-olefin / (anhydride) maleic acid copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, or isobutylene / (anhydride) maleic acid copolymers. Among these, at least one resin selected from acrylic resins having acidic groups and styrene / styrene sulfonic acid copolymers, particularly alkali-soluble resins having acidic groups and / or hydroxyl groups, are preferably used because they have high developability, heat resistance, and transparency.

[0069] <Alkali-soluble resin> The photosensitive colored composition of the present invention preferably contains an alkali-soluble resin as the binder resin (B2) from the viewpoint of developability, heat resistance, and transparency. This is for imparting developability in the alkaline development process when manufacturing color filters, and has acidic groups and / or hydroxyl groups. As the alkali-soluble resin, an alkali-soluble resin (B2-1) without an ethylenically unsaturated double bond and an alkali-soluble resin (B2-2) having an ethylenically unsaturated double bond to improve the photosensitivity of the composition may be used, either alone or in combination.

[0070] In the present invention, the alkali-soluble resin is preferably a resin with a spectral transmittance of 80% or more, and more preferably 95% or more, in the entire wavelength range of 400 to 700 nm in the visible light region.

[0071] In this invention, the weight-average molecular weight (Mw) of the alkali-soluble resin is 2,000 to 40,000, preferably 3,000 to 30,000, and more preferably 4,000 to 20,000, in order to impart alkali-developable solubility. Furthermore, the Mw / Mn value is preferably 10 or less. If the weight-average molecular weight (Mw) is less than 2,000, adhesion to the substrate decreases, and the exposure pattern becomes difficult to retain. If it exceeds 40,000, alkali-developable solubility decreases, residue is generated, and the linearity of the pattern deteriorates. In this invention, the acid value of the alkali-soluble resin is 50 to 200 (KOH mg / g) to impart alkali-developable solubility, preferably in the range of 70 to 180, and more preferably in the range of 90 to 170. If the acid value is less than 50, alkali-developable solubility decreases, residue is generated, and the linearity of the pattern deteriorates. If it exceeds 200, adhesion to the substrate decreases, and the exposure pattern becomes difficult to retain.

[0072] <Alkali-soluble resin (B2-1) without ethylenically unsaturated double bonds> The photosensitive colored composition of the present invention may contain an alkali-soluble resin (B2-1) that does not have an ethylenically unsaturated double bond in order to adjust the degree of curing of the coating film. An alkali-soluble resin that does not have an ethylenically unsaturated double bond can be obtained by synthesizing it using at least one carboxyl group-containing ethylenically unsaturated monomer and one or more other ethylenically unsaturated monomers, without imparting an ethylenically unsaturated bond to the side chain.

[0073] <Alkali-soluble resin (B2-2) containing ethylenically unsaturated double bonds> The alkali-soluble resin contained in the photosensitive coloring composition of the present invention preferably has an ethylenically unsaturated double bond. In particular, by using a resin into which an ethylenically unsaturated double bond has been introduced by the methods (i) and (ii) shown below, the resin undergoes three-dimensional crosslinking when exposed to active energy rays to form a coating film, increasing the crosslinking density and improving chemical resistance.

[0074] [Method (i)] Method (i) involves, for example, copolymerizing an ethylenically unsaturated monomer having an epoxy group with one or more other monomers to obtain a copolymer, then adding the carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond to the side-chain epoxy group of the copolymer, and further reacting the resulting hydroxyl group with a polybasic acid anhydride to introduce an ethylenically unsaturated double bond and a carboxyl group.

[0075] Examples of ethylenically unsaturated monomers having an epoxy group include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate, which may be used individually or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth)acrylate is preferred.

[0076] Examples of unsaturated monobasic acids include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and monocarboxylic acids such as α-haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted derivatives of (meth)acrylic acid. These can be used individually or in combination of two or more types.

[0077] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride, which may be used individually or in combination of two or more. If necessary, such as to increase the number of carboxyl groups, tricarboxylic acid anhydrides such as trimellitic anhydride or tetracarboxylic dianhydrides such as pyromellitic dianhydride may be used to hydrolyze the remaining anhydride groups. Furthermore, if tetrahydrophthalic anhydride or maleic anhydride, which have ethylenically unsaturated double bonds, are used as polybasic acid anhydrides, the number of ethylenically unsaturated double bonds can be further increased.

[0078] A method similar to method (i) is, for example, a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with one or more other monomers, to which an ethylenically unsaturated monomer having an epoxy group is added to some of the side-chain carboxyl groups of the copolymer, thereby introducing an ethylenically unsaturated double bond and a carboxyl group.

[0079] [Method (ii)] Method (ii) involves using an ethylenically unsaturated monomer having a hydroxyl group and copolymerizing it with another unsaturated monobasic acid monomer having a carboxyl group, or with other monomers, to obtain a copolymer in which the side-chain hydroxyl group of the copolymer is reacted with the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group.

[0080] Examples of ethylenically unsaturated monomers having a hydroxyl group include 2-hydroxyethyl(meth)acrylate. Relate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3 - Alternatively, hydroxyalkyl methacrylates such as 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate can be used, and these may be used alone or in combination of two or more types. In addition, polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide, etc. to the above hydroxyalkyl (meth)acrylate, or polyester mono(meth)acrylate obtained by addition of polyγ-valerolactone, polyε-caprolactone, and / or poly12-hydroxystearic acid, etc. can also be used. From the viewpoint of suppressing foreign matter in the coating film, 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferred, and from the viewpoint of sensitivity, it is preferable to use one having 2 to 6 hydroxyl groups, and glycerol mono(meth)acrylate is even more preferred.

[0081] Examples of ethylenically unsaturated monomers having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate, but the composition is not limited to these, and two or more types can be used in combination.

[0082] Examples of monomers that constitute alkali-soluble resins include the following: For example, 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, or ethoxypolyethylene glycol (meth)acrylate, and other (meth)acrylates. Alternatively, examples include (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or styrenes such as acryloylmorpholine, or styrenes such as α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, and vinyl fatty acid compounds such as vinyl acetate or vinyl propionate.

[0083] Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 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-tri N-substituted maleimides such as chlorophenyl)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-benzoimidazolyl)phenyl]maleimide, and 9-maleimidacridine. Compounds represented by the following general formula (5) include, specifically, EO-modified cresol acrylate, n-nonylphenoxypolyethylene 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.

[0084] General formula (5) [ka]

[0085] (General formula (5), R6 is a hydrogen atom or a methyl group, R7 is an alkylene group having 2 or 3 carbon atoms, R8 is an alkyl group having 1 to 20 carbon atoms which may have a benzene ring, and n is an integer from 1 to 15.)

[0086] Furthermore, carboxyl group-containing ethylenically unsaturated monomers can also be used. Examples of carboxyl group-containing ethylenically unsaturated monomers include acrylic acid, methacrylic acid, ε-caprolactone-added acrylic acid, ε-caprolactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

[0087] Furthermore, hydroxyl group-containing ethylenically unsaturated monomers can also be used. Examples of hydroxyl group-containing ethylenically unsaturated monomers include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, or 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 the above-mentioned hydroxyalkyl (meth)acrylates, and (poly)ester mono(meth)acrylates obtained by adding (poly)γ-valerolactone, (poly)ε-caprolactone, and / or (poly)12-hydroxystearic acid.

[0088] Furthermore, ethylenically unsaturated monomers containing phosphate ester groups can also be used. Examples of ethylenically unsaturated monomers containing phosphate ester groups include monomers that can be obtained by reacting the hydroxyl group of the above-mentioned ethylenically unsaturated monomer containing hydroxyl group with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphate.

[0089] <Resin containing epoxy groups (B3)> In the present invention, resin (B) may further contain resin (B3) having epoxy groups in an amount that does not inhibit the effects of resin (B1) and resin (B2), for example, 0 to 30% by mass of resin (B) per 100% by mass. As a result, when a color filter is made using the coloring composition for color filters of the present invention, the crosslinking density increases due to the shrinkage of the coating film caused by the reaction during post-baking (firing) of the filter segment, thereby improving the heat resistance of the filter segment and suppressing pigment aggregation during the firing of the filter segment, resulting in a film with even better optical properties such as contrast ratio despite a high colorant concentration.

[0090] Examples of epoxy resins (B3) include polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), and phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropyl alcohol, etc.). Examples include polymers of lopenylbiphenyl (such as butadiene and isoprene), polycondensates of phenols and ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone), polycondensates of phenols and aromatic dimethanols (such as benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, and α,α,α',α'-biphenyldimethanol), polycondensates of phenols and aromatic dichloromethyls (such as α,α'-dichloroxylene and bischloromethylbiphenyl), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine epoxy resins, and glycidyl ester epoxy resins, but are not limited to these as long as they are commonly used epoxy compounds. These may be used individually or in combination of two or more.

[0091] Commercially available products include, for example, Epicote 807, Epicote 815, Epicote 825, Epicote 827, Epicote 828, Epicote 190P, Epicote 191P (all product names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicote 1004, Epicote 1256 (all product names; manufactured by Japan Epoxy Resin Co., Ltd.), TECHMORE VG3101L (product name; manufactured by Mitsui Chemicals, Inc.), EPPN-501H, 502H (product name; manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (product name; manufactured by Japan Epoxy Resin Co., Ltd.), JER 157S65, 157S70 (product name; manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-201 (product name; manufactured by Nippon Kayaku Co., Ltd.), JER152, JER154 (product names; manufactured by Japan Epoxy Resin Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (product names; manufactured by Nippon Kayaku Co., Ltd.), Ceroxide 2021, EHPE- Examples include 3150 (product name; manufactured by Daicel Chemical Industries), Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 (product names; manufactured by Nagase ChemteX), TEPIC-L, TEPIC-H, TEPIC-S (manufactured by Nissan Chemical Industries), etc. These are some examples, but are not limited to them.

[0092] <Other resins (B4)> In this invention, materials not belonging to resins (B1) to (B3) may be included as other resins (B4) to the extent that the effects of this invention are effective.

[0093] (Compounds containing an oxetane group) The photosensitive coloring composition of the present invention may contain a compound having an oxetane group. Examples of compounds having an oxetane group include those in which the oxetane group is monofunctional, those in which the oxetane group is bifunctional, and those in which the oxetane group is triplifunctional or more.

[0094] Examples of monofunctional oxetane groups include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyl oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane. Specific examples include OXE-10 and OXE-30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101 and OXT-212 manufactured by Toagosei Co., Ltd.

[0095] Examples of difunctional oxetane groups include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether-3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethyleneglycosyl bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl Examples include bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, and EO modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether. Specific examples include OXBP and OXTP manufactured by Ube Industries, and OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

[0096] As for substances with three or more oxetane groups, Pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa Examples of polymers include (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (for example, the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30. Such polymers can be obtained using known polymerization methods.

[0097] The content of the oxetane group-containing compound used in the photosensitive coloring composition of the present invention is usually 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of the coloring agent. It is preferable that the content of the oxetane group-containing compound be within the above range because it yields an excellent coating film with high chemical resistance.

[0098] (Hardening agent) Furthermore, the photosensitive coloring composition of the present invention may optionally contain a curing agent (curing accelerator) to assist in the curing of the thermosetting compound. Effective curing agents include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds, but are not limited to these; any curing agent that can react with the thermosetting compound may be used. Examples of curing agents include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2) These can be used as curing accelerators, such as phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, phosphorus compounds (e.g., triphenylphosphine), and S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid adduct, etc.). These may be used individually or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by mass per 100 parts by mass of the thermosetting compound.

[0099] <Polymerizable compound (C)> Polymerizable compound (C) is a monomer or oligomer containing a polymerizable unsaturated group. Examples of polymerizable compound (C) include alkylene oxide group-containing monomers, hydroxyl group-containing monomers, acid group-containing monomers, urethane bond-containing monomers, and other monomers. From the viewpoint of film shrinkage due to exposure and bonding, alkylene oxide group-containing monomers, hydroxyl group-containing monomers, and acid group-containing monomers are preferred. Examples of polymerizable unsaturated groups include vinyl groups, (meth)acryloyl groups, and (meth)allyl groups. The oligomer is a compound with a molecular weight of 1000 or more.

[0100] (alkylene oxide group-containing monomer) Preferred examples of alkylene oxide group-containing monomers include 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, and ethylene oxide 12 molar-modified dipentaerythritol hexaacrylate.

[0101] (Hydroxyl group-containing monomer) The hydroxyl group-containing monomer is preferably the compound represented by general formula (6). A film containing the compound represented by general formula (6) has increased solubility in alkaline developers due to the action of the hydroxyl group, which suppresses development residue. Furthermore, the presence of the hydroxyl group results in the film having highly polar hydrophilic sites, making it difficult for nonpolar oxygen molecules to coexist. This reduces polymerization inhibition by oxygen during exposure, making it easier to create highly rectangular patterns. General formula (6) [ka]

[0102] However, in general formula (6), X is a substructure shown in general formula (7), general formula (8), or general formula (9) below. 1 , R 2 represents a hydrogen atom or a methyl group. [ka]

[0103] In general formula (7), n represents an integer from 1 to 4, and R 3 represents a hydrogen atom or a methyl group. In general formula (8), n represents an integer from 1 to 4. In general formula (9), n represents an integer from 1 to 4.

[0104] Compounds represented by general formula (6) include, for example, ethylene glycol diglycidyl ether diacrylate, diethylene glycol diglycidyl ether diacrylate, triethylene glycol diglycidyl ether diacrylate, tetraethylene glycol diglycidyl ether diacrylate, propylene glycol diglycidyl ether diacrylate, dipropylene glycol diglycidyl ether diacrylate, tripropylene glycol diglycidyl ether diacrylate, tetrapropylene glycol diglycidyl ether diacrylate, 1,3-propanediol diglycidyl ether diacrylate, butylene glycol diglycidyl ether diacrylate, glycerin diglycidyl ether diacrylate, diglycerin diglycidyl ether diacrylate, triglycerin diglycidyl ether diacrylate, and tetraglycerin diglycidyl ether diacrylate. Among these, propylene glycol diglycidyl diacrylate is more preferred in terms of polymerizable unsaturated group equivalent and inter-polymerizable unsaturated group distance, and glycerin diglycidyl ether diacrylate is more preferred in terms of hydroxyl group equivalent. Both contribute to improved curability, making it easier to create highly rectangular patterns.

[0105] The content of the compound represented by general formula (6) is preferably 1 to 50% by mass, and more preferably 2 to 40% by mass, based on 100% by mass of the solid content of the colored composition.

[0106] (Acid group-containing monomer) Examples of acidic groups in acidic monomers include sulfonic acid groups, carboxyl groups, and phosphate groups.

[0107] Examples of acid group-containing monomers include esters of polyhydric alcohols and (meth)acrylic acid-containing poly(meth)acrylates with free hydroxyl groups and dicarboxylic acids; and esters of polyhydric acids and monohydroxyalkyl (meth)acrylates. Specific examples include monoesterified compounds containing free carboxyl groups between monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate and dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; and oligoesterified compounds containing free carboxyl groups between tricarboxylic acids such as propane-1,2,3-tricarboxylic acid (tricarbaryl 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 and monohydroxymonoacrylates or monohydroxymonomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

[0108] (Urethane bond-containing monomer) Examples of urethane bond-containing monomers include polyfunctional urethane acrylates obtained by reacting a polyfunctional isocyanate with a hydroxyl group-containing (meth)acrylate, and polyfunctional urethane acrylates obtained by reacting an alcohol with a polyfunctional isocyanate and then reacting that with a hydroxyl group-containing (meth)acrylate.

[0109] Examples of hydroxyl group-containing (meth)acrylates 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, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, and hydroxyl group-containing polyol polyacrylates.

[0110] Examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanates.

[0111] (Other monomers) Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol di(meth)acrylate Examples include xanediol 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, various acrylic acid esters and methacrylic acid esters such as (meth)acrylic acid esters of methylolated melamine, epoxy(meth)acrylate, and urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, and acrylonitrile.

[0112] Polymerizable compound (C) can be used alone or in combination of two or more types.

[0113] The amount of polymerizable compound (C) is preferably 5% by mass or more and less than 25% by mass of the total solids content of the photosensitive colored composition. Adding an appropriate amount further improves curability and developability.

[0114] (Photopolymerization initiator (D)) Various photopolymerization initiators can be used as the photopolymerization initiator (D), but in this specification, oxime ester-based photopolymerization initiators are preferred. Oxime ester-based photopolymerization initiators undergo cleavage of the NO bond in the oxime upon absorption of ultraviolet light, generating iminyl radicals and alkyloxy radicals. These radicals further decompose to generate highly active radicals, allowing for pattern formation with less exposure compared to other photopolymerization initiators. This improves photocurability, resulting in higher film density and greater shrinkage during the exposure and heating process, which is preferable.

[0115] Examples of oxime ester-based photopolymerization initiators include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. Commercially available oxime compounds include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (all manufactured by BASF Japan), TR-PBG-304, TR-PBG-305, TR-PBG-3057, TR-PBG-345, TR-PBG-358 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Optomer N-1919, ADEKA Arclus NCI-730, NCI-831, and NCI-930 (manufactured by ADEKA).

[0116] Oxime ester-based photopolymerization initiators include monooxime-based initiators having one oxime ester group and a carbazole, fluorene, or diphenyl skeleton in the molecule, and dioxime-based initiators having two oxime ester groups. Furthermore, preferred specific structures of oxime ester-based photopolymerization initiators include, for example, hydroxyl groups, nitro groups, carbonyl groups, fluorocarbon groups, and benzofurans.

[0117] (Monoxime ester photopolymerization initiators with a carbazole skeleton) [ka] JPEG2026115098000009.jpg105149

[0118] (A monooxime ester-based photopolymerization initiator having a fluorene skeleton) [ka]

[0119] (Monoxime ester photopolymerization initiator having a diphenyl skeleton) [ka]

[0120] (Photopolymerization initiator having two oxime ester groups) Examples of photopolymerization initiators include those having two oxime ester groups on either side of a carbazole skeleton or a phenothiazine skeleton, as shown below. [ka]

[0121] For the photopolymerization initiator (D), other polymerization initiators other than oxime ester-based photopolymerization initiators can be used. Other photopolymerization initiators include, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4- Acetophenone compounds such as methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t- Benzophenone compounds such as butylperoxycarbonyl)benzophenone; thioxanthone compounds such as thioxanthone, 2-chlorthioxanthone, 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( Triazine compounds such as trichloromethyl-(4'-methoxystyryl)-6-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;Examples include 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; and titanocene compounds.

[0122] The content of the photopolymerization initiator (D) is preferably 1% by mass or more and less than 5% by mass of the total solids content of the photosensitive colored composition. When an appropriate amount is added, the photocurability and developer resistance are improved and the surface condition of the coating tends to become smoother.

[0123] The photopolymerization initiator (D) can be used alone or in combination of two or more types.

[0124] (Other additives) The photosensitive colored composition of the present invention may contain, in appropriate combinations, other additives such as sensitizers, thiol-based chain transfer agents, polymerization inhibitors, ultraviolet absorbers, antioxidants, leveling agents, storage stabilizers, and adhesion improvers. Preferably, the total amount of solids of the other additives is 0.1% by mass or more and less than 2% by mass of the total solids content of the photosensitive colored composition.

[0125] <Sensitizer (F)> 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 benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiaidine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyradinoporphyrazine derivatives. Examples include phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxaliloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrillium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospilopyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxyesters, acylphosphine oxides, methylphenylglyoxylates, 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.

[0126] Among the sensitizers mentioned above, thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives are particularly suitable for sensitizing. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N-ethylcarbazole, etc., can be used.

[0127] These sensitizers can be used individually or mixed in any ratio as needed. Examples of commercially available products include "KAYACURE DETX-S" (2,4-diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.) and "CHEMARK DEABP" (4,4'-bis(diethylamino)benzophenone, manufactured by Chemark Chemical Co., Ltd.).

[0128] More specifically, examples of sensitizers include, but are not limited to, those described in "Pigment Handbook" (1986, Kodansha) edited by Shin Okawara et al., "Chemistry of Functional Pigments" (1981, CMC) edited by Shin Okawara et al., and "Special Functional Materials" (1986, CMC). In addition, sensitizers that exhibit absorption in the ultraviolet to near-infrared region can also be included.

[0129] When using a sensitizer, the amount contained is preferably 3 to 60 parts by mass per 100 parts by mass of the photopolymerization initiator contained in the coloring composition, and more preferably 5 to 50 parts by mass from the viewpoint of photocurability and developability.

[0130] <Thiol-based chain transfer agent (G)> The photosensitive colored composition of the present invention preferably contains a thiol-based chain transfer agent. By using thiols together with a photopolymerization initiator, thiyl radicals are generated in the radical polymerization process after light irradiation that act as chain transfer agents and are less susceptible to polymerization inhibition by oxygen, resulting in a highly sensitive colored composition.

[0131] Furthermore, polyfunctional aliphatic thiols bonded to aliphatic groups such as methylene or ethylene groups, which have two or more SH groups, are preferred. More preferably, polyfunctional aliphatic thiols with four or more SH groups are preferred. Increasing the number of functional groups improves the polymerization initiation function, allowing curing from the surface of the pattern to near the substrate.

[0132] 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, and pen Examples include tetraerythritol tetrakisthiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. Preferably, examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

[0133] These thiol-based chain transfer agents can be used individually or in combination of two or more.

[0134] Furthermore, the content of the thiol-based chain transfer agent is preferably 0.1 to 2 parts by mass, and more preferably 0.2 to 1 part by mass, per 100 parts by mass of the coloring agent. Within this range, the effect of the chain transfer agent is enhanced, resulting in improved sensitivity, tapered shape, wrinkles, film shrinkage, and other properties.

[0135] <Polymerization inhibitor (H)> The photosensitive colored composition of the present invention may contain a polymerization inhibitor to prevent photosensitivity due to diffracted light from the mask during exposure. Adding a polymerization inhibitor prevents the curing from progressing beyond the desired pattern through photosensitive chain polymerization.

[0136] Polymerization inhibitors include alkylcatechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, and 2-n-butyl Examples include alkylresorcinol compounds such as ruresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, and 4-tert-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tripenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphine and trisnonylphenylphosphine; pyrogallol and phloroglucin. The polymerization inhibitor content is preferably 0.01 to 0.4 parts by mass per 100 parts by mass of the solid content of the colored composition excluding the solvent. Within this range, the effect of the polymerization inhibitor becomes greater, resulting in improved linearity of the taper, reduction of wrinkles in the coating film, and improved pattern resolution.

[0137] <UV absorber (I)> The photosensitive colored composition of the invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function, and examples include benzotriazole organic compounds, triazine organic compounds, benzophenone organic compounds, salicylate ester organic compounds, cyanoacrylate organic compounds, and salicylate organic compounds.

[0138] The UV absorber content is preferably 5 to 70% by mass of the total 100% by mass of the photopolymerization initiator and UV absorber. If the UV absorber content is less than the above, the effect of the UV absorber will be small and resolution cannot be ensured, and if it is more than the above, the sensitivity will be low and problems such as pixel detachment and hole diameter becoming larger than the design value may occur.

[0139] Furthermore, the total content of the photopolymerization initiator and UV absorber is preferably 1 to 20% by mass of 100% by mass of the solid content of the photosensitive colored composition. If the total content of the photopolymerization initiator and UV absorber is less than the above, adhesion will be weakened and pixel peeling may occur, and if it is more than the above, the sensitivity may be too high and the resolution may be poor.

[0140] Benzotriazole organic compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, and 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, a mixture of 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy,C7-9 side chain and linear alkyl ester, 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 Reaction product of 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t- Examples include 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-benzotriazole-2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2-yl)phenyl]propionate. Other oligomeric and polymer-type compounds having a benzotriazole structure can also be used.

[0141] More specifically, examples include TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, and 1130 from BASF Corporation; ADEKA LA-29, LA-31RG, LA-32, and LA-36 from ADEKA Corporation; KEMISORB 71, 73, 74, 79, and 279 from Chemipro Chemical Co., Ltd.; and RUVA-93 from Otsuka Chemical Co., Ltd.

[0142] Examples of triazine-based organic 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 of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. Products 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. Other oligomeric and polymeric compounds having a triazine structure can also be used.

[0143] More specifically, examples include KEMISORB 102 from Chemipro Chemical Co., Ltd., TINUVIN 400, 405, 460, 477, 479, and 1577ED from BASF, ADEKA LA-46 and LA-F70 from ADEKA Corporation, and CYASORB UV-1164 from Sun Chemical Co., Ltd.

[0144] Examples of benzophenone-based organic compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3-water, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. Other oligomeric and polymer-type compounds having a benzophenone structure can also be used.

[0145] More specifically, examples include KEMISORB 10, 11, 11S, 12, and 111 from Chemipro Chemical Co., Ltd., SEESORB 101 and 107 from Cipro Chemical Co., Ltd., ADEKA Stab 1413 from ADEKA Corporation, and UV-12 from Sun Chemical Co., Ltd.

[0146] Examples of salicylic acid ester organic compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Other oligomeric and polymeric compounds having a salicylic acid ester structure can also be used.

[0147] <Antioxidant (J)> The photosensitive colored composition of the present invention may contain an antioxidant. The antioxidant prevents the photopolymerization initiator and thermosetting compound contained in the photosensitive colored composition from oxidizing and yellowing due to the heat process during thermosetting and ITO annealing, thereby increasing the transmittance of the coating film. In particular, when the colorant concentration of the colored composition is high, the amount of coating film crosslinking component decreases, so countermeasures such as using a highly sensitive crosslinking component or increasing the amount of photopolymerization initiator are taken, which can lead to a phenomenon intensifying yellowing during the heat process. 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.

[0148] In the present invention, the "antioxidant" can be any compound having radical scavenging or peroxide decomposition functions. Specifically, examples of antioxidants include hindered phenol, hindered amine, phosphorus, sulfur, and hydroxylamine compounds, and known antioxidants can be used. Furthermore, it is preferable that the antioxidant used in the present invention does not contain halogen atoms.

[0149] Among these antioxidants, preferred ones from the viewpoint of achieving both the permeability and sensitivity of the coating film include hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, or sulfur-based antioxidants.

[0150] Examples of hindered phenol antioxidants include 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), stearyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5] Undecane, 1,3,5-Tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-Tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-Methylenebis(6-t-butyl-4-ethylphenol), 2,2'-Thiodiethylbis-(3,5-di- t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), i-octyl3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4, 6-Bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid]ethylenebisoxybisethylene, 1,6-Hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-Bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, Examples include 2,2'-thio-bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethylphenol), 2,2'-methylene-bis-(6-(1-methylcyclohexyl)-p-cresol), and 2,4-dimethyl-6-(1-methylcyclohexyl)-phenol. Other oligomeric and polymer-type compounds having a hindered phenol structure can also be used.

[0151] More specifically, examples include ADEKA stubs AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330 from ADEKA Corporation; KEMINOX 101, 179, 76, and 9425 from Chemipro Corporation; IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 from BASF Corporation; and Cyanox CY-1790 and CY-2777 from Sun Chemical Co., Ltd.

[0152] Examples of hindered amine antioxidants include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidine-4-yl)carbonate, and 1,2,2,6,6-penta Methyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1-pi Ester of peridineethanol and 3,5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazine-2-yl]-4,7-diazadecane-1,10-diamine, reaction product of bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) decandioate, 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyriperidyl)[[3,5-bi (1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonatemethyl 1,2,2,6,6-pentamethyl-4-pyriperidyl sebacate, poly[[6-morpholino-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid ester, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,Examples include 6-hexamethylenediamine and 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide. Other oligomeric and polymeric compounds having a hindered amine structure can also be used.

[0153] More specifically, examples include ADEKA Corporation's ADEKA Stab LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, LA-502XP; Chemipro Chemical's KAMISTAB29, 62, 77, 94; BASF Corporation's Tinuvin249, TINUVIN111FDL, 123, 144, 292, 5100; and Sun Chemical's Siasorb UV-3346, UV-3529, UV-3853, etc.

[0154] Phosphorus-based antioxidants include di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl)2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tetra(C12~C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, and diphenyl mono(2 -Ethylhexyl) phosphite, diphenylisodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4-biphenyl diphosphonate, tris(tridecyl) phosphite, phenylisooctyl phosphite, phenylisodecyl phosphite, phenyldi(tridecyl) phosphite, diphenylisooctyl phosphite, diphenyltridecyl phosphite, 4,4'-isopropylide Diphenolalkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl Examples include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butanetriphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphitediethyl ester, sodium bis(4-t-butylphenyl)phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)benzene, and ethylbis(2,4-ditert-butyl-6-methylphenyl) phosphite. Other oligomer and polymer type compounds having a phosphite structure can also be used.

[0155] More specifically, examples include ADEKA Corporation's ADEKA Stub PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP; BASF Corporation's IRGAFOS168; and Clariant Chemicals' Hostanox P-EPQ.

[0156] Examples of sulfur-based antioxidants include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], 3,3'-thiobispropionate ditridecyl, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol. Other oligomeric and polymer-type compounds having a thioether structure can also be used.

[0157] More specifically, examples include ADEKA Corporation's ADEKA stub AO-412S and AO-503, and Chemipro Chemicals' KEMINOXPLS.

[0158] These antioxidants can be used individually or mixed in any ratio as needed.

[0159] Furthermore, adding an antioxidant in an amount of 0.05 to 5.0 parts by mass per 100 parts by mass of colorant may improve transmittance, spectral characteristics, and sensitivity.

[0160] <Leveling agent (K)> In order to improve the coatability of the composition on a transparent substrate and the drying properties of the colored film, it is preferable to add a leveling agent to the photosensitive colored composition of the present invention. Various surfactants such as silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants can be used as leveling agents.

[0161] Examples of silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0162] More specifically, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345 / 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 from BIC Chemie, and FZ-7002, 2110 from Toray Dow Corning. Examples include 2122, 2123, 2191, 5609, and Shin-Etsu Chemical Co., Ltd.'s X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341, etc.

[0163] Examples of fluorine-based surfactants include surfactants or leveling agents having fluorocarbon chains.

[0164] More specifically, examples include Surflon S-242, S-243, S-420, S-611, S-651, S-386 from AGC Seimi Chemical Co., Ltd., Megafac F-253, F-477, F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, DS-21 from DIC Corporation, FC-4430, FC-4432 from Sumitomo 3M Co., Ltd., EF-PP31N09, EF-PP33G1, EF-PP32C1 from Mitsubishi Materials Electronic Chemicals Co., Ltd., and Futergent 602A from Neos Co., Ltd.

[0165] Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristelle ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tripenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and sorbitan tristearate. Examples include sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkylimidazoline, etc.

[0166] More specifically, Kao's Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS -110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD450, Leodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L1 06, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amito 102, 10 Examples include 5, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Pluronic® L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R manufactured by ADEKA Corporation, and (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0167] Cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and their ethylene oxide adducts.

[0168] More specifically, examples include Kao Corporation's Acetamine 24, Cortamin 24P, 60W, and 86P Concentrate.

[0169] Examples of anionic surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate esters.

[0170] More specifically, examples include Neos Co., Ltd.'s Futergent 100 and 150, and ADEKA Corporation's Adeka Hope YES-25, Adeka Call TS-230E, PS-440E, EC-8600, etc.

[0171] Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.

[0172] More specifically, examples include Kao Corporation's Anchitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N.

[0173] When the photosensitive colored composition of the present invention contains a surfactant, the amount of surfactant added is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, relative to the total solid content of the composition of the present invention. Within this range, a good balance is achieved between the applicability, pattern adhesion, and transmittance of the colored composition. The photosensitive coloring composition of the present invention may contain only one type of surfactant or two or more types. If two or more types are included, it is preferable that their total amount be within the above range.

[0174] <Storage stabilizer (L)> The colored composition of the present invention may contain a storage stabilizer to stabilize the viscosity of the composition over time. Examples of storage stabilizers include benzyl trimethyl chloride, quaternary ammonium chlorides such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butyl pyrocatechol, tetraethylphosphine, and tetraphenylphosphine, and phosphates. The storage stabilizer can be used in an amount of 0.1 to 10% by mass, based on the total amount of the colorant (100% by mass).

[0175] <Adhesion enhancer (M)> The photosensitive colored composition of the present invention may contain adhesion-enhancing agents such as silane coupling agents to improve adhesion to the substrate. Improved adhesion due to the adhesion-enhancing agent results in better reproduction of fine lines and improved resolution.

[0176] Adhesion enhancers include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane, epoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, and N-2-(aminoethyl)-3 Silane coupling agents include aminosilanes such as -aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and hydrochloride salts 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-isocyanatetopropyltriethoxysilane. The adhesion enhancer can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, per 100 parts by mass of the coloring agent in the coloring composition. Within this range, the effect is greater, and the balance between adhesion, resolution, and sensitivity is good, making it more preferable.

[0177] <Organic solvent (S)> The photosensitive colored composition of the present invention contains an organic solvent to facilitate the formation of a colored film by coating it onto a substrate such as glass to a dry film thickness of 0.2 to 5 μm. The organic solvent is selected considering not only the good coatability of the colored composition, but also the solubility of each component of the colored composition, as well as safety.

[0178] The organic solvent (S) used in the present invention may be used in combination with other organic solvents commonly used in the field, as long as it does not impair the effects of the present invention. Considering properties such as boiling point, SP value, evaporation rate, and viscosity, the solvent may be used individually or in combination as appropriate according to the application conditions (speed, drying conditions, etc.).

[0179] Considering the aforementioned properties, the organic solvent (S) used in the present invention is preferably 70% by mass or more and less than 90% by mass of the total amount of the photosensitive composition.

[0180] Examples of organic solvents that can be used in combination in the present invention include ester solvents (solvents containing -COO- in the molecule but not -O-), ether solvents (solvents containing -O- in the molecule but not -COO-, although they may contain -OH), ether ester solvents (solvents containing both -COO- and -O- in the molecule), ketone solvents (solvents containing both -CO- in the molecule but not -COO-), alcohol solvents (solvents containing both -OH in the molecule but not -O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

[0181] Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0182] Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, anisole, phenethole, and methylanisole.

[0183] Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, ethyl 3-methyl Examples include toxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, and dipropylene glycol diacetate.

[0184] Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0185] Examples of alcoholic solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, and glycerin.

[0186] Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

[0187] Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone. These organic solvents may be used individually or in combination of two or more types.

[0188] <Method for producing a photosensitive colored composition> The photosensitive colored composition of the present invention can be manufactured by finely dispersing pigments in a dispersant, binder resin, and / or solvent, preferably together with a dispersion aid (pigment derivative or surfactant), using various dispersion methods such as a kneader, two-roll mill, three-roll mill, ball mill, horizontal sand mill, vertical sand mill, annular bead mill, or attritor. At this time, two or more pigments may be dispersed simultaneously on the colorant carrier, or they may be dispersed separately on pigment carriers and then mixed.

[0189] Furthermore, the photosensitive colored composition can be prepared as a solvent-developable or alkali-developable colored composition. The solvent-developable or alkali-developable colored composition can be prepared by mixing the colored composition with a polymerizable compound and / or a photopolymerization initiator, and optionally with a solvent, other dispersing aids, and additives. The photopolymerization initiator may be added during the preparation of the colored composition, or it may be added to the prepared colored composition afterward.

[0190] <Removal of coarse particles> The photosensitive colored composition of the present invention is preferably subjected to the removal of coarse particles of 5 μm or larger, preferably 1 μm or larger, and more preferably 0.5 μm or larger, as well as any impurities, by means of centrifugal separation, filtration using a sintered filter or a membrane filter. Thus, the colored composition is preferably substantially free of particles of 0.5 μm or larger. More preferably, the particles are 0.3 μm or smaller.

[0191] <Moisture content in photosensitive colored composition> The photosensitive colored composition of the present invention preferably contains 2% by mass or less of water.

[0192] If the water content of the photosensitive coloring composition is within the above range, it exhibits excellent dispersion stability and sensitivity even after storage over time.

[0193] The water content in the photosensitive coloring composition is preferably 1.8% by mass or less, and more preferably 1.6% by mass or less. If the water content is sufficiently low within this range, problems with dispersion stability and sensitivity are unlikely to occur even after storage over time.

[0194] There are no particular restrictions on the method for controlling the water content, and known methods can be used. For example, methods include manufacturing the photosensitive colored composition while blowing in a dry inert gas, or adding molecular sieves after manufacturing to dehydrate the mixture. Among these, the method of manufacturing while blowing in a dry inert gas is preferred.

[0195] The water content can be measured by known methods such as the Karl Fischer method.

[0196] <Amount of toluene in photosensitive colored composition> The photosensitive coloring composition of the present invention may contain toluene, and if so, the toluene content is preferably 0.1 to 10 ppm by mass. The upper limit of the toluene content is preferably 9 ppm by mass or less, more preferably 8 ppm by mass or less, and even more preferably 7 ppm by mass or less. The lower limit is preferably 0.2 ppm by mass or more, more preferably 0.3 ppm by mass or more, and even more preferably 0.4 ppm by mass or more.

[0197] Furthermore, in the present invention, the content of each solid component in 100% by mass of the total solid content of the photosensitive coloring composition is preferably as follows. Coloring agent (A): 40% by mass or more to less than 65% by mass Resin (B): 10% by mass or more to less than 50% by mass Polymerizable compound (C): 5% by mass or more to less than 25% by mass Photopolymerization initiator (D): 1% by mass or more and less than 5% by mass By using the above content, it is possible to provide a photosensitive colored composition in which the pigment concentration is increased within a range that satisfies the necessary characteristics of the photosensitive colored composition, and furthermore, the film formed after the heating step following the coating, exposure, and development of the photosensitive colored composition becomes thinner, and the colorant concentration in the thin film becomes even higher.

[0198] <Color Filter> 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. The color filter may further comprise a magenta filter segment, a cyan filter segment, and a yellow filter segment.

[0199] <How to manufacture color filters> Color filters can be manufactured using photolithography. Specifically, the process involves applying a photosensitive coloring composition to a substrate to produce a coating film. A step of exposing and developing the coated film to form a pattern, The process involves heat-treating the pattern at 240-300°C (post-bake or firing). It is manufactured from the above. For thinning by thermal shrinkage, a higher heat treatment temperature is preferable, preferably 260°C or higher, and more preferably 280°C or higher.

[0200] In the photolithography method, a colored composition prepared as a solvent-developable or alkali-developable colored resist material is applied to a transparent substrate by coating methods such as spray coating, spin coating, slit coating, or roll coating, so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed (irradiated with radiation) through a mask having a predetermined pattern, which is provided in contact with or without contact with the film. After that, the uncured areas are removed by immersion in a solvent or alkali developer or by spraying the developer to form the desired pattern, and the same operation is repeated for other colors to manufacture a color filter. Furthermore, heating can be applied as necessary to promote polymerization of the colored resist material. According to the photolithography method, color filters with higher precision can be manufactured than those produced by the printing method described above.

[0201] For developing, aqueous solutions of sodium carbonate, sodium hydroxide, etc., are used as alkaline developers, and organic alkalis such as dimethylbenzylamine and triethanolamine can also be used. Furthermore, defoamers and surfactants may be added to the developer. Furthermore, in order to increase the exposure sensitivity, after applying and drying the above-mentioned colored resist, a water-soluble or alkaline water-soluble resin, such as polyvinyl alcohol or water-soluble acrylic resin, may be applied and dried to form a film that prevents polymerization inhibition by oxygen, and then exposure may be performed.

[0202] The color filters of the present invention can be manufactured by methods other than those described above, such as electrodeposition, transfer, and inkjet, and the coloring composition of the present invention can be used in any of these methods. The electrodeposition method is a method of manufacturing color filters by using a transparent conductive film formed on a substrate and electrodepositing each color filter segment onto the transparent conductive film by electrophoresis of colloidal particles. The transfer method is a method in which filter segments are formed in advance on the surface of a peelable transfer base sheet, and these filter segments are transferred to a desired substrate.

[0203] A black matrix can be formed before each color filter segment is formed on a transparent or reflective substrate. The black matrix can be, but is not limited to, a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film with a light-shielding agent dispersed within it. Alternatively, thin-film transistors (TFTs) can be formed on the transparent or reflective substrate beforehand, and then each color filter segment can be formed. Furthermore, an overcoat film or a transparent conductive film may be formed on the color filter of the present invention as needed.

[0204] The color filter of the present invention is bonded to a counter substrate using a sealant, liquid crystal is injected through an injection port provided in the sealed portion, the injection port is sealed, and a polarizing film or phase difference film is bonded to the outside of the substrate as needed to manufacture a color liquid crystal display device. This color liquid crystal display device can be used in liquid crystal display modes that perform colorization using color filters such as twisted nematic (TN), super-twisted nematic (STN), in-plane switching (IPS), vertically aligned (VA), and optically convened bend (OCB).

[0205] The color filter of the present invention can be used not only for color liquid crystal display devices but also for the manufacture of solid-state image sensors, organic EL display devices, quantum dot display devices, and electronic paper.

[0206] <Liquid crystal display device> A liquid crystal display device equipped with the color filter of the present invention will be described. The liquid crystal 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 (CCFLs) and white LEDs, but in the present invention, it is preferable to use a white LED because it expands the red color reproduction range. Figure 1 is a schematic cross-sectional view of a liquid crystal display device 10 equipped with the color filter of the present invention. The device 10 shown in Figure 1 comprises a pair of transparent substrates 11 and 21 arranged spaced apart and facing each other, with liquid crystal LC sealed between them.

[0207] Liquid crystal (LC) is oriented according to the driving mode, such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), and OCB (Optically Compensated Birefringence). A TFT (Thin Film Transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed on top of it. An alignment layer 14 is provided on top of the transparent electrode layer 13. In addition, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0208] On the other hand, the color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. The red, green, and blue filter segments constituting the color filter 22 are separated by a black matrix (not shown).

[0209] A transparent protective film (not shown) is formed over the color filter 22 as needed, and a transparent electrode layer 23 made of, for example, ITO is formed on top of that, and an alignment layer 24 is provided covering the transparent electrode layer 23.

[0210] Furthermore, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. A backlight unit 30 is provided below the polarizing plate 15.

[0211] White LED light sources include those with a fluorescent filter formed on the surface of a blue LED, and those with a phosphor contained in the resin package of a blue LED. They have a wavelength (λ3) in which the emission intensity is maximum in the range of 430nm to 485nm, a wavelength (λ4) in which the emission intensity is maximum in the range of 530nm to 580nm, and a wavelength (λ5) in which the emission intensity is maximum in the range of 600nm to 650nm, and the ratio of the emission intensity I3 at wavelength λ3 to the emission intensity I4 at wavelength λ4 (I4 / I3) is between 0.2 and 0.4. Preferably, a white LED light source (LED1) has spectral characteristics in which the ratio of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 (I5 / I3) is 0.1 or more and 1.3 or less, or a white LED light source (LED2) has spectral characteristics in which the wavelength (λ1) at which the emission intensity is maximum is in the range of 430 nm to 485 nm, the peak wavelength (λ2) of the second emission intensity is in the range of 530 nm to 580 nm, and the ratio of the emission intensity I1 at wavelength λ1 to the emission intensity I2 at wavelength λ2 (I2 / I1) is 0.2 or more and 0.7 or less.

[0212] Examples of LED1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation) and NSSW304D-HG-V1 (manufactured by Nichia Corporation).

[0213] Examples of LED2 include the NSSW440 (manufactured by Nichia Corporation) and the NSSW304D (manufactured by Nichia Corporation).

[0214] <Solid-state image sensor> The film of the present invention can be used in solid-state image sensors. The form in which it is used in solid-state image sensors is not particularly limited, but for example, a substrate has a plurality of photodiodes and transfer electrodes made of polysilicon or the like that constitute the light-receiving area of ​​a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.), a light-shielding film has openings only for the light-receiving portion of the photodiodes on the photodiodes and transfer electrodes, a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiodes, and a filter has been placed on the device protection film. Furthermore, there may be a configuration in which a light-collecting means (e.g., a microlens, etc.; the same applies hereinafter) is placed on the device protection film below the filter (closer to the substrate), or a configuration in which the light-collecting means is placed on the filter. In addition, the filter may have a structure in which a hardened film that forms each colored pixel is embedded in a space partitioned, for example, in a grid pattern by partitions. In this case, it is preferable that the partitions have a low refractive index with respect to each colored pixel. The imaging device equipped with the solid-state image sensor of the present invention can be used in a variety of applications, such as digital cameras, electronic devices with imaging functions (smartphones, tablet terminals, etc.), in-vehicle cameras, surveillance cameras, and optical sensors.

[0215] <Infrared sensor> The film of the present invention can be used in infrared sensors. The form in which it is used in infrared sensors is not particularly limited. Figure 2 is a schematic cross-sectional view showing an example of the configuration of an infrared sensor equipped with the film of the present invention. The infrared sensor shown in Figure 2 comprises a 100 and a solid-state image sensor 110.

[0216] The imaging area on the solid-state image sensor 110 is formed by combining an infrared cut filter 111 and a color filter 112.

[0217] The infrared cut filter 111 can be formed using the resin composition of the present invention, and transmits light in the visible light region (for example, light with a wavelength of 400 to 700 nm) and blocks light in the infrared region.

[0218] The color filter 112 is a color filter in which pixels that transmit and absorb light of specific wavelengths in the visible light region are formed. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed is used.

[0219] Between the infrared transmission filter 113 and the solid-state image sensor 110, a resin film 114 is arranged that can transmit light of wavelengths that have passed through the infrared transmission filter 113. The infrared transmission filter 113 is a filter that blocks light in the visible light region and transmits infrared light of a specific wavelength, and can be formed using the resin composition of the present invention.

[0220] A microlens 115 is positioned on the incident light h side of the color filter 112 and the infrared transmission filter 113. A planarization film 116 is formed to cover the microlens 115.

[0221] In the configuration shown in Figure 2, a resin film 114 is arranged, but an infrared transmission filter 113 may be formed instead of the resin film 114.

[0222] This infrared sensor can simultaneously capture image information, enabling motion sensing and other applications that recognize moving objects. Furthermore, because it can acquire distance information, it can capture images containing 3D data. In addition, this infrared sensor can also be used as a biometric authentication sensor. [Examples]

[0223] The present invention will be described below with reference to examples. In the examples, "parts" and "%" refer to "parts by mass" and "mass%", respectively.

[0224] The weight-average molecular weight (Mw) and acid value (mgKOH / g) for resin (B) are as follows:

[0225] <Solid content, solid content concentration> In this invention, the solid content refers to the mass residue after standing in an oven at 200°C for 30 minutes.

[0226] <Weight-average molecular weight (Mw)> The resin weight-average molecular weight (Mw) was measured by gel permeation chromatography (GPC) equipped with a RI detector. Using HLC-8220GPC (manufactured by Tosoh Corporation) as the apparatus, two separation columns were connected in series, and for both packing materials, two "TSK-GEL SUPER HZM-N" were connected in series and used. The measurement was carried out at an oven temperature of 40 °C, using a THF solution as the eluent, and at a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1 mass% of the above eluent and 20 microliters were injected. All molecular weights are values in terms of polystyrene conversion.

[0227] <Acid value (mgKOH / g)> To 0.5 - 1 g of the resin solution, 80 ml of acetone and 10 ml of water were added and stirred to dissolve uniformly. Using a 0.1 mol / L aqueous KOH solution as the titrant, titration was carried out using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) to measure the acid value (mgKOH / g) of the resin solution. Then, from the acid value of the resin solution and the solid content concentration of the resin solution, the acid value per solid content of the resin was calculated.

[0228] <Refinement of colorant (A)> (Colorant (A-1)) 100 parts of C.I. Pigment Red 254 ("Irgaphor Red B-CF" manufactured by BASF), 10 parts of a dye derivative (b-1), 1000 parts of crushed salt, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 70 °C for 8 hours. This mixture was put into 2000 parts of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 80 °C to make it into a slurry state. After repeating filtration and washing with water to remove salt and the solvent, it was dried at 80 °C for 24 hours to obtain colorant (A-1).

[0229] (Colorant (A-2)) C.I. Pigment Red 177 (Chromophthal Red A2B manufactured by BASF): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 120 °C for 8 hours. Next, this kneaded material was put into 5 liters of warm water and stirred for 1 hour while heating to 70 °C to make it into a slurry state, and then filtration and washing with water were repeated to remove sodium chloride and diethylene glycol, and then dried at 80 °C for one day and night to obtain a colorant (A-2).

[0230] (Colorant (A-3)) C.I. Pigment Red 272 (Irgazin(r) Flame Red K 3800 manufactured by BASF Japan) 100 parts, sodium chloride 1600 parts, and diethylene glycol 190 parts were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 60 °C for 10 hours. Next, this mixture was put into 3 liters of warm water and stirred for about 1 hour with a high-speed mixer while heating to about 80 °C to make it into a slurry state, and then filtration and washing with water were repeated to remove sodium chloride and the solvent, and then dried at 80 °C for one day and night to obtain a colorant (A-3).

[0231] (Colorant (A-4)) C.I. Pigment Red 269 (Toner Magenta F8B manufactured by Clariant) 100 parts, sodium chloride 800 parts, and diethylene glycol 180 parts were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 70 °C for 5 hours. This mixture was put into 4000 parts of warm water and stirred for about 1 hour with a high-speed mixer while heating to about 80 °C to make it into a slurry state, and then filtration and washing with water were repeated to remove salt and the solvent, and then dried at 80 °C for 24 hours to obtain a colorant (A-4).

[0232] (Colorant (A-5)) 100 parts of CI Pigment Green 58 (DIC Corporation's "FASTGEN GREEN A110"), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 6 hours. This mixture was added to 3000 parts of warm water and stirred for 1 hour while heating to 70°C until it became slurry-like. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight to obtain 97 parts of coloring agent (A-5).

[0233] (Coloring agent (A-6)) 500 parts of CI Pigment Green 36 (Lionol Green 6YK, manufactured by Toyo Color Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120°C for 4 hours. Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight to obtain 490 parts of coloring agent (A-6).

[0234] (Coloring agent (A-7)) 500 parts of CI Pigment Green 63 (OPTLION GREEN 8885, manufactured by Toyo Color Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120°C for 4 hours. Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight to obtain 490 parts of coloring agent (A-7).

[0235] (Coloring agent (A-8)) 100 parts of CI Pigment Blue 15:6 (Lionol Blue ES, manufactured by Toyo Color Co., Ltd.), 1000 parts of crushed salt, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50°C for 12 hours. This mixture was added to 3000 parts of warm water and stirred in a high-speed mixer for about 1 hour while heating to about 70°C to form a slurry. After repeated filtration and washing to remove salt and solvent, it was dried at 80°C for 24 hours to obtain coloring agent (A-8).

[0236] (Coloring agent (A-9)) 100 parts of CI Pigment Yellow 138 (BAS-F's "Pariotol Yellow K0961HD"), 800 parts of crushed salt, and 180 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded at 70°C for 4 hours. 3000 parts of this mixture were added to warm water and stirred in a high-speed mixer for about 1 hour while heating to approximately 80°C to form a slurry. After repeated filtration and washing to remove salt and solvent, the mixture was dried at 80°C for 24 hours to obtain coloring agent (A-9).

[0237] (Coloring agent (A-10)) 100 parts of CI Pigment Yellow 139 (BAS-F's "Irgafore Yellow 2R-CF"), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 10 hours. Next, this mixture was added to 3 liters of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 80°C to form a slurry. After repeated filtration and washing to remove sodium chloride and solvent, it was dried at 80°C for 24 hours to obtain the coloring agent (A-10).

[0238] (Coloring agent (A-11)) 100 parts of CI Pigment Yellow 150 (LANXESS "Yellow Pigment E4GN"), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 10 hours. Next, this mixture was added to 3 liters of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 80°C to form a slurry. After repeated filtration and washing to remove sodium chloride and solvent, it was dried at 80°C for 24 hours to obtain coloring agent (A-11).

[0239] (Coloring agent (A-12)) 500 parts of CI Pigment Yellow 185 (BAS-F's "Paliotoll Yellow D1155"), 500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded at 120°C for 8 hours. Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight to obtain the coloring agent (A-12). (Coloring agent (A-13)) 300 parts of dioxazine-based purple pigment PV23 (Toyo Color Co., Ltd. "Lionogen Violet RL") were added to 3000 parts of 96% sulfuric acid and stirred for 1 hour, then poured into water at 5°C. After stirring for 1 hour, the mixture was filtered, washed with warm water until the washing solution was neutral, and dried at 70°C. 120 parts of the resulting acid-pasted pigment, 5 parts of pigment derivative (b-2), 1500 parts of pulverized salt, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 70°C for 20 hours. This mixture was added to 5000 parts of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 70°C to form a slurry. After repeated filtration and washing with water to remove salt and solvent, the mixture was dried at 80°C for 24 hours to obtain finely milled pigment (A-13).

[0240] (Dye derivative (a)) The structures of each dye derivative used (a-1 to a-5) are shown below.

[0241] Pigment derivative (a-1) [Chem.]

[0242] Pigment derivative (a-2) [Chem.]

[0243] Pigment derivative (a-3) Pc represents a phthalocyanine skeleton. [Chem.]

[0244] Pigment derivative (a-4) [Chem.]

[0245] Pigment derivative (a-5) [Chem.]

[0246] (Production of dispersion resin (B1-1) solution) Into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 5 parts of methacrylic acid, 30 parts of methyl methacrylate, 50 parts of t-butyl methacrylate, 15 parts of ethyl acrylate, and 25 parts of propylene glycol monomethyl ether acetate were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50°C, and 6 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90°C, and a solution prepared by adding 0.05 part of 2,2'-azobisisobutyronitrile to 45 parts of propylene glycol monomethyl ether acetate was added while reacting for 7 hours. It was confirmed by solid content measurement that 95% had reacted. 9.5 parts of pyromellitic anhydride, 25 parts of propylene glycol monomethyl ether acetate, 25 parts of cyclohexanone, and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and the mixture was reacted at 100°C for 7 hours. After confirming that more than 98% of the acid anhydride had been half-esterified by measuring the acid value, the reaction was terminated. Propylene glycol monomethyl ether acetate was added to dilute the solution to a solid content of 40% by measuring the solid content, yielding a dispersion resin (B1-1) solution with an acid value of 70 mg KOH / g and a weight-average molecular weight (Mw) of 8500.

[0247] (Preparation of dispersion resin (B1-2~B1-7, B4-1) solution) Dispersed resin (B1-2~B1-7, B4-1) solutions were prepared in the same manner as the production of dispersed resin (B1-1) solution, except that the composition was changed as shown in Table 1.

[0248] [Table 1] However, the abbreviations used in the table are as follows: MAA: Methacrylic acid MMA: Methyl methacrylate t-BMA: t-butyl methacrylate BzMA: Benzyl methacrylate EA: Ethyl acrylate PMA: Pyromellitic anhydride

[0249] (Preparation of binder resin (B2-1) solution) In a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, 149.3 parts of propylene glycol monomethyl ether were added, and the mixture was stirred while purging with nitrogen, and the temperature was raised to 78°C. Next, a monomer mixture consisting of 50 parts of 2-(3,5-dimethylpyrazole-1-yl)carbonylaminoethyl methacrylate (Karenz MOI-BP, manufactured by Showa Denko Corporation), 11.0 parts of methacrylic acid, and 39 parts of methyl methacrylate, and 11.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) were added to 62.8 parts of propylene glycol monomethyl ether acetate and dissolved. These mixtures were then added dropwise to the flask from the dropping funnel. After the addition was complete, the mixture was stirred at 78°C for 3 hours to carry out the copolymerization reaction and produce a copolymer. Subsequently, propylene glycol monomethyl ether acetate was added to achieve a solid content of 20% to obtain a binder resin (B2-1) solution containing a blocked isocyanate group. The weight-average molecular weight (Mw) of the copolymer in the obtained polymer composition was 8,100, and the acid value was 80 KOH mg / g.

[0250] (Preparation of binder resin (B2-2~B2-8, B4-2) solutions) Binder resin (B2-2~B2-8, B4-2) solutions were prepared in the same manner as the production of binder resin (B2-1) solution, except that the composition was changed as shown in Table 2.

[0251] (Epoxy-containing resin (B3-1): Commercially available resins as shown below) 1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2,2'-bis(hydroxymethyl)-1-butanol [EHPE-3150 (manufactured by Daicel Corporation)] [Table 2] However, the abbreviations used in the table are as follows: MAA: Methacrylic acid MMA: Methyl methacrylate t-BMA: t-butyl methacrylate BzMA: Benzyl methacrylate DCPMA: Dicyclopentanyl methacrylate MOI-BP: 2-(3,5-dimethylpyrazole-1-yl)carbonylaminoethyl tacrylate

[0252] <Preparation of colored composition> (Manufacturing of coloring compositions) [Manufacturing Example 1] After stirring and mixing the following mixture until homogeneous, it was dispersed for 3 hours using 0.5 mm diameter zirconia beads in an Eiger mill (Eiger Japan's "Mini Model M-250 MKII"), and then filtered through a 5.0 μm pore size filter to prepare a colored composition (X-1) with a solid component content of 20% by mass. Pigment (A-1): 15.0 parts Dispersion resin (B4-1: 40% solids liquid): 12.5 parts Solvent (SM): 72.5 parts Furthermore, the solvent (SM) is prepared by mixing (S-1) to (S-6) below in the parts by mass indicated for each component. (S-1) PGMAc (boiling point 146℃) 20 parts (S-2) Cyclohexanone (boiling point 155°C) 20 parts (S-3)3-Ethoxypropionate ethyl (boiling point 169°C) 20 parts (S-4) Propylene glycol monomethyl ether (boiling point 121°C) 20 parts (S-5) Cyclohexanol acetate (boiling point 172°C) 10 parts (S-6) Dipropylene glycol methyl ether acetate (boiling point 188°C) 10 parts

[0253] [Manufacturing Examples 2-25] (Manufacturing of colored compositions (X-2~25)) As shown in Table 3, colored compositions (X-2 to X-25) were prepared in the same manner as colored composition (X-1), except that the composition of the colorant (A), pigment derivative (a), and resin (B) was changed.

[0254] [Table 3]

[0255] [Example 1] After stirring and mixing the mixture with the following composition until homogeneous, filter it through a 1 μm filter. A photosensitive colored composition (Y-1) was obtained. (Photosensitive coloring composition (Y-1)) The following raw materials were mixed and stirred, and filtered through a 1.0 μm pore size filter to obtain a photosensitive colored composition (Y-1). Coloring composition solution (X-2: solid content 20%): 65.0 parts Binder resin solution (B2-4: 40% solids): 10.0 parts Polymerizable compound (C-1): 2.0 parts Photopolymerization initiator (D): 0.4 parts Sensitizer (F): 0.1 part Thiol chain transfer agent (G): 0.4 parts Polymerization inhibitor (H): 0.05 parts UV absorber (I): 0.1 part Antioxidant (J): 0.1 part Leveling agent (K: 3% solids): 1.55 parts Storage stabilizer (L): 0.1 part Adhesion enhancer (M): 0.1 part Solvent (SM): 20.1 parts

[0256] [Examples 2-50, Comparative Examples 1-3] (Photosensitive coloring composition (Y-2~53)) Except for the changes in composition and amount (parts by mass) shown in Tables 4-1 to 4-4 and below, the mixtures were stirred and mixed uniformly in the same manner as for photosensitive colored composition (Y-1), and then filtered through a 1 μm filter to obtain photosensitive colored compositions (Y-2 to 53). In Example 50, a photosensitive colored composition (Y-50) was obtained using the following formulation. Coloring composition solution (X-2: solid content 20%): 54.0 parts Binder resin solution (B2-4: 40% solids): 10.0 parts Resin (B3-1): 1.0 part Polymerizable compound (C-1): 3.0 parts Photopolymerization initiator (D): 0.4 parts Sensitizer (F): 0.1 part Thiol chain transfer agent (G): 0.4 parts Polymerization inhibitor (H): 0.05 parts UV absorber (I): 0.1 part Antioxidant (J): 0.1 part Leveling agent (K: 3% solids): 1.55 parts Storage stabilizer (L): 0.1 part Adhesion enhancer (M): 0.1 part Solvent (SM): 29.1 parts

[0257] [Table 4-1]

[0258] [Table 4-2]

[0259] [Table 4-3]

[0260] [Table 4-4]

[0261] Details of each component used in Tables 4-1 to 4-4 are as follows.

[0262] <Polymerizable compound (C)> (C-1) Ethylene oxide 12 molar modified dipentaerythritol hexaacrylate [KAYARAD DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.)] (C-2) Trimethylolpropane EO modified tri(meth)acrylate [Aronix M-350 (manufactured by Toagosei Co., Ltd.)] (C-3) Tripropylene glycol diglycidyl ether acrylic acid adduct [Epoxy ester 200PA (manufactured by Kyoeisha Chemical Co., Ltd.)] (C-4) Glycerin diglycidyl ether acrylate adduct [Epoxy ester 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.)] (C-5) Dipentaerythritol penta and hexaacrylate [Aronix M-402 (manufactured by Toagosei Co., Ltd.)]

[0263] <Photopolymerization initiator (D)> (D1)2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one [Omnirad 907 (manufactured by IGM Resins)] (D2)2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [Omnirad 379EG (manufactured by IGM Resins)] (D3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [Omnirad TPO (manufactured by IGM Resins)] (D4)2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole [Biimidazole (manufactured by Kurogane Kasei Co., Ltd.)] (D5) p-dimethylaminoacetophenone [DMA (manufactured by Daikifine Co., Ltd.)] [Omnirad 2959 (manufactured by IGM Resins)] (D6) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide [Omnirad 819 (manufactured by IGM Resins)] The above (D1) to (D6) were mixed in equal amounts to form a photopolymerization initiator (DM).

[0264] (D-1) Oxime ester photopolymerization initiator having a carbazole skeleton as shown in formula (10) below Formula (10) [ka] (D-2) A mixture of oxime ester photopolymerization initiators having a carbazole skeleton, obtained by mixing equal amounts of the four photopolymerization initiators shown in formula (11) below. Formula (11) [ka]

[0265] (D-3) A mixture obtained by mixing equal amounts of three oxime ester photopolymerization initiators having the carbazole skeleton shown in formula (12) below. Formula (12) [ka]

[0266] (D-4) Oxime ester photopolymerization initiator having a diphenyl skeleton as shown in formula (13) below Formula (13) [ka]

[0267] (D-5) Oxime ester photopolymerization initiator having a diphenyl skeleton as shown in formula (14) below Formula (14) [ka]

[0268] (D-6) Oxime ester photopolymerization initiator having a fluorene skeleton as shown in formula (15) below Formula (15) [ka]

[0269] (D-7) Photopolymerization initiator having two oxime ester groups as shown in formula (16) below Formula (16) [ka]

[0270] <Sensitizer (F)> (F-1)2,4-Diethylthioxanthone [Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)] (F-2)4,4'-Bis(diethylamino)benzophenone [CHEMARK DEABP (manufactured by Chemark Chemical)] As described above, (F-1) and (F-2) were mixed in equal amounts to form the sensitizer (F).

[0271] <Thiol-based chain transfer agent (G)> (G-1) Trimethylolethantris(3-mercaptobutyrate) [TEMB (manufactured by Showa Denko)] (G-2) Trimethylolpropanetris(3-mercaptobutyrate) [TPMB (manufactured by Showa Denko)] (G-3) Pentaerythritol tetrakis(3-mercaptopropionate) [PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)] (G-4) Trimethylolpropanetris(3-mercaptopropionate) [TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)] (G-5) Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate [TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)] The above (G-1) to (G-5) were mixed in equal amounts to form the thiol-based chain transfer agent (G).

[0272] <Polymerization inhibitor (H)> (H-1)3-methylcatechol (H-2)methylhydroquinone (H-3)tert-butylhydroquinone The above (H-1) to (H-3) were mixed in equal amounts to form polymerization inhibitor (H).

[0273] <UV absorber (I)> (I-1)2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine[TINUVIN400 (manufactured by BASF Japan)] (I-2)2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol [TINUVIN900 (manufactured by BASF Japan)] As described above, (I-1) and (I-2) were mixed in equal amounts to obtain the ultraviolet absorber (I).

[0274] <Antioxidant (J)> (J-1) Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (J-2) 3,3'-Dioctadecyl Thiodipropanoate (J-3) Tris[2,4-di-(t)-butylphenyl]phosphine (J-4) Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (J-5) p-octylphenyl salicylate The above (J-1) to (J-5) were mixed in equal amounts to form antioxidant (J).

[0275] <Leveling agent (K)> One unit of "BYK-330" manufactured by Big Chemistry Co., Ltd. One unit of DIC's "Megafuck F-551", and A mixed solution prepared by dissolving 1 part of Kao Corporation's "Emulgen 103" in 97 parts of PGMAc.

[0276] <Storage stabilizer (L)> (L-1)2,6-bis(1,1-dimethylethyl)-4-methylphenol (manufactured by Honshu Chemical Industry Co., Ltd. as "BHT") (L-2) Triphenylphosphine (manufactured by Hokko Chemical Industry Co., Ltd. as "TPP") The above (L-1) and (L-2) were mixed in equal amounts to form storage stabilizer (L).

[0277] <Adhesion enhancer (M)> (M-1) "KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.)" (M-2)3-Glycidoxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (M-3)3-Methacryloxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (M-4)N-2-(aminoethyl)-3-aminopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (M-5)3-mercaptopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)] The above (M-1) to (M-5) were mixed in equal amounts to form adhesion improver (M).

[0278] <Solvent (S)> The solvent (SM) is prepared by mixing (S-1) to (S-6) below in the parts by mass indicated for each. (S-1) PGMAc (boiling point 146℃) 20 parts (S-2) Cyclohexanone (boiling point 155°C) 20 parts (S-3)3-Ethoxypropionate ethyl (boiling point 169°C) 20 parts (S-4) Propylene glycol monomethyl ether (boiling point 121°C) 20 parts (S-5) Cyclohexanol acetate (boiling point 172°C) 10 parts (S-6) Dipropylene glycol methyl ether acetate (boiling point 188°C) 10 parts

[0279] <Evaluation of photosensitive colored compositions> The obtained photosensitive colored compositions (Y-1 to 5346) were subjected to the following tests. The test results are shown in Table 5. The evaluation rank was on a 5-point scale, with higher numbers indicating better results.

[0280] <Developability> The obtained photosensitive composition was coated onto a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) by spin coating to a dry film thickness of 1.0 μm, and dried on a hot plate at 100°C for 1 minute. After the substrate cooled to room temperature, an i-line stepper (Canon Inc.) was used to irradiate it at an illuminance of 20 kW / m². 2 , exposure amount 5kJ / m 2 The substrate was then exposed to ultraviolet light through a photomask with a 100 μm wide stripe pattern. After cooling the substrate to room temperature, it was spray-developed at two levels, 40 seconds and 70 seconds, using an aqueous developer containing 0.12% nonionic surfactant and 0.3% tetramethylammonium hydroxide (TMAH) at 23°C. The substrate was then washed with deionized water and air-dried. The pattern was observed under an optical microscope to evaluate for development residue in unexposed areas and for any pattern defects. The evaluation criteria are as follows, with a score of 3 or higher indicating usability. 5: At a development time of 70 seconds, there was no development residue in the unexposed areas, and no pattern defects. 4. At a development time of 70 seconds, slight development residue occurred in the unexposed areas, and / or slight pattern defects occurred. 3: At a development time of 70 seconds, some development residue occurred in the unexposed areas, and / or some pattern defects occurred. 2: At a development time of 70 seconds, development residue occurred in the unexposed areas, and / or pattern defects occurred. 1: Pattern defects occurred during a development time of 40 seconds.

[0281] <Percentage of remaining film> The obtained photosensitive composition was coated onto a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) by spin coating to a dry film thickness of 1.0 μm, and dried on a hot plate at 100°C for 1 minute. After the substrate cooled to room temperature, an i-line stepper was used to illuminate it through a photomask with a 100 μm wide stripe pattern at an illumination of 20 kW / m². 2 , exposure amount 5kJ / m 2 The substrate was exposed to light. Then, the substrate was spray-developed for 70 seconds using an aqueous developer containing 0.12% nonionic surfactant and 0.3% tetramethylammonium hydroxide (TMAH) at 23°C. The film thickness was measured after washing with deionized water and air-drying. This thickness was defined as the post-development film thickness. Next, the substrate was post-baked on a hot plate at the temperatures shown in Table 6 for 5 minutes, and the film thickness was measured at the same location where the post-development film thickness was measured. This thickness was defined as the post-baked film thickness. The residual film percentage was calculated from the two film thicknesses using the following formula (17). The evaluation criteria were as follows, with a score of 3 or higher indicating that thinning was achieved. The film thickness was measured using a Dektak XT (Bruker Japan Co., Ltd.). Formula (17): Residual film percentage (%) = Post-baked film thickness ÷ Post-development film thickness × 100 5: Residual film rate less than 70% 4: Residual film rate 70% or more but less than 75% 3: Residual film rate 75% or more but less than 80% 2: Residual film rate 80% or more but less than 85% 1: Remaining film rate 85% or more

[0282] [Table 5] [Explanation of Symbols]

[0283] 10 LCD display device 11 Transparent substrate 12 TFT arrays 13 Transparent electrode layer 14. Orientation layer 15 Polarizing plates 21 Transparent substrate 22 Color Filters 23 Transparent electrode layer 24 orientation layer 25 Polarizing plates 30 backlight units 31 White LED light source LC LCD 100 Infrared Sensors 110 Photodetector 111 Infrared Absorption Filter 112 Color Filters 113 Infrared Absorption and Transmission Filter 114 Resin film 115 Microlenses 116 Flat membrane

Claims

1. A photosensitive colored composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), The resin (B) comprises a dispersion resin (B1) and / or a binder resin (B2), Either the dispersion resin (B1) and the binder resin (B2) contained in the resin (B) include a structural unit (b1) having a t-butyl group and / or a structural unit (b2) having a blocked isocyanate group. A photosensitive colored composition characterized in that the total content of the structural unit having the t-butyl group (b1) and the structural unit having the blocked isocyanate group (b2) is 30 to 70% by mass of 100% by mass of the resin (B).

2. The photosensitive colored composition according to claim 1, characterized in that the content of the constituent unit (b3) having a cyclic structure is 0 to 10% by mass of the binder resin (B2) in 100% by mass.

3. The photosensitive coloring composition according to claim 1, characterized in that the resin (B) further comprises a resin (B3) having an epoxy group.

4. The photosensitive resin composition according to claim 1, wherein the content of each solid component in 100% by mass of the total solid content of the photosensitive colored composition is as follows. Coloring agent (A): 40% by mass or more and less than 65% by mass Resin (B): 10% by mass or more and less than 50% by mass Polymerizable compound (C): 5% by mass or more and less than 25% by mass Photopolymerization initiator (D): 1% by mass or more and less than 5% by mass

5. A color filter having a filter segment formed by a photosensitive colored composition according to any one of claims 1 to 4.

6. A solid-state image sensor comprising the color filter described in claim 5.

7. A liquid crystal display device comprising the color filter described in claim 5.

8. A photosensitive resin composition according to any one of claims 1 to 4, The process involves applying the coating to a substrate to create a coating film, A step of exposing and developing the coated film to form a pattern, The process involves heat-treating the pattern at 240 to 300°C, A method for manufacturing a color filter that includes [the specified component].

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