TWI911219B - Color filter pigment composition, coloring composition, color filter, liquid crystal display device and solid-state imaging element - Google Patents

Abstract

The purpose of this invention is to provide a color filter pigment composition, a coloring composition, and a color filter formed using the coloring composition, which have excellent preservation stability and can form pixels with good brightness, contrast ratio, heat resistance, solvent resistance, and migration properties. The problem can be solved by a color filter pigment composition containing a diketopyrrolopyrrole pigment represented by general formula (1) and a diketopyrrolopyrrole pigment represented by general formula (2), wherein the mass ratio of general formula (1) to general formula (2) is 99.9:0.1 to 90.0:10.0.

Description

Color filter pigment composition, coloring composition, color filter, liquid crystal display device and solid-state imaging element

This invention relates to a colored composition for use in the manufacture of color filters for solid-state imaging devices, such as color liquid crystal displays, complementary metal oxide semiconductors (C-MOS), charge-coupled devices (CCDs), organic electroluminescence (EL) displays, and electronic paper, as well as a color filter comprising a filter segment formed using said colored composition.

In color filters used in color liquid crystal display devices, transparent electrodes for driving liquid crystals are typically formed by evaporation or sputtering, and then alignment films for aligning the liquid crystals in a certain direction are formed on the transparent electrodes. To fully obtain the performance of these transparent electrodes and alignment films, the formation process needs to be carried out at a high temperature, typically above 230°C, and the color filter requires heat resistance.

Contrast ratio and brightness are important quality requirements for color filters. Using a color filter with a low contrast ratio disrupts the polarization controlled by the liquid crystal, causing light leakage when light must be blocked (OFF state) and light attenuation when light must pass through (ON state), resulting in a blurry image. Therefore, increasing the contrast ratio is essential for achieving high-quality liquid crystal displays. Conversely, using a color filter with low brightness results in low light transmittance, leading to a dark image. To achieve a bright image, the number of backlights used as the light source needs to be increased. However, from the perspective of minimizing power consumption, increasing the brightness of color filters is becoming a trend.

As colorants used to form the red filter segment, C.I. Pigment Red 254, C.I. Pigment Red 291, C.I. Pigment Red 242, and C.I. Pigment Red 177 are commonly used. C.I. Pigment Red 254 or C.I. Pigment Red 291, as diketopyrrolopyrrole pigments, are pigments with particularly excellent brightness. However, in recent years, there has been a strong demand for higher contrast in color filters. Therefore, it is necessary to minimize the primary particle size of diketopyrrolopyrrole pigments as much as possible. However, micronized diketopyrrolopyrrole pigments have the property of easy crystallization growth due to their intermolecular hydrogen bonds, which causes the following problem: crystallization is caused during the heating step of forming color filters, resulting in the generation of foreign matter.

Patent 1 discloses a method to suppress crystallization during the heating process by combining C.I. Pigment Red 291 with a diketylpyrrolopyrrole pigment of a specific structure; however, further improvements are required in terms of brightness, contrast ratio, heat resistance, and solvent resistance. [Prior Art Documents] [Patent Documents]

[Patent Document 1] Japanese Patent Application Publication No. 2012-155232

[Problem Solved by the Invention] The purpose of this invention is to provide a color filter pigment composition, a coloring composition, and a color filter formed using said coloring composition that preserves pixels with excellent stability and can form good brightness, contrast ratio, heat resistance, solvent resistance, and migration properties. [Means for Solving the Problem]

Through repeated research, the inventors discovered that the aforementioned problem could be solved by using a pigment composition containing two diketolpyrrolopyrrole pigments with different structures in a specific mass ratio, thus completing this invention.

That is, the present invention relates to a pigment composition for a color filter, comprising a diketopyrrolopyrrole pigment represented by general formula (1) and a diketopyrrolopyrrole pigment represented by general formula (2), wherein the mass ratio of general formula (1) to general formula (2) is 99.9:0.1 to 90.0:10.0. General formula (1) [Chemical 1] [In general formula (1), X represents a halogen atom] General formula (2) [Chemistry 2] [In general formula (2), Y and Z are independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group with 1 to 20 carbon atoms that may have substituents, or a phenyl group that may have substituents; wherein at least one of Y and Z is an alkyl group with 3 to 18 carbon atoms]

Furthermore, the present invention relates to the pigment composition of the aforementioned color filter, which further contains pigment derivatives.

In addition, the present invention relates to a coloring composition for a color filter, which contains a colorant, a resin and a solvent, and the colorant contains the aforementioned pigment composition for a color filter.

In addition, the present invention relates to the color composition for the color filter, which further contains photopolymerizable monomers and/or photopolymerization initiators.

In addition, the present invention relates to a color filter, which includes a filter section formed by the color filter with a colored composition.

In addition, the present invention relates to a liquid crystal display device, which includes the aforementioned color filter.

Furthermore, this invention relates to a solid-state imaging element comprising the aforementioned color filter. [Effects of the Invention]

According to the present invention, a color filter pigment composition, a coloring composition, and a color filter formed using said coloring composition can be provided, which have excellent preservation stability and can form pixels with good brightness, contrast ratio, heat resistance, solvent resistance and migration.

The components of the color filter pigment composition and the coloring composition of the color filter constituting this invention will be described in detail below. Furthermore, "C.I." in this application refers to the Colour Index (C.I.). Furthermore, in the cases expressed as "(meth)acrylic," "(meth)acrylate," "(meth)acrylic acid," "(meth)acrylate," and "(meth)acryloxy," unless otherwise specified, they respectively represent "acrylic and/or methacrylic," "acrylic and/or methacrylic acid," "acrylic acid and/or methacrylic acid," "acrylate and/or methacrylate," and "acryloxy and/or methacryloxy."

<Color Filter Pigment Composition> The color filter pigment composition of this invention, containing diketopyrrolopyrrole pigments of general formulas (1) and (2) in a mass ratio ranging from 99.9:0.1 to 90.0:10.0, exhibits excellent brightness, contrast ratio, heat resistance, solvent resistance, and migration properties.

(Diketopyrrolopyrrole pigment of general formula (1) (A1)) A description will be given of the diketopyrrolopyrrole pigment (A1) represented by general formula (1), which is an essential component of the pigment composition of the present invention.

General formula (1) [Chemistry 3] [In general formula (1), X represents a halogen atom]

In X, fluorine, bromine, chlorine, and iodine can be listed as "halogen atoms," with chlorine and bromine being preferred from the viewpoint of lightness to contrast ratio. C.I. Pigment Red 254 and 291 are examples of diketopyrrolopyrrole pigments of general formula (1) that can be used in this invention, but are not limited to these. C.I. Pigment Red 291 is preferred from the viewpoint of lightness.

(Diketopyrrolopyrrole pigment of general formula (2) (A2)) A description will be given of the diketopyrrolopyrrole pigment (A2) represented by general formula (2), which is an essential component of the pigment composition of the present invention.

General formula (2) [Chemistry 4] [In general formula (2), Y and Z are independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group with 1 to 20 carbon atoms that may have substituents, or a phenyl group that may have substituents; wherein at least one of Y and Z is an alkyl group with 3 to 18 carbon atoms]

In Y and Z, fluorine, bromine, chlorine, and iodine can be listed as "halogen atoms".

In Y and Z, as "alkyl groups having 1 to 20 carbon atoms that may have substituents", there are unsubstituted or oxyalkyl groups with ether bonds, which can be linear or branched. Specifically, examples include methyl, ethyl, propyl, isopropyl, butyl, dibutyl, tributyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, octadecyl, eicosyl, 1,5-dimethylhexyl, 1,6-dimethylheptyl, 2-ethylhexyl, 2-methoxyethyl, 2-ethoxyethyl, 3-ethoxypropyl, polyoxyethyl, etc., but are not limited to these.

In Y and Z, "phenyl groups that may have substituents" can include phenyl groups having alkyl, trifluoromethyl, halogen, nitro, cyano, aminomethyl, sulfamoyl, or alkoxy groups having 1 to 4 carbon atoms. More specifically, phenyl, p-methylphenyl, 4-tert-butylphenyl, p-nitrophenyl, p-methoxyphenyl, p-chlorophenyl, 2,4-dichlorophenyl, 3-aminomethylphenyl, etc., can be listed, but are not limited to these.

At least one of Y and Z is an alkyl group having 3 to 18 carbon atoms. Examples of alkyl groups having 3 to 18 carbon atoms include propyl, isopropyl, butyl, dibutyl, tributyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, octadecyl, 1,5-dimethylhexyl, 1,6-dimethylheptyl, 2-ethylhexyl, cyclohexyl, isobornyl, etc., but are not limited to these. In terms of heat resistance (crystallization during processing), contrast ratio, and solvent resistance, the carbon number of the alkyl group is preferably 4 to 12, and more preferably 4 to 8. If the length of the alkyl group is long, the thermal aggregation caused by the diketopyrrolopyrrole pigment of general formula (1) can be suppressed by the stereotactic effect, and the contrast ratio or heat resistance becomes better. On the other hand, if the alkyl group is too long, the dispersion stability will be poor and the solubility in the solvent will be increased, thus tending to worsen the solvent resistance or migration.

The following are specific examples of diketopyrrolopyrrole pigments of general formula (2) that may be used in this invention, but are not limited to those.

[Chemistry 5]

In this invention, the total mass of diketopyrrolopyrrole pigments of general formula (1) and general formula (2) is used as the standard, and the content of diketopyrrolopyrrole pigments represented by general formula (2) is in the range of 0.1% by mass to 10% by mass. More preferably, it is in the range of 0.1% by mass to 5.0% by mass, and even more preferably, it is in the range of 0.1% by mass to 3.0% by mass.

If the proportion of the diketopyrrolopyrrole pigment of general formula (2) exceeds 10% by mass, an improved heat resistance (inhibition of crystallization) effect is obtained, but the excellent brightness of the diketopyrrolopyrrole pigment of general formula (1) is compromised, and the stability or solvent resistance also deteriorates. On the other hand, if the proportion of the diketopyrrolopyrrole pigment represented by general formula (2) is less than 0.1% by mass, the high contrast and heat resistance (inhibition of crystallization) are insufficient. In the case of insufficient inhibition of crystallization, light scattering is caused by crystalline foreign matter precipitated on the coating surface during the heating step, thereby causing a decrease in brightness and contrast ratio. Therefore, by using a coloring composition containing diketopyrrolopyrrole pigment of general formula (2) in the stated ratio, high brightness and high contrast ratio can be achieved, and the crystallization of diketopyrrolopyrrole pigment of general formula (1) can be suppressed even by using a heating step.

(Method for manufacturing diketopyrrolopyrrole pigments) Diketopyrrolopyrrole pigments represented by general formula (1) or general formula (2) can be manufactured using a succinate diester synthesis method. Specifically, 1 mole of succinate diester and 2 moles of any benzonitrile compound of general formula (50) or general formula (60) are condensed in an inert organic solvent such as pentanol, in the presence of an alkali metal or alkali metal alkoxide, at a high temperature of 80°C to 110°C, to generate an alkali metal salt of the diketopyrrolopyrrole compound. Then, the alkali metal salt of the diketopyrrolopyrrole compound is protonated using water, alcohol, acid, etc., thereby obtaining a diketopyrrolopyrrole pigment of general formula (1) or general formula (2). At this point, the size of the primary particle obtained can be controlled by the temperature, and the type, ratio, or amount of water, alcohol, or acid used in protonation. The method for manufacturing diketopyrrolopyrrole pigments represented by general formula (1) or general formula (2) is not limited to that method.

General formula (50) [Chemistry 6] [In general formula (50), X represents a halogen atom]

General formula (60) [Chemistry 7] [In general formula (60), Y and Z are independently a hydrogen atom, a halogen atom, a cyano group, a substitutable alkyl group, or a substitutable phenyl group, respectively; wherein at least one of Y and Z is a substitutable alkyl group having 3 to 18 carbon atoms.]

(Other Coloring Agents) In addition to the essential component of diketopyrrolopyrrole pigments represented by general formulas (1) and (2), the pigment and coloring compositions of this invention may also contain, arbitrarily selected, various existing pigments and dyes in combination as coloring agents. Representative pigments and dyes that can be used in this invention are listed below.

The red pigments that can be used in this invention include, for example, C.I. 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, 1 The following are examples of red dyes: 71, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 221, 224, 226, 242, 246, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 295, 296, etc., but are not specifically limited to these. Additionally, red dyes such as oxanthracene, anthocyanin, azo, and anthraquinone dyes can also be used. Specifically, examples include the salt-forming compounds of oxoanthracene acid dyes such as C.I. Acid Red 52, 87, 92, 289, and 338.

Orange pigments that can be used in this invention include, for example, C.I. Pigment Orange 38, 43 or 71, but are not specifically limited to those.

Yellow pigments that can be used in this invention include, for example, C.I. Pigment Yellow. yellow) 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 1 The following are examples of quinoline-based pigments as described in Japanese Patent No. 4993026, but are not specifically limited to them. Alternatively, quinoline, azo, methine, coumarin, and isoindoline yellow dyes can also be used.

The green pigments that can be used in this invention include, for example, those described in C.I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, Japanese Patent Application Publication No. 2008-19383, Japanese Patent Application Publication No. 2007-320986, Japanese Patent Application Publication No. 2004-70342, International Publication No. 2015/118720, and aluminum phthalocyanine pigments, but are not specifically limited to these. Additionally, triarylmethane-based, phthalocyanine-based, and squaric acid-based green dyes can also be used.

Blue pigments that can be used in this invention include, for example, C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, aluminum phthalocyanine pigments as described in Japanese Patent Application Publication No. 2004-333817 and Japanese Patent Application Publication No. 4893859, but are not specifically limited to these.

Purple pigments that can be used in this invention include, for example, C.I. pigment violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc., but are not specifically limited to these.

In the pigment composition of the present invention, inorganic pigments such as titanium dioxide, iron oxide, antimony pentoxide, zinc oxide, silicon dioxide and other metal oxides, cadmium sulfide, calcium carbonate, barium carbonate, barium sulfate, clay, talc, yellow lead, carbon black and other inorganic pigments can also be used.

When the pigment composition of the present invention is used in combination with other colorants, red or yellow pigments are mostly used in combination, in terms of their relationship to color properties. Specifically, as the combined red pigment, C.I. Pigment Red 177, C.I. Pigment Red 242, C.I. Pigment Red 269, and C.I. Pigment Red 296 are preferred from the viewpoint of color properties. As the yellow pigment, C.I. Pigment Yellow 138, or the quinoline ketone pigments, C.I. Pigment Yellow 139, C.I. Pigment Yellow 185, and C.I. Pigment Yellow 150 disclosed in Japanese Patent No. 4993026 are preferred from the viewpoint of color properties.

<Pigment Derivatives> The pigment composition or coloring composition of the present invention may contain pigment derivatives for the purpose of inhibiting pigment crystal growth and improving pigment dispersibility. As pigment derivatives usable in the present invention, known pigment derivatives having acidic, basic, or neutral groups in the organic pigment residue can be used. Examples include compounds having acidic functional groups such as sulfonyl, carboxyl, or phosphate groups and their amine salts; compounds having basic functional groups such as sulfonamide groups or tertiary amino groups at the terminal end; and compounds having neutral functional groups such as phenyl or orthophthalimide alkyl groups. As organic pigments, examples include: diketopyrrolopyrrole pigments; phthalocyanine pigments such as copper phthalocyanine, zinc phthalocyanine, aluminum phthalocyanine, halogenated copper phthalocyanine, halogenated zinc phthalocyanine, halogenated aluminum phthalocyanine, and metal-free phthalocyanine; anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthraquinone, flavin anthraquinone, anthraquinone succinate, tanstanone, pinanthraquinone, and violanthrone; quinacridone pigments; and dioxinone pigments. Oxazine pigments; perinone pigments; perylene pigments; thiazide-indigo pigments; triazine pigments; benzimidazole pigments; indole pigments such as benzisonidinole; isoindoline pigments; isoindolineone pigments; quinoline pigments; naphthol pigments; threne pigments; metal complex pigments; azo, diazo, polyazo, and other azo pigments, etc. More specifically, examples include Japanese Patent Application Publication Nos. 61-246261, 63-264674, 09-272812, 10-245501, 10-265697, 11-199796, 2001-172520, and 2001-220520. Japanese Patent Application Publication No. 2002-201377, Japanese Patent Application Publication No. 2003-165922, Japanese Patent Application Publication No. 2003-168208, Japanese Patent Application Publication No. 2003-171594, Japanese Patent Application Publication No. 2004-217842, Japanese Patent Application Publication No. 2005-213404, Japanese Patent Application Publication No. 2006-291194, Japanese Patent Application Publication No. 2007-079094, Japanese Patent Application Publication No. 200 Japanese Patent Publication No. 7-226161, Japanese Patent Publication No. 2007-314681, Japanese Patent Publication No. 2007-314785, Japanese Patent Publication No. 2008-31281, Japanese Patent Publication No. 2009-57478, WO2009/025325, WO2009/081930, Japanese Patent Publication No. 2011-162662, WO2011/052617, Japanese Patent Publication No. 20 The known pigment derivatives described in Japanese Patent Application Publication No. 12-172092, Japanese Patent Application Publication No. 2012-208329, Japanese Patent Application Publication No. 2012-226110, Japanese Patent Application Publication No. WO2012/102399, Japanese Patent Application Publication No. 2014-5439, Japanese Patent Application Publication No. WO2016/163351, Japanese Patent Application Publication No. 2017-156397, and Japanese Patent Application Publication No. 5753266, etc., may be used alone or in combination of two or more. Furthermore, in these documents, pigment derivatives are sometimes described as derivatives, pigment derivatives, pigment dispersants, or simply compounds, but the compounds having functional groups such as acidic, basic, or neutral groups in the organic pigment residues have the same meaning as pigment derivatives.

In the use of pigment derivatives in this invention, pigment derivatives having alkaline substituents are preferred in terms of significantly inhibiting the aggregation of pigments. Furthermore, from the viewpoint of hue or contrast ratio, organic pigment residues are preferably derived from diketopyrrolopyrrole pigments, anthraquinone pigments, thiamethoxam-indigo pigments, quinoline ketone pigments, or azo pigments.

<Micronization of Pigments> When the colorant used in the coloring composition of the present invention is a pigment, it is preferable to use a micronized pigment. The micronization method is not particularly limited; for example, wet milling, dry milling, or solvent extraction can be used. As illustrated in the present invention, salt milling, a type of wet milling, can be used for micronization. The average primary particle size of the pigment, determined by a transmission electron microscope (TEM), is preferably in the range of 5 nm to 90 nm. If the particle size is less than 5 nm, it is difficult to disperse in organic solvents; if the particle size is greater than 90 nm, a sufficient contrast ratio cannot be obtained. For this reason, a better average first-order particle diameter is in the range of 10 nm to 70 nm.

The so-called salt milling process involves the following steps: using batch or continuous mixing machines such as kneaders, two-rod roll mills, three-rod roll mills, ball mills, grinders, sand mills, and planetary mixers, the mixture of pigments, water-soluble inorganic salts, and water-soluble organic solvents is heated and mechanically mixed simultaneously. The water-soluble inorganic salts and solvents are then removed by washing with water. The water-soluble inorganic salts act as a crushing agent; during salt milling, the high hardness of the inorganic salts helps to break down the pigments. By optimizing the conditions during salt milling of pigments, pigments with very fine primary particle sizes, narrow distribution ranges, and sharp particle size distributions can be obtained.

As water-soluble inorganic salts, sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc., can be used. In terms of price, sodium chloride (table salt) is preferred. In terms of both processing and production efficiency, for 100 parts by weight of pigment, it is better to use 50 to 2000 parts by weight of water-soluble inorganic salts, and optimally 300 to 1000 parts by weight.

Water-soluble organic solvents serve to wet pigments and water-soluble inorganic salts. There are no particular limitations on organic solvents that dissolve (mix) in water but do not actually dissolve the inorganic salts used. However, because the temperature rises during salt milling, making the solvent prone to evaporation, high-boiling-point solvents with a boiling point above 120°C are preferred for safety reasons. Examples of solvents that can be used include: 2-methoxyethanol, 2-butoxyethanol, 2-(isopentoxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and liquid polypropylene glycol. For 100 parts by weight of pigment, a water-soluble organic solvent is preferably used from 5 to 1000 parts by weight, with the optimal use being 50 to 500 parts by weight.

During salt milling, pigment derivatives may be used to improve mixing efficiency. This is very effective for the micronization and granulation of pigments. In the micronization of the diketopyrrolopyrrole pigment composition used in this invention, the aforementioned pigment derivatives are preferred, but not limited to them. The amount of pigment derivative used is preferably such that it does not affect the hue, i.e., in the range of 0.5% to 30% by weight relative to 100% by weight of the pigment.

Additionally, resin may be added as needed during salt milling. There are no particular limitations on the type of resin used; natural resins, modified natural resins, synthetic resins, and synthetic resins modified from natural resins may be used. Preferably, the resin used is solid at room temperature and water-insoluble, and more preferably, partially soluble in the organic solvent. The amount of resin used is preferably in the range of 5 to 200 parts by weight relative to 100 parts by weight of pigment.

<Coloring Composition for Color Filters> The coloring composition for color filters of this invention comprises at least a colorant, resin, and solvent containing the colorant composition for color filters of this invention. Additionally, resin-based dispersants, photopolymerizable monomers for imparting photosensitivity, photopolymerization initiators, etc., may be used as needed.

<Resin-based Dispersants> The coloring composition of this invention can be used in conjunction with resin-based dispersants. The dispersant includes a colorant-affinity site having the property of adsorbing onto the added colorant or pigment derivative, and a site compatible with the colorant carrier, and functions to stabilize the dispersion of the colorant carrier by adsorption onto the added colorant. As a resin-type dispersant, specifically, polycarboxylic acid esters such as polyurethane and polyacrylate can be used; unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyurethane amide phosphates, polycarboxylic acid esters containing hydroxyl groups, or modified versions thereof; amides or their salts formed by the reaction of poly(lower alkylimides) with polyesters having free carboxyl groups, etc. Dispersants; water-soluble resins or water-soluble polymers such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone; polyester-based, modified polyacrylate-based, ethylene oxide/propylene oxide addition compounds, phosphate ester-based, etc., which may be used alone or in combination of two or more, but are not necessarily limited to these.

Among the resin-type dispersants, it is well known that graft copolymers containing nitrogen atoms can reduce the viscosity of the dispersion and exhibit a high contrast ratio with a small amount of addition; or acrylic block copolymers and carbamate polymeric dispersants containing nitrogen atoms that have functional groups such as tertiary amine groups, quaternary ammonium alkali, or nitrogen-containing heterocyclic rings in the side chains.

When resin-type dispersants are used in conjunction with the present invention, resin-type dispersants with acidic substituents are preferred. Among them, resin-type dispersants with aromatic carboxyl or phosphate groups are particularly effective in preventing the re-agglomeration of the dispersed colorant, and are therefore especially preferred. Resin-type dispersants having aromatic carboxyl groups include, but are not limited to, the resin-type dispersants described in Japanese Patent Application Publication No. WO2008/007776, Japanese Patent Application Publication No. 2008-029901, Japanese Patent Application Publication No. 2009-155406, Japanese Patent Application Publication No. 2009-155406, Japanese Patent Application Publication No. 2010-185934, and Japanese Patent Application Publication No. 2011-157416.

Relative to the total amount of colorant, the resin-type dispersant is preferably used in the range of 5 to 200 parts by weight, and from the viewpoint of film formation, it is even more preferably used in the range of 5 to 100 parts by weight.

<Resin> The resin, an essential component of the coloring composition of this invention, disperses, stains, or impregnates the colorant; examples include thermoplastic resins. Furthermore, when used in the form of an alkaline developing type coloring and anti-corrosion agent, it is preferable to use an alkaline-soluble vinyl resin copolymerized from vinyl unsaturated monomers containing acidic groups. Additionally, to further improve photosensitivity, an active energy line curing resin having vinyl unsaturated double bonds can also be used.

In particular, when an active energy line curing resin with ethylene-unsaturated double bonds on its side chains is used in alkaline developing coloring and anti-corrosion agents, the resin undergoes three-dimensional cross-linking during the formation of the coating through exposure using active energy lines. This fixes the colorant, improves heat resistance, and inhibits heat-induced fading of the colorant (deterioration of spectrophotometric properties). Furthermore, it also inhibits the aggregation and precipitation of colorant components during the developing process.

As a resin, it is preferably a resin with a spectral transmittance of 80% or more, and more preferably 95% or more, in all wavelength regions of the visible light region from 400 nm to 700 nm.

To ensure better dispersion of the colorant, the weight average molecular weight (Mw) of the resin is preferably in the range of 2,000 to 80,000, more preferably in the range of 3,000 to 40,000. Additionally, the number average molecular weight (Mn) is preferably in the range of 3,000 to 40,000, and the Mw/Mn ratio is preferably 10 or less.

When resins are used as photosensitive coloring components for color filters, the balance between the carboxyl groups, which act as adsorbent groups and alkali-soluble groups during development, and the aliphatic and aromatic groups, which act as affinity groups for the colorant carrier and solvent, is important for the dispersibility, penetration, development, and durability of the colorant. It is preferable to use resins with an acid value of 20 mgKOH/g to 300 mgKOH/g. If the acid value is less than 20 mgKOH/g, the following issues arise: poor solubility in the developing solution makes it difficult to form fine patterns. If it exceeds 300 mgKOH/g, the following issues arise: no fine patterns are left.

Regarding the resin, in terms of good film-forming properties and resistance, it is preferable to use an amount of 20 parts by weight or more relative to 100 parts by weight of the total colorant. In terms of high colorant concentration and good color characteristics, it is preferable to use an amount of 1000 parts by weight or less.

Examples of thermoplastic resins used in resins include: acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, ethylene resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclic rubber resins, cellulose resins, polyethylene (high-density polyethylene (HDPE), low-density polyethylene (LDPE)), polybutadiene, and polyimide resins. Among these, acrylic resins are preferred.

Ethylene-based alkali-soluble resins, which are copolymers of ethylene-containing unsaturated monomers with acidic groups, include, for example, resins with acidic groups such as carboxyl and sulfonyl groups. Specifically, alkali-soluble resins include: acrylic resins with acidic groups, α-olefin/maleic anhydride copolymers, styrene/styrene sulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, or isobutylene/maleic anhydride copolymers. Among these, resins selected from at least one of acrylic resins with acidic groups and styrene/styrene sulfonic acid copolymers, especially acrylic resins with acidic groups, have high heat resistance and transparency, and are therefore suitable for use.

As an active energy line curing resin having ethylene unsaturated double bonds, examples include resins incorporating unsaturated ethylene double bonds by means of (i) or (ii) shown below.

[Method (i)] Method (i) includes, for example, the following method: An addition reaction is performed on the carboxyl group of an unsaturated monocarboxylic acid having an unsaturated vinyl double bond to the side-chain epoxy group of a copolymer obtained by copolymerizing an unsaturated vinyl monomer having an epoxy group with one or more other monomers; the resulting hydroxyl group then reacts with a polycarboxylic acid anhydride, thereby introducing an unsaturated vinyl double bond and a carboxyl group.

As unsaturated vinyl monomers with epoxy groups, examples include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidyl oxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. These can be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monocarboxylic acid in the next step, glycidyl (meth)acrylate is preferred.

As unsaturated monocarboxylic acids, examples include (meth)acrylic acid, butenoic acid, ortho-vinylbenzoic acid, meta-vinylbenzoic acid, p-vinylbenzoic acid, and monocarboxylic acids with α-haloalkyl, alkoxy, halogen, nitro, or cyano substituents of (meth)acrylic acid. These can be used alone or in combination of two or more.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These can be used alone or in combination. The number of carboxyl groups can also be increased by using tricarboxylic anhydrides such as trimellitic anhydride, or tetracarboxylic dianhydrides such as pyromellitic dianhydride, to hydrolyze residual anhydride groups, as needed. Furthermore, as polybasic acid anhydrides, using tetrahydrophthalic anhydride or maleic anhydride, which have unsaturated vinyl double bonds, can further increase the number of unsaturated vinyl double bonds.

As a similar method to method (i), there is, for example, the following method: for part of the side chain carboxyl group of a copolymer obtained by copolymerizing an unsaturated vinyl monomer having a carboxyl group with one or more other monomers, an addition reaction is performed on an unsaturated vinyl monomer having an epoxy group, thereby introducing an unsaturated vinyl double bond and a carboxyl group.

[Method (ii)] Method (ii) includes reacting the isocyanate group of an unsaturated vinyl monomer having an isocyanate group with the side-chain hydroxyl groups of a copolymer obtained by copolymerizing an unsaturated vinyl monomer having a hydroxyl group with other unsaturated monocarboxylic acid monomers having carboxyl groups, or other monomers.

As unsaturated vinyl monomers with hydroxyl groups, examples include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate or 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate or 3-hydroxybutyl methacrylate or 4-hydroxybutyl methacrylate, glycerol methacrylate or cyclohexanediol mono(meth)acrylate, and other hydroxyalkyl methacrylates. These can be used alone or in combination of two or more. Alternatively, polyether mono(meth)acrylates formed by the addition polymerization of hydroxyalkyl methacrylates with ethylene oxide, propylene oxide, and/or butane, or poly(meth)acrylates formed by the addition polymerization of γ-valerol, ε-caprolactone, and/or 12-hydroxystearic acid, may be used. From the viewpoint of suppressing foreign matter in the coating, 2-hydroxyethyl methacrylate or glycerol (meth)acrylate is preferred.

Examples of unsaturated vinyl monomers having an isocyanate group include 2-(meth)acryloxyethyl isocyanate or 1,1-bis[(meth)acryloxy]ethyl isocyanate, but are not limited to these, and two or more may be used together.

<Thermosetting Compounds> The coloring composition of this invention may contain thermosetting compounds. Examples of thermosetting compounds include, for instance, epoxy compounds and/or resins, benzoguanamine compounds and/or resins, rosin-modified maleic acid compounds and/or resins, rosin-modified fumaric acid compounds and/or resins, melamine compounds and/or resins, urea compounds and/or resins, and phenolic compounds and/or resins, but this invention is not limited to these. When using thermosetting compounds in this invention, epoxy compounds are preferred from the viewpoint of heat resistance, solvent resistance, etc. As an epoxy compound, there are no particular limitations as long as it contains epoxy groups; it can be a low-molecular-weight compound or a high-molecular-weight compound such as a resin. For obtaining a coating with high crosslinking density, a multifunctional epoxy compound is particularly preferred.

The preferred weight-average molecular weight of the epoxide is 200 or more and 100,000 or less. More preferably, the molecular weight is 300 or more and 10,000 or less, and even more preferably, 500 or more and 5,000 or less.

As epoxides, bisphenol A type epoxides, bisphenol F type epoxides, cresol phenolic varnish type epoxides, biphenyl type epoxides, and alicyclic epoxides can all be used. Phenolic varnish type epoxides and alicyclic epoxides are preferred, and alicyclic epoxides are particularly preferred. The functional group is preferably difunctional or higher, and trifunctional or higher is more preferred in terms of excellent thermal crosslinking properties.

Examples of difunctional epoxy compounds include: EPICLON 830, 840, 850, 860, 1050, 2050, 3050, 4050, 7050, HM-091, and 101 manufactured by DIC; and Denacol EX-211, 212, 252, 711, and 721 manufactured by Nagase ChemteX.

Examples of multifunctional epoxy compounds with three or more functions include phenolic varnish-type epoxy compounds and EHPE3150 (manufactured by Daicel Chemical Co., Ltd.), a high-molecular-weight alicyclic main-chain epoxy compound. Specifically, examples of phenolic varnish-type epoxy compounds include: EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-4500, EOCN-4600, XD-1000, XD-1000-L, XD-1000-2L, NC-3000, NC-3000-H (manufactured by Nippon Kayaku Co., Ltd.); YDPN-638, YDCN-700-2, YDCN-700-3. YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-704, YDCN-704A (all manufactured by Nippon Steel Chemicals); N-660, N-665, N-670, N-673, N-680, N-690, N-695, N-665-EXP, N-672-EXP, N-655-EXP-S, N-662-EXP-S (all manufactured by DIC), etc. In addition, examples include Techmore VG3101 (manufactured by Printec), a trifunctional epoxide; and TETRAD-C and TETRAD-X (manufactured by Mitsubishi Gas Chemical), both tetrafunctional epoxides. Additionally, examples include Denacol EX-313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, and 622, manufactured by Nagase ChemteX. Furthermore, examples include JER1031S, 1302H60, 604, 630, and 630LSD, manufactured by Mitsubishi Chemical.

<Organic Solvent> To facilitate the following operation, the coloring composition of the present invention contains an organic solvent: the colorant is fully dispersed and impregnated in a colorant carrier, and then coated onto a substrate such as a glass substrate to form a colored film with a dried film thickness of 0.2 μm to 5 μm. The organic solvent is selected considering not only good coatability of the coloring composition but also the solubility and safety of each component of the coloring composition.

Examples of organic solvents include: ethyl lactate, benzyl alcohol, 1,3-butanediol, 1,3-butylene glycol, 1,3-butanediol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutylacetate, 3-methoxybutanol, 3-methoxybutylacetate, and 4-heptanone. m-Xylene, m-Diethylbenzene, N,N-Dimethylacetamide, N,N-Dimethylformamide, n-Butanol, n-Butylbenzene, n-Propyl acetate, Ortho-xylene, Ortho-Diethylbenzene, p-Diethylbenzene, Dibutylbenzene, Tertiary Butylbenzene, γ-Butyrolactone, Isobutanol, Isophorone, Ethylene glycol diethyl ether, Ethylene glycol dibutyl ether, Ethylene glycol monoisopropyl ether, Ethylene glycol monoethyl ether, Ethylene glycol monoethyl ether acetate, Ethylene glycol monotertyl ether, Ethylene glycol monobutyl ether, Ethylene glycol monobutyl ether acetate Ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether The solvents include: dipropylene glycol monomethyl ether, diacetone alcohol, glyceryl triacetate, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and diesters. These solvents can be used alone or in mixtures of two or more in any ratio as needed.

In terms of the good dispersibility, penetration and coatability of the colorant and the coloring composition, it is preferable to use ethylene glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, etc., alcohols such as benzyl alcohol, diacetone alcohol, 3-methoxybutanol, propylene glycol monomethyl ether, etc., or ketones such as cyclohexanone.

In addition, regarding the organic solvent, in order to adjust the coloring composition to an appropriate viscosity and form a colored film of uniform thickness as desired, it is preferable to use an amount of 500 to 4000 parts by weight of the colorant, rather than 100 parts by weight.

<Photopolymerizable Monomers> The coloring composition of this invention may also contain photopolymerizable monomers. Photopolymerizable monomers include monomers or oligomers that are cured by ultraviolet light or heat to form a transparent resin.

Monomers and oligomers that harden and form transparent resins by ultraviolet light or heat include, for example, methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, cyclohexyl methacrylate, β-carboxyethyl methacrylate, polyethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, triethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, and 1,6-hexanediol diglycidyl ether dimethacrylate. Bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecyl methacrylate, ester acrylates, hydroxymethylated melamine methacrylate, epoxy(meth)acrylates, carbamate acrylates, and various other acrylates, as well as methacrylates, methacrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylmethylamine, acrylonitrile, etc., but not necessarily limited to these. These photopolymerizable monomers can be used alone, or two or more can be mixed in any ratio as needed.

Based on the total mass of the colorant (100 parts by mass), the preferred amount of photopolymerizable monomer is 5 to 400 parts by mass, and from the perspective of photocurability and development, it is more preferably 10 to 300 parts by mass.

<Photopolymerization Initiator> A photopolymerization initiator may also be included in the colorimetric composition of the present invention for hardening the composition by ultraviolet irradiation and forming filter segments using photolithography. Furthermore, it can be prepared in the form of solvent-developed or alkali-developed photosensitive colorimetric compositions.

As photopolymerization initiators, the following acetophenone compounds can be used: 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone, or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one; benzoin, benzoin methyl Benzoin-based compounds, including benzoin ether, benzoin isopropyl ether, or benzyl dimethyl ketone; benzophenone-based compounds, including benzoylbenzoic acid, methyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, or 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone; thioanthraquinone-based compounds, including 2-chlorothioanthraquinone, 2-methylthioanthraquinone, isopropylthioanthraquinone, 2,4-diisopropylthioanthraquinone, or 2,4-diethylthioanthraquinone; and 2,4,6-trichloro-triazine. 2-Phenylacetyl-4,6-bis(trichloromethyl)-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-triazine, 2-piperyl-4,6-bis(trichloromethyl)-triazine, 2,4-bis(trichloromethyl)-6-styryl-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-triazine, 2-(4-methoxy-naphtho-1-yl)-4,6-bis(trichloromethyl)-triazine, 2,4-trichloromethyl-(piperyl)-6-triazine or 2,4-trichloromethyl-(4 Triazine compounds such as '-methoxystyryl'-6-triazine; oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)] or O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxy-naphthyl)ethylene)hydroxylamine; phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthroquinone, camphorquinone, and ethylanthraquinone; borate ester compounds; carbazole compounds; imidazole compounds; or titanium thiocenene compounds, etc. These photopolymerization initiators can be used alone, or two or more can be mixed in any ratio as needed.

The content of photopolymerization initiator is preferably 2 to 200 parts by weight relative to 100 parts by weight of colorant, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and development.

<Sensitizer> Furthermore, the coloring composition of this invention may contain a sensitizer. Examples of sensitizers include: unsaturated ketones represented by chalcone derivatives and dibenzalacetone; 1,2-dione derivatives represented by benzoin or camphorquinone; benzoin derivatives; fluorene derivatives; naphthoquinone derivatives; anthraquinone derivatives; oxanthracene derivatives; thioanthracene derivatives; oxanthracene ketone derivatives; thioanthracene ketone derivatives; coumarin derivatives; ketocoumarin derivatives; anthocyanin derivatives; benzoin derivatives; oxanthracene derivatives; polymethine pigments such as oxazine derivatives; acridine derivatives; arazine derivatives; thiazine derivatives; oxazine derivatives; indoline derivatives; azulene derivatives; azulenium derivatives; squaric acid lactone derivatives; and porphyrin derivatives. Tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalinoporphyrazine derivatives, naphthylphthalocyanine derivatives, subphthalocyanine derivatives, pyranone derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spiroxazine derivatives, thiospiropyran derivatives, metal aromatic hydrocarbon complexes, organorhodium complexes, or Michler's ketones. These sensitizers include ketone derivatives, bimidazole derivatives, α-acetylated esters, acetylated phosphine oxides, methyl phenyl glyoxylate, 9,10-phenanthrenequinone, ethyl anthraquinone, 4,4'-diethyl isophthalophenone, 3,3'-tetra(tert-butylperoxycarbonyl)benzophenone or 4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 4,4'-diethylaminobenzophenone, etc. These sensitizers can be used alone or in mixtures of two or more in any ratio as needed.

Furthermore, specifically, sensitizers described in "The Pigment Handbook" (1986, Kodan Co., Ltd.) edited by Nobuo Okawara et al., "Chemistry of Functional Pigments" (1981, CMC) edited by Nobuo Okawara et al., and "Special Functional Materials" (1986, CMC) edited by Tadazaburo Ikemori et al., can be listed, but are not limited to these. In addition, sensitizers that exhibit absorption of light in the ultraviolet to near-infrared region may also be included.

The content of sensitizer is preferably 3 to 60 parts by weight relative to 100 parts by weight of photopolymerization initiator contained in the coloring composition, and more preferably 5 to 50 parts by weight from the viewpoint of photocurability and development.

<Thiol Compounds> The coloring composition of this invention may contain thiol compounds that function as chain transfer agents. As thiol compounds, polyfunctional thiol compounds having two or more thiol groups are preferred, such as: hexanedithiol, decanedithiol, 1,4-butanediol dithiopropionate, 1,4-butanediol dithioglycolate, ethylene glycol dithioglycolate, ethylene glycol dithiopropionate, trihydroxymethylpropane trithioglycolate, trihydroxymethylpropane trithiopropionate, trihydroxymethylpropane tri(3-hydroxybutyrate), pentaerythritol tetrathioglycolate, pentaerythritol tetrathiopropionate, tri(2-hydroxyethyl)isocyanurate of trihydroxypropionate, 1,4-dimethylhydroxybenzene, 2,4,6-trihydroxy-triazine, 2-(N,N-dibutylamino)-4,6-dihydroxy-triazine, etc. These multifunctional thiols can be used alone, or two or more can be mixed in any ratio as needed.

Based on the total solid content (100% by mass) of the color composition of the color filter, the content of thiol compounds is preferably 0.1% to 30% by mass, more preferably 0.1% to 20% by mass. If the content of thiol compounds is less than 0.1% by mass, the effect of adding thiol compounds is insufficient; if it exceeds 30% by mass, the following situation occurs: the sensitivity is too high, and the resolution is reduced instead.

<Antioxidant> The coloring composition of this invention may contain an antioxidant. The antioxidant prevents the photopolymerization initiator or thermosetting compound contained in the coloring composition from oxidizing and yellowing due to the thermal steps during thermosetting or indium tin oxide (ITO) annealing, thereby improving the transmittance of the coating film. Therefore, by including an antioxidant, yellowing caused by oxidation during the heating process can be prevented, resulting in high coating film transmittance.

The "antioxidant" in this invention can be any compound that has ultraviolet absorption, free radical scavenging, or peroxide decomposition functions. Specifically, hindered phenolic, hindered amine, phosphorus, sulfur, benzotriazole, benzophenone, hydroxylamine, salicylate, and triazine compounds can be used as antioxidants.

Among these antioxidants, considering both the transmittance and sensitivity of the coating, the following are considered superior antioxidants: hindered phenolic antioxidants, hindered amine antioxidants, phosphorus-based antioxidants, or sulfur-based antioxidants. Furthermore, hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus-based antioxidants are preferred.

These antioxidants can be used alone, or two or more can be mixed in any ratio as needed.

Based on the solid content of the color composition used in color filters (100% by mass), and with an antioxidant content of 0.1% to 5.0% by mass, the brightness and sensitivity are good, and therefore even better.

<Amine Compounds> Furthermore, the coloring composition of this invention may contain amine compounds that have the function of reducing dissolved oxygen. Such amine compounds include: triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, ethyl 2-dimethylaminobenzoate, ethylhexyl 4-dimethylaminobenzoate, and N,N-dimethyl-p-toluidine, etc.

<Leveling Agent> To ensure good leveling of the composition on the transparent substrate, a leveling agent may be added to the colored composition of the present invention. Preferably, the leveling agent is a dimethylsiloxane having a polyether structure or a polyester structure in its main chain. Specific examples of dimethylsiloxanes having a polyether structure in their main chain include FZ-2122 manufactured by Toray Dow Corning and BYK-333 manufactured by BYK-Chemie. Specific examples of dimethylsiloxanes having a polyester structure in their main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie. It can also be used in combination with dimethylsiloxanes whose main chain has a polyether structure and dimethylsiloxanes whose main chain has a polyester structure. Based on the total mass of the colored components (100% by mass), the leveling agent content is generally preferred to be 0.003% to 0.5% by mass.

A particularly good leveling agent is a surfactant containing both hydrophobic and hydrophilic groups within its molecule. It is advantageous to have the characteristic of low water solubility despite containing hydrophilic groups, resulting in low surface tension reduction when added to the coloring composition. Furthermore, even with low surface tension reduction, it provides good wetting of the glass plate. It is preferable to use a leveling agent that sufficiently suppresses charge at an addition amount that does not cause coating defects due to foaming. Dimethylpolysiloxane, having polyepoxide units, is a preferred leveling agent with these desirable properties. As a polyoxyalkylene unit, it can contain polyethylene oxide units and polypropylene oxide units. Dimethyl polysiloxane can also contain both polyethylene oxide units and polypropylene oxide units.

Furthermore, the bonding morphology between the polyepoxide unit and the dimethylpolysiloxane can be any of the following: a pendant type where the polyepoxide unit is bonded to a repeating unit of the dimethylpolysiloxane; an end-modified type where the polyepoxide unit is bonded to the end of the dimethylpolysiloxane; or a linear block copolymer type where the polyepoxide unit is alternately and repeatedly bonded to the dimethylpolysiloxane. Dimethylpolysiloxanes containing polyepoxide units are commercially available from Toray Dow Corning Inc., such as FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, and FZ-2207, but are not limited to these.

Anionic, cationic, nonionic, or amphoteric surfactants can also be added to the leveling agent as an adjunct. Two or more surfactants can be used in combination. Anionic surfactants that can be added to the leveling agent as an adjunct include: polyoxyethylene alkyl ether sulfates, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymers, polyoxyethylene alkyl ether phosphates, etc.

Examples of cationic surfactants added to the leveling agent include alkyl quaternary ammonium salts or their ethylene oxide adducts. Examples of nonionic surfactants added to the leveling agent include: polyoxyethylene oleyl ethers, polyoxyethylene lauryl ethers, polyoxyethylene nonylphenyl ethers, polyoxyethylene alkyl ether phosphates, polyoxyethylene dehydrated sorbitan monostearate, polyethylene glycol monolaurate, and other polyoxyalkylene-based surfactants; alkyl betaine and other alkyl dimethylaminoacetic acid betaine, alkyl imidazoline and other amphoteric surfactants; and fluorinated or silicone-based surfactants.

<Curing Agent, Curing Accelerator> Furthermore, to assist in the curing of thermosetting resins, the coloring composition of this invention may also include a curing agent, a curing accelerator, etc., as needed. Effective curing agents include phenolic resins, amine compounds, acid anhydrides, reactive esters, carboxylic acid compounds, sulfonic acid compounds, etc., but are not particularly limited to these; any curing agent that can react with thermosetting resins may be used. Among these, compounds having two or more phenolic hydroxyl groups per molecule and amine curing agents are preferably listed. As the hardening accelerator, for example, the following can be used: amine compounds (e.g., dicyandiamine, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salts (e.g., triethylbenzylammonium chloride, etc.), block isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivative dicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazolium, 2-ethylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 4-phenylimidazolium, 1-cyano- Examples of compounds include ethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, phosphorus compounds (e.g., triphenylphosphine), guanidine compounds (e.g., melamine, guanidine, acetoguanamine, benzoguanamine), and S-triazine derivatives (e.g., 2,4-diamino-6-methacryloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanate adduct, 2,4-diamino-6-methacryloxyethyl-S-triazine isocyanate adduct, etc.). These can be used individually or in combination. The content of the curing accelerator is preferably 0.01 to 15 parts by weight relative to 100 parts by weight of the thermosetting resin.

<Other Additives> To stabilize viscosity over time, the coloring composition of this invention may contain a storage stabilizer. Additionally, to improve adhesion to the transparent substrate, adhesion enhancers such as silane coupling agents may be included.

Examples of storage stabilizers include: quaternary ammonium chlorides such as benzyltrimethylammonium chloride and diethylhydroxylamine; organic acids such as lactic acid and oxalic acid and their methyl ethers; tributylhydroquinone; organophosphines such as tetraethylphosphine and tetraphenylphosphine; and phosphites. For every 100 parts by weight of the colorant, the storage stabilizer can be used in amounts ranging from 0.1 to 10 parts by weight.

Examples of seal-enhancing agents include: vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, vinyltrimethoxysilane, and other vinyl silanes; γ-methacrylic silanes such as γ-methacryloxypropyltrimethoxysilane; β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. Epoxysilanes such as triethoxysilanes; aminosilanes such as N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane; and thiosilanes such as γ-thiopropyltrimethoxysilane and γ-thiopropyltriethoxysilane. For every 100 parts by weight of the colorant in the coloring composition, the adhesion enhancer can be used in amounts of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight.

<Method for Manufacturing the Colored Composition> The colored composition of the present invention is preferably manufactured by using various dispersion methods such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, a ring bead mill, or a grinder to finely disperse the colorant together with a pigment derivative or a resin-based dispersant and other dispersing aids in a resin or other colorant carrier and/or a solvent (colorant dispersion). In this case, two or more colorants can be simultaneously dispersed in the colorant carrier, or the products obtained from dispersing separately in the colorant carrier can be mixed. When the colorants, such as dyes, have high solubility—specifically, if they dissolve easily in the solvent used, dissolve by stirring, and no foreign matter is detected—then fine dispersion as described above is unnecessary.

Additionally, when used as a photosensitive coloring composition (anti-corrosion agent), it can be prepared as a solvent-developing or alkaline-developing coloring composition. The solvent-developing or alkaline-developing coloring composition can be prepared by mixing the aforementioned colorant dispersion, photopolymerizable monomer and/or photopolymerization initiator, solvent as needed, other dispersing agents, and additives. The photopolymerization initiator can be added during the preparation of the coloring composition or added later to the prepared coloring composition.

<Dispersion Aids> When dispersing colorants in a colorant carrier, dispersion aids such as pigment derivatives, resin-based dispersants, and surfactants are suitable. Dispersion aids are highly effective in preventing the re-aggregation of the dispersed colorant; therefore, coloring compositions formed by dispersing colorants in a colorant carrier using dispersion aids exhibit good stability in lightness and viscosity. Regarding pigment derivatives and resin-based dispersants, as described above.

<Surfactants> Examples of surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium stearate, sodium alkylnaphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymers, and anionic surfactants such as polyoxyethylene alkyl ether phosphates; polyoxyethylene oleyl... Nonionic surfactants include ethers, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene dehydrated sorbitan monostearate, and polyethylene glycol monolaurate; cationic surfactants include alkyl quaternary ammonium salts or their ethylene oxide adducts; amphoteric surfactants include alkyl betaines such as alkyl dimethylaminoacetic acid betaine, and alkyl imidazolines. These can be used alone or in combination of two or more, but are not necessarily limited to these.

When adding surfactant, the amount is preferably 0.1 to 55 parts by weight, and more preferably 0.1 to 45 parts by weight, relative to 100 parts by weight of colorant. If the amount of surfactant is less than 0.1 parts by weight, it is difficult to obtain the desired effect. If the amount is greater than 55 parts by weight, the following situation arises: the excess dispersant affects dispersion.

<Removal of Coarse Particles> The colored composition of this invention preferably removes coarse particles of 5 μm or larger, more preferably 1 μm or larger, and even more preferably 0.5 μm or larger, as well as any mixed dust, through centrifugal separation, filtration using a sintering filter or a membrane filter. As mentioned above, the colored composition preferably does not substantially contain particles larger than 0.5 μm. More preferably, particles smaller than 0.3 μm are preferred.

<Color Filter> Next, the color filter of the present invention will be described. The color filter of the present invention includes a red filter segment, a green filter segment, and a blue filter segment. Furthermore, the color filter may also include a magenta filter segment, a cyan filter segment, and a yellow filter segment. Regarding the color filter of the present invention, at least one of the red filter segments is formed from the pigment composition of the present invention.

<Manufacturing Method of Color Filters> Color filters can be manufactured using printing or photolithography. Regarding the formation of filter segments using the printing method, patterns can be achieved simply by repeatedly printing and drying the colored components prepared as printing inks. Therefore, this method is low-cost and highly producible for color filter manufacturing. Furthermore, advancements in printing technology have enabled the printing of fine patterns with high dimensional accuracy and smoothness. For printing, it is preferable to design components that prevent the ink from drying and curing on the printing plate or blanket. Additionally, controlling the flowability of the ink on the printing press is important; dispersants or extender pigments can be used to adjust the ink viscosity.

When the filter segment is formed using photolithography, the colored composition prepared as the solvent-developing or alkaline-developing colored corrosion inhibitor is coated onto a transparent substrate with a dried film thickness of 0.2 μm to 5 μm using coating methods such as spray coating, spin coating, slit coating, or roller coating. The dried film, as needed, is then exposed (irradiated) by a mask with a predetermined pattern, positioned in contact with or without contact with the film. Then, the uncured areas are removed by immersion in a solvent or alkaline developer, or by spraying the developer with a spray gun, to form the desired pattern. The same process is repeated for other colors to produce color filters. Furthermore, heating can be applied as needed to promote the polymerization of the colored anti-corrosion agent. Using photolithography, color filters with higher precision than those produced by the printing method can be manufactured.

During development, aqueous solutions of sodium carbonate, sodium hydroxide, etc., or organic bases such as dimethylbenzylamine and triethanolamine can be used as alkaline developing solutions. Additionally, defoamers or surfactants can be added to the developing solution. Furthermore, to improve exposure sensitivity, after the aforementioned coloring and corrosion-resistant agent has been applied and dried, a water-soluble or alkaline-water-soluble resin, such as polyvinyl alcohol or water-soluble acrylic resin, can be applied and dried to form a film that prevents polymerization inhibition caused by oxygen, before exposure.

In addition to the methods described above, the color filter of the present invention can also be manufactured using electrodeposition, transfer printing, inkjet printing, etc., and the coloring composition of the present invention can be used in any of these methods. Furthermore, the electrodeposition method involves depositing color filter segments onto a transparent conductive film formed on a substrate by electrophoresis of colloidal particles, thereby manufacturing a color filter. Additionally, the transfer printing method involves pre-forming filter segments on the surface of a peelable transfer substrate and transferring these filter segments onto the desired substrate.

A black matrix can be pre-formed before forming the color filter segments on the transparent or reflective substrate. The black matrix can be a multilayer film of chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film with dispersed light-shielding agents, but is not limited to these. Alternatively, a thin-film transistor (TFT) can be pre-formed on the transparent or reflective substrate before forming the color filter segments. Furthermore, an outer coating or a transparent conductive film can be formed on the color filter of this invention as needed.

<Liquid Crystal Display Device> The liquid crystal display device of this invention includes the color filter of this invention. The color filter of this invention is bonded to an opposing substrate using a sealant. Liquid crystal is injected through an injection port provided in a sealed portion. The injection port is then sealed, and a polarizing film or retardation film is bonded to the outer side of the substrate as needed, thereby manufacturing a color liquid crystal display device. This color liquid crystal display device can be used in liquid crystal display modes that use color filters for colorization, such as Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertical Alignment (VA), and Optically Compensated Bend (OCB).

<Flat-State Imaging Element> The solid-state imaging element of this invention includes the color filter of this invention. The structure of the solid-state imaging element of this invention includes the color filter used in the solid-state imaging element. There are no particular limitations on the structure, as long as it is a structure that enables the solid-state imaging element to perform its function; for example, the following structures can be listed. The structure is as follows: A substrate has multiple photodiodes constituting a light-receiving area of a solid-state imaging element (CCD sensor, CMOS sensor, organic CMOS sensor, etc.) and a transmitting electrode containing polysilicon or the like. A light-shielding film containing tungsten or the like is provided on the photodiodes and the transmitting electrode, opening only to the light-receiving portion of the photodiodes. A device protective film containing silicon nitride or the like is formed on the light-shielding film, covering the entire surface of the film and the light-receiving portion of the photodiodes. A color filter for a solid-state imaging element according to the present invention is provided on the device protective film. Furthermore, the structure may also include a light-concentrating unit (e.g., a microlens; hereinafter the same) on the protective film of the device and below the color filter (on the side near the substrate), or a structure with a light-concentrating unit on the color filter. Furthermore, the organic CMOS sensor is composed of a panchromatic photosensitive organic photoelectric conversion film as a photoelectric conversion layer and a CMOS signal readout substrate. It is a hybrid structure consisting of two layers: an organic material that carries and converts light into an electrical signal, and an inorganic material that conducts the electrical signal to the outside. In principle, this allows for an aperture ratio of 100% relative to the incident light. Organic photoelectric conversion films are structurally free continuous films that can be laid on CMOS signal readout substrates, thus eliminating the need for expensive microfabrication processes and making them suitable for miniaturizing filter sections. The configuration of color filter sections is not particularly limited and can be achieved using known methods.

In addition to color liquid crystal displays, the color filter of this invention can also be used in the manufacture of color imaging elements, organic EL displays, electronic paper, etc. [Example]

The present invention will now be described based on embodiments, but the invention is not limited thereto. Furthermore, in the embodiments, "parts" and "%" represent "parts by mass" and "% by mass," respectively. Additionally, the average primary particle size of the pigment and the weight-average molecular weight (Mw) of the resin are as follows.

(Average First-Order Particle Size of Pigments) The average first-order particle size of pigments is determined by directly measuring the size of the first-order particles using a transmission electron microscope (TEM) and the electron microscope images. Specifically, the minor and major axes of the first-order particles of each pigment are measured, and the average is taken as the particle size of that pigment's first-order particle. Next, for more than 100 pigment particles, the volume (mass) of each particle is calculated approximately as a cube with the calculated particle size, and the volume-averaged particle size is taken as the average first-order particle size.

(Weight-average molecular weight (Mw) of the resin) The weight-average molecular weight (Mw) of the resin is the converted weight-average molecular weight (Mw) of polystyrene, determined using a TSKgel column (manufactured by Tosoh Corporation) and a gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector, using tetrahydrofuran (THF) as the developing solvent.

Next, the manufacturing methods of the resin solutions, resin-type dispersant solutions, pigment derivatives, and colorants used in the embodiments and comparative examples will be explained.

<Preparation of Acrylic Resin Solution> (Preparation of Acrylic Resin Solution 1) 100 parts of propylene glycol monomethyl ether acetate were placed in a reaction vessel equipped with a thermometer, coolant, nitrogen inlet tube, and stirrer in a separable four-necked flask. While injecting nitrogen into the vessel, the mixture was heated to 120°C. At this temperature, a mixture of 16.2 parts styrene, 35.5 parts glycidyl methacrylate, 25.0 parts dicyclopentyl methacrylate, 16 parts methyl methacrylate, and 1.0 part azobisisobutyronitrile (AIB) as a catalyst for this stage of the reaction was added dropwise via a dropper over 2.5 hours to carry out the polymerization reaction. Next, the air in the flask was replaced, and 17.0 parts of acrylic acid, 0.3 parts of tri-dimethylaminomethylphenol and 0.3 parts of hydroquinone (catalysts required for the precursor reaction in this stage) were added. The reaction was carried out at 120°C for 5 hours to obtain a resin solution with a weight average molecular weight of approximately 12,000 (determined using GPC). The added acrylic acid forms an ester bond with the epoxy terminus of the glycidyl methacrylate unit, thus no carboxyl groups are generated in the resin structure. Then, 30.4 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine (catalysts required for the precursor reaction in this stage) were added, and the reaction was carried out at 120°C for 4 hours. The added tetrahydrophthalic anhydride undergoes cleavage at its carboxylic anhydride site, resulting in two carboxyl groups. One of these carboxyl groups forms an ester bond with a hydroxyl group in the resin structure, while the other forms a carboxyl terminus. Propylene glycol monomethyl ether acetate is added at a non-volatile content of 20% to obtain acrylic resin solution 1.

(Preparation of Acrylic Resin Solution 2) 100 parts by weight of propylene glycol monomethyl ether acetate were added to a separable flask equipped with a cooler, purged with nitrogen, and then heated to 90°C. Meanwhile, in dropping tank 1, 10.0 parts of dimethyl-2,2'-[oxybis(methylenebis)]-2-propionate, 40.1 parts of cyclohexyl methacrylate, 24.2 parts of tetrahydrofurfuryl methacrylate, 24.7 parts of methacrylic acid, 2.0 parts of tributyl peroxide-2-ethylhexanoate, and 80 parts of propylene glycol monomethyl ether acetate were mixed. In addition, in dropping tank 2, 3.1 parts of β-propionic acid and 6 parts of propylene glycol monomethyl ether acetate were mixed. While maintaining the reaction temperature at 90°C, the solution was added dropwise from dropping tank 1 and dropping tank 2 at a constant rate for 2.5 hours. After the addition was completed, the temperature was maintained at 90°C for 30 minutes, and then 0.5 parts of tributyl peroxide-2-ethylhexanoate were added, and the reaction continued at 90°C for another 30 minutes. Then, the reaction temperature was raised to 115°C, and the reaction continued for 1.5 hours. After temporarily cooling to room temperature, 24.7 parts of glycidyl methacrylate, 0.038 parts of 6-tert-butyl-2,4-dimethylphenol, and 0.38 parts of dimethylbenzylamine were added. While bubbling a nitrogen-air mixture adjusted to an oxygen concentration of 7%, the temperature was raised to 110°C, and the reaction was carried out for 6 hours. Then, the temperature was raised to 115℃ and the reaction was carried out for 2 hours to complete the reaction. After cooling to room temperature, approximately 2 g of the resin solution was sampled and dried at 180℃ for 20 minutes. The non-volatile components were determined. Propylene glycol monomethyl ether acetate was added to the previously synthesized resin solution to achieve a non-volatile component concentration of 20% by mass, thereby obtaining acrylic resin solution 2. The weight-average molecular weight of the resin was 9000, and the acid value per unit solid component was 70 mgKOH/g.

<Preparation of Resin-Based Dispersant Solution> (Preparation of Resin-Based Dispersant Solution 1) 1.0 parts by weight of 2,2'-azobisisobutyronitrile (AIBN) and 186 parts by weight of propylene glycol monomethyl ether acetate were added to a flask including a cooler and a stirrer. Then, 27 parts by weight of methyl methacrylate, 27 parts by weight of butyl methacrylate, 21 parts by weight of 2-ethylhexyl methacrylate, 18 parts by weight of benzyl methacrylate, and 3.6 parts by weight of cumyl dithiobenzoate were added, and the mixture was purged with nitrogen for 30 minutes. Then, the mixture was slowly stirred, and the temperature of the reaction solution was raised to 60°C and maintained at this temperature for 24 hours to carry out living radical polymerization. Next, a solution was added to the reaction solution containing 1.0 parts by weight of AIBN and 35 parts by weight of dimethylaminoethyl methacrylate dissolved in 70 parts by weight of propylene glycol monomethyl ether acetate, and subjected to nitrogen replacement for 30 minutes. This solution was then subjected to living radical polymerization at 60°C for 24 hours to obtain a block copolymer solution. 25 parts by weight of benzyl chloride and 50 parts by weight of propylene glycol monomethyl ether were added to the obtained block copolymer solution, and the reaction was carried out at 80°C for 2 hours, adjusting the solid content to 40% to obtain resin-type dispersant solution 1. Resin-type dispersant 1 is a block copolymer comprising block A and block B. Block A has repeating units derived from methacryloyloxyethyl benzyl dimethyl ammonium chloride and dimethylaminoethyl methacrylate, and block B has repeating units derived from methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and benzyl methacrylate. According to proton nuclear magnetic resonance (NMR) measurements, the copolymerization ratio of each repeating unit is methacryloyloxyethyl benzyl dimethyl ammonium chloride/dimethylaminoethyl methacrylate/methyl methacrylate/butyl methacrylate/2-ethylhexyl methacrylate/benzyl methacrylate = 34/4/18/18/14/12 (mass ratio).

(Preparation of Resin-based Dispersant Solution 2) 6.5 parts of 3-pyromellitic-1,2-propanediol, 4.0 parts of pyromellitic anhydride, 0.01 parts of dimethylbenzylamine, and 41.8 parts of methoxypropyl acetate were charged into a reaction vessel including a gas inlet pipe, thermometer, condenser, and stirrer. Nitrogen gas was used for purging. The reaction vessel was heated to 100°C and reacted for 7 hours. The acid value was determined to confirm that over 98% of the anhydride had undergone semi-esterification. The system was then cooled to 70°C, and 67 parts of methyl methacrylate, 5.0 parts of methacrylic acid, 16.0 parts of tributyl acrylate, 10.0 parts of (3-ethyloxacyclobutane-3-yl)methyl methacrylate, and 2.0 parts of ethyl acrylate were added. Additionally, 0.10 parts of 2,2'-azobisisobutyronitrile and 60.0 parts of methoxypropyl acetate were added, and the reaction was allowed to proceed for 10 hours. Solid composition analysis confirmed that 95% polymerization had occurred. The reaction was then terminated, yielding a polyester dispersant with an acid value of 47 mgKOH/g and a number average molecular weight of 15000. Methoxypropyl acetate was added to the solution to achieve a solid content of 40%, thereby obtaining a resin-type dispersant solution 2 with aromatic carboxyl groups.

(Preparation of Resin-Based Dispersant Solution 3) Disperbyk-110 (52% solids) manufactured by BYK-Chemie was used as resin-based dispersant solution 3.

<Manufacturing of Pigment Derivatives>

(Preparation of Pigment Derivative 1) Pigment derivative 1, as represented by the following structure, was prepared by referring to Synthesis Example 3 of Japanese Patent No. 5748665. [Chemical 8] Pigment Derivative 1

(Preparation of Pigment Derivative 2) The organic pigment derivative (D4) disclosed in Japanese Patent Application Publication 2010-163500 is used as pigment derivative 2. [Chemical 9] Pigment Derivative 2

(Preparation of Pigment Derivative 3) Pigment derivative 3 was obtained according to the synthetic method described in Japanese Patent Application Publication No. 2004-067715. [Chemical 10]

(Preparation of Pigment Derivative 4) Pigment derivative 4 with the structure shown below was prepared by referring to Manufacturing Example 6 of Japanese Patent No. 4983061. [Chemical 11] Pigment Derivative 4

<Manufacturing Method of Pigment> <Manufacturing of Diketolpyrrolopyrrole Pigment of General Formula (2)> (Manufacturing of Diketolpyrrolopyrrole Pigment (A2-1)) Under a nitrogen atmosphere, 200 parts of dehydrated tripentanol and 140 parts of sodium tripentyl alkoxide, dehydrated by molecular sieve, were added to a stainless steel reaction vessel equipped with a reflux tube. The mixture was stirred and heated to 100°C to prepare an alkoxide solution. Meanwhile, 88 parts of diisopropyl succinate and 122.5 parts of 4-propylbenzonitrile were added to a glass flask. The mixture was stirred and heated to 90°C to dissolve the substances, thus preparing a solution of the mixture. The heated solution of the mixture was added dropwise over a constant rate for 2 hours while being vigorously stirred. After the addition was completed, the mixture was heated and stirred at 90°C for another 2 hours to obtain an alkaline metal salt of diketopyrrolopyrrole compounds. Then, 600 parts methanol, 600 parts water, and 304 parts acetic acid were added to a reaction vessel with a glass jacket, and the mixture was cooled to -10°C. The cooled mixture was then gradually added in small amounts to a solution of the previously obtained alkaline metal salt of diketopyrrolopyrrole compounds, cooled to 75°C, while using a high-speed agitator with an 8 cm diameter shear disk rotating at 4000 rpm. Meanwhile, the mixture, containing methanol, acetic acid, and water, was kept at a temperature below -5°C while being cooled. The addition rate of the alkali metal salt of the diketopyrrolopyrrole compound at 75°C was adjusted, and the salt was added gradually in small amounts over approximately 120 minutes. After the addition of the alkali metal salt, red crystals precipitated, forming a red suspension. The resulting red suspension was then washed with an ultrafiltration device at 5°C, followed by filtration to obtain a red paste. The paste was redispersed in 3500 parts of methanol cooled to 0°C to prepare a suspension with a methanol concentration of approximately 90%. The suspension was stirred at 5°C for 3 hours to allow for particle granulation and washing during crystallization. Subsequently, the mixture was filtered using an ultrafiltration machine, and the resulting aqueous paste of the diketopyrrolopyrrole compound was dried at 80°C for 24 hours and then pulverized to obtain 129.6 parts of diketopyrrolopyrrole pigment of the following formula (A2-1).

[Chemistry 12] Equation (A2-1)

(Preparation of Diketopyrrolopyrrole Pigment (A2-2)) Except for replacing 122.5 parts of 4-propylbenzonitrile with 134.4 parts of 4-tert-butylbenzonitrile, the preparation was carried out in the same manner as that of diketopyrrolopyrrole pigment (A2-1), to obtain 135.4 parts of diketopyrrolopyrrole pigment represented by the following formula (A2-2).

[Chemistry 13] Equation (A2-2)

(Preparation of Diketopyrrolopyrrole Pigment (A2-3)) Except for replacing 122.5 parts of 4-propylbenzonitrile with 134.4 parts of 3-tert-butylbenzonitrile, the preparation was carried out in the same manner as that of diketopyrrolopyrrole pigment (A2-1), to obtain 133.4 parts of diketopyrrolopyrrole pigment represented by the following formula (A2-3).

[Chemistry 14] Equation (A2-3)

(Preparation of Diketopyrrolopyrrole Pigment (A2-4)) Except for replacing 122.5 parts of 4-propylbenzonitrile with 181.7 parts of 4-(2-ethylhexyl)benzonitrile, the preparation was carried out in the same manner as that of diketopyrrolopyrrole pigment (A2-1), yielding 173.3 parts of diketopyrrolopyrrole pigment represented by the following formula (A2-4).

[Chemistry 15] Equation (A2-4)

(Preparation of Diketopyrrolopyrrole Pigment (A2-5)) Except for replacing 122.5 parts of 4-propylbenzonitrile with 229.1 parts of 4-dodecylbenzonitrile, the preparation was carried out in the same manner as that of diketopyrrolopyrrole pigment (A2-1), yielding 206.2 parts of diketopyrrolopyrrole pigment represented by the following formula (A2-5).

[Chemistry 16] Equation (A2-5)

(Preparation of Diketopyrrolopyrrole Pigment (A2-6)) Except for replacing 122.5 parts of 4-propylbenzonitrile with 300.1 parts of 4-octadecylbenzonitrile, the preparation was carried out in the same manner as that of diketopyrrolopyrrole pigment (A2-1), yielding 238.8 parts of diketopyrrolopyrrole pigment represented by the following formula (A2-6).

[Chemistry 17] Equation (A2-6)

<Preparation of Other Diketolpyrrolopyrrole Pigments> (Preparation of Diketolpyrrolopyrrole Pigment (A3-1)) 220 parts of tripentanol were added to reaction vessel 1. While cooling in a water bath, 32 parts of 60% NaH were added and the mixture was heated and stirred at 90°C. Then, 100 parts of tripentanol, 99.2 parts of the compound of formula (700) synthesized by the method of "Tetrahedron", 58 (2002) 5547-5565, and 71.8 parts of the benzonitrile compound of formula (N-1) were dissolved in reaction vessel 2 by heating. The resulting mixture was then added dropwise to reaction vessel 1 over a period of 2 hours. The reaction was carried out at 120°C for 10 hours, then cooled to 60°C. 400 parts methanol and 50 parts acetic acid were added, followed by filtration and methanol washing to obtain 79.1 parts of diketopyrrolopyrrole pigment represented by formula (A3-1).

[Chemistry 18] Equation (700) Equation (N-1)

[Chemistry 19] Equation (A3-1)

<Preparation of Diketopyrrolopyrrole Pigment Composition> [Example 1] (Preparation of Diketopyrrolopyrrole Pigment Composition (P-1)) 97.0 parts of C.I. Pigment Red 254 (Cinilex DPP Red ST) from CINIC, 3.0 parts of formula (A2-1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were placed into a stainless steel 1-gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and mixed at 60°C for 12 hours. Next, the mixed materials were added to warm water and stirred for 1 hour while heating to approximately 80°C to form a slurry. The slurry was then filtered and washed to remove the salt and diethylene glycol. It was then dried at 80°C for 24 hours and pulverized to obtain 98.3 parts of diketopyrrolopyrrole pigment composition (P-1). The average primary particle size was 28.5 nm.

[Examples 2 to 14] (Preparation of Diketopyrrolopyrrole Pigment Compositions (P-2 to P-14)) Except for changing "97.0 parts of C.I. Pigment Red 254 (Cinilex DPP Red ST) and 3.0 parts of Formula (A2-1)" to the types and amounts of diketopyrrolopyrrole pigments and pigment derivatives listed in Table 1, the diketopyrrolopyrrole pigment compositions (P-2 to P-14) were obtained by the same method as in Example 1. The average primary particle size of each pigment composition is as shown in Table 1.

[Comparative Examples 1 to 6] (Preparation of Diketopyrrolopyrrole Pigment Compositions (P-S1 to P-S6)) Except for changing "97.0 parts of C.I. Pigment Red 254 (Cinilex DPP Red ST) and 3.0 parts of Formula (A2-1)" to the types and amounts of diketopyrrolopyrrole pigments and pigment derivatives listed in Table 1, diketopyrrolopyrrole pigment compositions (P-S1 to P-S6) were obtained by the same method as in Example 1. The average primary particle size of each pigment composition is as shown in Table 1.

[Table 1] Pigment composition Composition of diketopyrr ... Average first particle diameter (nm) Diketonepyrrolopyrrole pigment Pigment derivatives General formula (1) mass General formula (2) mass other mass Kind mass Implementation Example 1 P-1 PR254 97.0 Equation (A2-1) 3.0 - - - - 28.5 Implementation Example 2 P-2 PR254 97.0 Equation (A2-2) 3.0 - - - - 27.8 Implementation Example 3 P-3 PR254 97.0 Equation (A2-3) 3.0 - - - - 27.2 Implementation Example 4 P-4 PR254 97.0 Equation (A2-4) 3.0 - - - - 29.4 Implementation Example 5 P-5 PR254 97.0 Equation (A2-5) 3.0 - - - - 30.9 Implementation Example 6 P-6 PR254 97.0 Equation (A2-6) 3.0 - - - - 31.2 Implementation Example 7 P-7 PR254 99.9 Equation (A2-2) 0.1 - - - - 28.0 Implementation Example 8 P-8 PR254 99.5 Equation (A2-2) 0.5 - - - - 28.1 Implementation Example 9 P-9 PR254 99.0 Equation (A2-2) 1.0 - - - - 27.6 Implementation Example 10 P-10 PR254 95.0 Equation (A2-2) 5.0 - - - - 27.5 Implementation Example 11 P-11 PR254 90.0 Equation (A2-2) 10.0 - - - - 28.9 Implementation Example 12 P-12 PR254 99.0 Equation (A2-2) 1.0 - - Pigment Derivative 2 5.0 26.5 Implementation Example 13 P-13 PR291 99.0 Equation (A2-2) 1.0 - - - - 29.2 Implementation Example 14 P-14 PR291 99.0 Equation (A2-2) 1.0 - - Pigment Derivative 1 5.0 26.1 Comparative example 1 P-S1 PR254 100.0 - - - - - - 33.4 Comparative example 2 P-S2 PR254 85.0 Equation (A2-2) 15.0 - - - - 31.3 Comparative example 3 P-S3 PR254 97.0 - - PR272 3.0 - - 29.5 Comparative example 4 P-S4 PR254 97.0 - - Equation (A3-1) 3.0 - - 30.3 Comparative example 5 P-S5 PR291 100.0 - - - - - - 33.1 Comparative example 6 P-S6 PR291 85.0 Equation (A2-2) 15.0 - - - - 29.8 PR254: Cinilex DPP Red ST (CINIC) PR291: Cinilex DPP Red MT-CF (CINIC) PR272: Irgazin RED K3800 (BASF)

<Preparation of Diketopyrrolopyrrole Coloring Compound> [Example 101] (Preparation of Diketopyrrolopyrrole Coloring Compound (DR-1)) The mixture of the following components was stirred and mixed in a homogeneous manner, then dispersed for 5 hours using 0.5 mm diameter zirconium oxide beads in an Eiger mill (M-250 MKII mini model manufactured by Eiger Japan). The mixture was then filtered using a 5.0 μm pore size filter to produce the coloring compound (DR-1). Diketolpyrrolopyrrole Pigment Composition (P-1) 10.7 parts Pigment Derivative 1 1.0 part Pigment Derivative 4 0.3 parts Resin Dispersant Solution 1 6.0 parts Resin Dispersant Solution 2 6.0 parts Resin Dispersant Solution 3 1.0 part Acrylic Resin Solution 1 13.4 parts Propylene Glycol Monomethyl Ether Acetate 56.6 parts Propylene glycol monomethyl ether 5.0 parts

[Examples 102-114, Comparative Examples 101-106] (Preparation of Diketopyrrolopyrrole Coloring Compounds (DR-2-DR-14, DR-S1-DR-S6)) The coloring compounds (DR-2-DR-14, DR-S1-DR-S6) were manufactured in the same manner as the coloring compound (DR-1), except that the diketopyrrolopyrrole pigment compound (P-1) was replaced with the pigment compounds shown in Table 2.

<Preparation of Other Coloring Components> (Preparation of PR177 Coloring Component (DR-177A) for Tinting) The following mixture was stirred and mixed to achieve homogeneity. Then, using 0.5 mm diameter zirconium oxide beads, it was dispersed for 5 hours using an Eiger mill (Eiger Japan, "mini model" M-250 MKII). Finally, it was filtered using a 5.0 μm pore size filter to produce PR177 coloring component (DR-177A). Anthraquinone pigment (Cinilex Red SR3C from CINIC) 11.6 parts Pigment derivative 3 0.4 parts Resin-based dispersant solution 1 6.0 parts Resin-based dispersant solution 2 6.0 parts Acrylic resin solution 2 16.0 parts Propylene glycol monomethyl ether acetate 55.0 parts Propylene glycol monomethyl ether 5.0 parts

<Evaluation of Coloring Compositions> The obtained coloring compositions (DR-1 to DR-14, DR-S1 to DR-S6) were evaluated using the following methods. The results are shown in Table 2.

(Evaluation of Contrast Ratio) Using a rotary coating machine, the colored components (DR-1 to DR-14, DR-S1 to DR-S6) were applied to a 100 mm × 100 mm, 1.1 mm thick glass substrate. The solvent was removed by heating at 80°C for 15 minutes in a clean oven, followed by heating at 230°C for 60 minutes in a clean oven. After cooling, a red-coated substrate was obtained. Furthermore, the red-coated substrate, after heat treatment at 230°C, exhibited a chromaticity of x = 0.660 under a C light source. Next, the method for determining the contrast ratio is explained. Light emitted from the backlight unit of a liquid crystal display is polarized by a polarizing plate and then reaches the polarizing plate through a dried coating of a colored composition applied to a glass substrate. If the polarizing plates are parallel, the light passes through the polarizing plate; however, if the polarizing plates are orthogonal, the light is blocked by the polarizing plate. However, when the polarized light passes through the dried coating of the colored composition, scattering caused by pigment particles occurs, resulting in a partial shift in the polarizing plane. Therefore, when the polarizing plates are parallel, the amount of light passing through the polarizing plate decreases; when the polarizing plates are orthogonal, some light passes through the polarizing plate. This transmitted light is measured as the brightness on the polarizing plate, and the ratio (contrast ratio) between the brightness when the polarizing plates are parallel and the brightness when they are orthogonal is calculated. Furthermore, a colorimeter (Topcon BM-5A) was used as the luminance meter, and a polarizing plate (Nitto Denko Nippon ...

(Evaluation of Stability) The initial viscosity at 25°C was measured using an E-type viscometer (ELD type viscometer manufactured by Toki Sangyo Co., Ltd.) for the colored components (DR-1 to DR-14, DR-S1 to DR-S6). Subsequently, the viscosities were stored in a thermostat at 40°C for two weeks with time acceleration. The viscosity after time acceleration was then measured using the same method as the viscosity measurement described above. The rate of change in viscosity before and after two weeks of storage at 40°C was calculated, and the results were evaluated in three stages according to the following criteria. ◎: Absolute viscosity change rate less than 10% (Good) ○: Absolute viscosity change rate between 10% and 20% (Average) ×: Absolute viscosity change rate exceeding 20% (Poor)

[Table 2] Coloring components Pigment composition Evaluation results of coloring components Contrast Ratio Maintain stability Implementation Example 101 DR-1 P-1 ○ ◎ Implementation Example 102 DR-2 P-2 ◎ ◎ Implementation Example 103 DR-3 P-3 ◎ ◎ Implementation Example 104 DR-4 P-4 ◎ ◎ Implementation Example 105 DR-5 P-5 ◎ ◎ Implementation Example 106 DR-6 P-6 ◎ ○ Implementation Example 107 DR-7 P-7 ○ ◎ Implementation Example 108 DR-8 P-8 ○ ◎ Implementation Example 109 DR-9 P-9 ○ ◎ Implementation Example 110 DR-10 P-10 ◎ ◎ Implementation Example 111 DR-11 P-11 ○ ○ Implementation Example 112 DR-12 P-12 ◎ ◎ Implementation Example 113 DR-13 P-13 ○ ◎ Implementation Example 114 DR-14 P-14 ◎ ◎ Comparative example 101 DR-S1 P-S1 × ◎ Comparative example 102 DR-S2 P-S2 ○ × Comparative example 103 DR-S3 P-S3 × ◎ Comparative example 104 DR-S4 P-S4 △ ○ Comparative example 105 DR-S5 P-S5 × ◎ Comparative example 106 DR-S6 P-S6 ○ ×

As shown in Table 2, the coloring compositions using the diketopyrrolopyrrole pigment composition of the present invention exhibit good contrast ratio and storage stability.

<Method for Manufacturing Photosensitive Coloring Composition> [Example 201] (Manufacturing of Photosensitive Coloring Composition (RR-1)) The mixture of the following components was uniformly stirred and mixed, and then filtered using a filter with a pore size of 1.0 μm to obtain a red photosensitive coloring composition (RR-1). PR177 coloring composition (DR-177A) 16.28 parts Diketopyrrolopyrrole coloring composition (DR-1) 33.72 parts Acrylic resin solution 1 3.60 parts Epoxy compound (Daicel's "EHPE-3150") 0.16 parts Photopolymerizable monomer (Dong-A Synthetic Co., Ltd.'s "Aronix M402") 1.10 parts Photopolymerizable monomer (Dong-A Synthetic Co., Ltd.'s "Aronix M350") 1.45 parts Photopolymerization initiator (BASF IRGACURE OXE02) 0.15 parts Photopolymerization initiator (BASF IRGACURE 369) 0.30 parts Sensitizer (Nippon Kayaku Co., Ltd. KAYACURE DETX-S) 0.05 parts Thiol compound (Pentaerythritol tetrathiopropionate) 0.20 parts Leveling agent (BYK-330, manufactured by BYK-Chemie) 0.05 parts Antioxidant (IRGANOX 1010, manufactured by BASF) 0.10 parts Propylene glycol monomethyl ether acetate 32.84 parts Ethyl 3-ethoxypropionate 10.00 parts

[Examples 202-214, Comparative Examples 201-206] (Manufacturing of Photosensitive Coloring Compositions (RR-2-RR-14, RR-S1-RR-S6)) The total content of the coloring components in the photosensitive coloring compositions is fixed at 50.00 parts. The types and mixing ratios of the coloring components are varied. Otherwise, the photosensitive coloring compositions (RR-2-RR-14, RR-S1-RR-S6) are obtained in the same manner as in Example 201. The types of coloring components are set as shown in Table 3, and the mixing ratio of the coloring components is set to the ratio of the chromaticity of the substrate after fabrication to (x=0.660, y=0.324) under a C light source.

[Example 215] (Preparation of photosensitive tinting composition (RR-15)) The mixture of the following components was uniformly stirred and mixed, and then filtered using a filter with a pore size of 1.0 μm to obtain a red photosensitive tinting composition (RR-15). PR177 coloring compound (DR-177A) 15.09 parts Diketopyrrolopyrrole coloring compound (DR-14) 34.91 parts Acrylic resin solution 1 3.85 parts Epoxy compound (TEPIC-S, manufactured by Nissan Chemical Industries) 0.16 parts Photopolymerizable monomer (KAYARAD DPCA-30, manufactured by Nippon Kayaku Co., Ltd.) 1.85 parts Photopolymerizable monomer (UA-510H, manufactured by Kyoei Chemical Co., Ltd.) 0.50 parts Photopolymerization initiator (BASF IRGACURE OXE01): 0.55 parts Photopolymerization initiator (BASF IRGACURE 907): 0.20 parts Sensitizer (HODOO Chemicals Co., Ltd. EAB-F): 0.05 parts Silane coupling agent (Shin-Etsu Silicones Co., Ltd. KBM-403): 0.03 parts Polymerization inhibitor (Cetyl hydroquinone): 0.02 parts UV absorber (TINUVIN P, manufactured by BASF) 0.05 parts Leveling agent (Megafac F-551, manufactured by DIC) 0.05 parts Propylene glycol monomethyl ether acetate 32.69 parts 1,3-Butanediol diacetate 5.00 parts 3-Methoxybutanol 5.00 parts

<Evaluation of Photosensitive Coloring Compositions> The obtained photosensitive coloring compositions were evaluated using the following method. The results are shown in Table 3. (Evaluation of Brightness) Using a rotary coating machine, the photosensitive coloring compositions (RR-1 to RR-15, RR-S1 to RR-S6) were coated onto a 100 mm × 100 mm, 1.1 mm thick glass substrate. The solvent was removed by heating at 80°C for 15 minutes in a clean oven to obtain a coating film. Subsequently, ultraviolet light exposure was performed using an ultra-high pressure mercury lamp with a cumulative light intensity of 100 mJ/ ^cm² , and development was performed using an alkaline developer at 23°C to obtain the coated substrate. Next, the substrate was heated to 230°C for 30 minutes in a clean oven, and after cooling, the lightness Y(C) of the coated substrate was measured using a microspectrophotometer (OSP-SP100 manufactured by Olympus Optics). Furthermore, the red coated substrate, after heat treatment at 230°C, exhibited a chromaticity of (x=0.660, y=0.324) under C light source. An alkaline developer was used, comprising 1.5% sodium carbonate, 0.5% sodium bicarbonate, 8.0% anionic surfactant (Pelex NBL manufactured by Kao Corporation), and 90% water. Lightness was evaluated using the following four stages. ◎: 18.5 or above (Excellent) ○: 18.3 or above, but less than 18.5 (Good) △: 18.1 or above, but less than 18.3 (Poor) ×: Less than 18.1 (Extremely Poor)

(Contrast Ratio Evaluation) The contrast ratio is measured using the same substrate used in the brightness evaluation. The contrast ratio is evaluated using the following four levels: ◎: 5000 or higher (Extremely Good) ○: 4000 or higher, less than 5000 (Good) △: 3000 or higher, less than 4000 (Poor) ×: Less than 3000 (Extremely Poor)

(Evaluation of Stability) The initial viscosity of the obtained photosensitive coloring composition at 25°C was measured using an E-type viscometer ("ELD type viscometer" manufactured by Toki Kogyo Co., Ltd.). Then, it was stored in a thermostat at 40°C for two weeks with time acceleration. The viscosity after time acceleration was then measured using the same method as the viscosity measurement described above. The rate of viscosity change before and after two weeks of storage at 40°C was calculated, and an evaluation was conducted in three stages based on the following criteria: ◎: Absolute value of viscosity change rate less than 5% (Good) ○: Absolute value of viscosity change rate 5% to 10% (Average) ×: Absolute value of viscosity change rate more than 10% (Poor)

(Evaluation of heat resistance) Using a rotary coating machine, photosensitive tinting compositions (RR-1 to RR-15, RR-S1 to RR-S6) were applied to a 100 mm × 100 mm, 1.1 mm thick glass substrate. The solvent was removed by heating at 70°C for 15 minutes in a clean oven to obtain a dried coating. At this point, the coating was applied with a dry coating thickness of 2.5 μm. Subsequently, ultraviolet light exposure was performed using an ultra-high pressure mercury lamp with a photomask of a 100 μm wide (200 μm spacing) stripe pattern at a cumulative light intensity of 100 mJ/ ^cm². The substrate was then developed using an alkaline developer at 23°C to obtain a striped coating substrate. Next, a heat treatment was performed at 230°C for 60 minutes, followed by a heat treatment at 240°C for 60 minutes, and then a heat treatment at 280°C for 60 minutes. The coating surface of the substrate after the heat treatment was observed using an optical microscope, and the presence or absence of crystal precipitation was determined according to the following four-stage criteria. ◎…No crystals precipitated after heating at 230℃ for 60 minutes, then at 240℃ for 60 minutes, and then at 280℃ for 60 minutes. ○…No crystals precipitated after heating at 230℃ for 60 minutes and then at 240℃ for 60 minutes, but crystals precipitated after heating at 280℃ for 60 minutes. △…No crystals precipitated after heating at 230℃ for 60 minutes, but crystals precipitated after heating at 240℃ for 60 minutes. ×…Crystals precipitated after heating at 230℃ for 60 minutes.

(Evaluation of Solvent Resistance) Using a rotary coating machine, photosensitive tinting compositions (RR-1 to RR-15, RR-S1 to RR-S6) were applied to a 100 mm × 100 mm, 1.1 mm thick glass substrate. The solvent was removed by heating at 70°C for 15 minutes in a clean oven, resulting in a dried coating. At this point, the coating was applied with a dry coating thickness of 2.5 μm. Subsequently, ultraviolet light exposure was performed using an ultra-high pressure mercury lamp with a photomask of a 100 μm wide (200 μm spacing) stripe pattern at a cumulative light intensity of 100 mJ/ ^cm². Development was then performed using an alkaline developer at 23°C to obtain a striped coating substrate. Next, the coating was heated in a clean oven at 230°C for 60 minutes. Here, the colorimetric values (L*(1), a*(1), b*(1)) under light source C were measured. Then, the coating was immersed in N-methyl pyrrolidone (NMP) at 40°C for 30 minutes, and the colorimetric values (L*(2), a*(2), b*(2)) under light source C were measured. The colorimetric values before and after immersion in NMP were used, and the color difference ΔE*ab was calculated according to the following formula. The solvent resistance of the coating was evaluated in the following three stages. Calculation formula: ΔE*ab=[[L*（2）-L*（1）] ² +[a*（2）-a*（1）] ² +[b*（2）-b*（1）] ² ] ^1/2 ◎：ΔE*ab less than 1.0 (Very good) ○：ΔE*ab is 1.0 or more but less than 3.0 (Good) △：ΔE*ab is 3.0 or more but less than 5.0 (Poor) ×：ΔE*ab is 5.0 or more (Very poor)

(Evaluation of Migration) The photosensitive pigment composition was applied to a glass substrate using a slit-die coating machine, followed by pre-baking at 90°C for 2 minutes to form a 2.4 μm thick coating. The coated substrate was then cooled to room temperature, and exposed to radiation at wavelengths of 365 nm, 405 nm, and 436 nm using a high-pressure mercury lamp and a striped photomask with an exposure dose of 1,000 J/ ^m² . After alkaline development, the substrate was cleaned with ultrapure water and then baked at 230°C for 20 minutes, thereby forming red striped pixels on the substrate. Next, the transmittance at 520 nm on a glass substrate 8 μm away from the red striped pixels was measured (T1). Then, acrylic resin solution 2 was applied to the substrate using a slit die coating machine, followed by pre-baking at 90°C for 2 minutes to form a 2.5 μm thick coating. This was then baked at 230°C for 20 minutes. Next, the transmittance at 520 nm on the glass substrate 8 μm away from the red striped pixels was measured (T2). The difference between T1 and T2 was taken as ΔT (%) and evaluated in four stages as described below. A smaller ΔT value indicates less brightness reduction due to color migration to adjacent filter segments of other colors, indicating suppressed color migration. ◎: ΔT less than 1.0% (Extremely Good) ○: ΔT 1.0% or more but less than 2.0% (Good) △: ΔT 2.0% or more but less than 3.0% (Poor) ×: ΔT 3.0% or more (Extremely Poor)

[Table 3] Photosensitive coloring components Diketolpyrrolopyrrole chromogenic composition PR177 coloring composition Evaluation results of photosensitive coloring components Name Pigment composition Name Brightness Contrast Ratio Maintain stability Heat resistance Solvent resistance transmissibility Implementation Example 201 RR-1 DR-1 P-1 DR-177A 〇 〇 ◎ 〇 ◎ ◎ Implementation Example 202 RR-2 DR-2 P-2 DR-177A 〇 ◎ ◎ ◎ ◎ ◎ Implementation Example 203 RR-3 DR-3 P-3 DR-177A 〇 ◎ ◎ ◎ ◎ ◎ Implementation Example 204 RR-4 DR-4 P-4 DR-177A 〇 ◎ ◎ ◎ ◎ ◎ Implementation Example 205 RR-5 DR-5 P-5 DR-177A 〇 ◎ ◎ ◎ 〇 〇 Implementation Example 206 RR-6 DR-6 P-6 DR-177A 〇 ◎ 〇 ◎ 〇 〇 Implementation Example 207 RR-7 DR-7 P-7 DR-177A ◎ 〇 ◎ 〇 ◎ ◎ Implementation Example 208 RR-8 DR-8 P-8 DR-177A ◎ 〇 ◎ ◎ ◎ ◎ Implementation Example 209 RR-9 DR-9 P-9 DR-177A ◎ 〇 ◎ ◎ ◎ ◎ Implementation Example 210 RR-10 DR-10 P-10 DR-177A 〇 ◎ ◎ ◎ 〇 ◎ Implementation Example 211 RR-11 DR-11 P-11 DR-177A 〇 〇 〇 ◎ 〇 〇 Implementation Example 212 RR-12 DR-12 P-12 DR-177A 〇 ◎ ◎ ◎ ◎ ◎ Implementation Example 213 RR-13 DR-13 P-13 DR-177A ◎ 〇 ◎ ◎ ◎ ◎ Implementation Example 214 RR-14 DR-14 P-14 DR-177A ◎ ◎ ◎ ◎ ◎ ◎ Implementation Example 215 RR-15 DR-14 P-14 DR-177A ◎ ◎ ◎ ◎ ◎ ◎ Comparative example 201 RR-S1 DR-S1 P-S1 DR-177A △ × ◎ × ◎ ◎ Comparative example 202 RR-S2 DR-S2 P-S2 DR-177A × 〇 × ◎ × △ Comparative example 203 RR-S3 DR-S3 P-S3 DR-177A △ × ◎ × ◎ ◎ Comparative example 204 RR-S4 DR-S4 P-S4 DR-177A △ △ 〇 △ ○ 〇 Comparative example 205 RR-S5 DR-S5 P-S5 DR-177A △ × ◎ × ◎ ◎ Comparative example 206 RR-S6 DR-S6 P-S6 DR-177A × 〇 × ◎ × △

As shown in Table 3, the photosensitive coloring compositions of Examples 201 to 215, which contain diketopyrrolopyrrole pigments of general formulas (1) and (2) in a mass ratio of 99.9:0.1 to 90.0:10.0, which are characteristic of the present invention, show no practical problems in terms of lightness, contrast ratio, storage stability, heat resistance, solvent resistance, and migration. On the other hand, the comparative examples 210, 203 to 205, which do not contain diketopyrrolopyrrole pigments of general formula (2), show poor crystallization during the heating process compared to the examples. As a result of the crystallization, their lightness or contrast ratio is also worse than that of the examples. Furthermore, Comparative Examples 202 and 206, which contained more than 10% by mass of diketopyrrolopyrrole pigment of general formula (2), showed poorer stability, solvent resistance, and migration properties than the embodiments. This is believed to be because, compared with the diketopyrrolopyrrole pigment of general formula (1), the diketopyrrolopyrrole pigment of general formula (2) itself has poorer dispersion stability, solvent resistance, and migration properties.

<Production of Color Filters> First, the green and blue photosensitive colorants used in making the color filters are prepared.

(Preparation of Green Photosensitive Coloring Compound (RG-100)) The mixture of the following components was stirred and mixed to achieve homogeneity. Then, using 0.5 mm diameter zirconium oxide beads, it was dispersed for 5 hours using an Eiger mill (Eiger Japan, "mini model" M-250 MKII). Finally, it was filtered using a 5.0 μm pore size filter to produce the green coloring compound (DG-100). Green pigment (C.I. Pigment Green 58) 8.6 parts Yellow pigment (C.I. Pigment Yellow 138) 3.4 parts Resin-based dispersant (BASF's "EFKA 4300") 3.0 parts Acrylic resin solution 1 25.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

Next, the mixture of the following components was stirred to achieve homogeneity, and then filtered using a 1.0 μm pore size filter to produce a green photosensitive tinting compound (RG-100). Green coloring component (DG-100): 42.0 parts Acrylic resin solution: 13.2 parts Photopolymerizable monomer (Aronix M402, manufactured by Toa Synthetic Co., Ltd.): 2.8 parts Photopolymerization initiator (IRGACURE 907, manufactured by BASF): 2.0 parts Sensitizer (EAB-F, manufactured by Hotoko Chemical Co., Ltd.): 0.4 parts Propylene glycol monomethyl ether acetate: 39.6 parts

(Preparation of Blue Photosensitive Coloring Compound (RB-100)) The mixture of the following components was stirred and mixed to achieve homogeneity. Then, using 0.5 mm diameter zirconium oxide beads, it was dispersed for 5 hours using an Eiger mill (Eiger Japan, "mini model" M-250 MKII). Finally, it was filtered using a 5.0 μm pore size filter to produce the blue coloring compound (DB-100). Blue pigment (C.I. Pigment Blue 15:6) 7.2 parts Purple pigment (C.I. Pigment Violet 23) 4.8 parts Resin-based dispersant (BASF's "EFKA 4300") 1.0 part Acrylic resin solution 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

Next, the mixture of the following components was stirred to achieve homogeneity, and then filtered using a 1.0 μm pore size filter to produce a blue photosensitive tinting composition (RB-100). Blue coloring component (DB-100): 34.0 parts Acrylic resin solution 2: 15.2 parts Photopolymerizable monomer (Aronix M402, manufactured by Toa Synthetic Co., Ltd.): 3.3 parts Photopolymerization initiator (IRGACURE 907, manufactured by BASF): 2.0 parts Sensitizer (EAB-F, manufactured by Hotoko Chemical Co., Ltd.): 0.4 parts Propylene glycol monomethyl ether acetate: 45.1 parts

(Fabrication of a Color Filter for a Liquid Crystal Display Device) A black matrix pattern is fabricated on a glass substrate, and the red photosensitive coloring composition (RR-14) of the present invention is applied to the substrate using a rotary coating machine to form a colored film. The film is then shielded by a photomask and irradiated with 200 mJ/ ^cm² ultraviolet light using an ultra-high pressure mercury lamp. Next, unexposed areas are removed by spray development using an alkaline developing solution containing 0.2% sodium carbonate aqueous solution. The substrate is then cleaned with ion-exchanged water and heated at 230°C for 30 minutes to form the red filter section. Here, the red filter section is heat-treated at 230°C to achieve a chromaticity of x=0.660 under a C light source. Similarly, using the same method, a green filter section is formed with a green photosensitive colorant (RG-100) to achieve a chromaticity of y=0.570, and a blue filter section is formed with a blue photosensitive colorant (RB-100) to achieve a chromaticity of y=0.045. These filter sections are then used to obtain a color filter.

The photosensitive coloring composition (RR-14) of this invention is used in the formation of the red filter section, thereby achieving high brightness and high contrast of the color filter, and it is suitable for use without any problems in other physical properties. In addition, the color filter of this invention is bonded to the opposing substrate using a sealant, liquid crystal is injected through the injection port provided in the sealing part, the injection port is sealed, and a polarizing film or retardation film is bonded to the outer side of the substrate, thereby obtaining a liquid crystal display device with excellent brightness and contrast ratio.

(Fabrication of Color Filters for Solid State Imaging Components) On a 6-inch silicon wafer, a planarization film resist solution (HL-18s; manufactured by Nippon Steel Chemical Co., Ltd.) is coated using a spin coating method. As a pre-baking process, the wafer is heated at 100°C for 6 minutes. Then, it is dried in a 230°C oven for 1 hour to harden the coating, forming a 1.0 μm planarization film, thus obtaining a wafer with a planarization film.

A green photosensitive coloring composition (RG-100) was coated onto a silicon wafer with a planarization film using a rotary coating machine as a pre-baking process. The wafer was then heated for 1 minute using a heating plate at 100°C. The pre-baked film thickness was then adjusted to 0.9 μm.

Subsequently, the pattern was exposed at a wavelength of 365 nm using an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) to separate a photomask for forming a 1.0 μm square red pixel and an exposure dose of ¹⁵⁰ mJ/cm².

The exposed coating was developed using an organic base developer for 1 minute. After development, it was rinsed with pure water for 20 seconds using a rotating spray method, followed by a 20-second water rinse with pure water. Then, residual water droplets on the wafer were blown away with high-pressure air, and the substrate was allowed to air dry. Finally, it was heat-treated for 5 minutes on a heated plate at a surface temperature of 230°C to form a square pixel pattern. The thickness of the green pattern after heat treatment was 0.80 μm.

Next, a red color pixel layer is formed using a red photosensitive coloring composition (RR-12), similar to the green color pixel layer, and then a blue color pixel layer is formed using a blue photosensitive coloring composition (RB-100), thereby obtaining a color filter for a solid-state imaging device. The red spectral characteristics of the color filter for a solid-state imaging device manufactured in this manner are very good and the heat resistance is excellent. Therefore, the skin color reproduction of solid-state imaging devices using this color filter for solid-state imaging devices is particularly excellent.

without

without

Claims (7)

A color filter pigment composition comprising a diketopyrrolopyrrole pigment (A1) represented by general formula (1) and a diketopyrrolopyrrole pigment (A2) represented by general formula (2), wherein the mass ratio of diketopyrrolopyrrole pigment (A1) to diketopyrrolopyrrole pigment (A2) is 99.9:0.1 to 90.0:10.0; In general formula (1), X represents a halogen atom. In general formula (2), Y and Z independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group with 1 to 20 carbon atoms that may have substituents, or a phenyl group that may have substituents; wherein at least one of Y and Z is an alkyl group with 3 to 18 carbon atoms, and the two Ys in general formula (2) are the same, and the two Zs are the same. The color filter pigment composition as described in claim 1 further contains pigment derivatives. A color filter coloring composition comprising a colorant, a resin, and a solvent, wherein the colorant comprises a color filter pigment composition as described in claim 1 or claim 2. The color filter composition as described in claim 3 further contains photopolymerizable monomers and/or photopolymerization initiators. A color filter includes a filter section formed from a colored composition of the color filter as described in claim 3 or claim 4. A liquid crystal display device includes a color filter as described in claim 5. A solid-state imaging element comprising a color filter as described in claim 5.