JP7219378B1 - Photosensitive coloring composition, optical filter, image display device, and solid-state imaging device - Google Patents

Abstract

Kind Code: A1 The present invention provides a desired pixel width even with a low exposure dose during development, suppresses wrinkles on the pixel surface, has heat resistance in the pixel, and facilitates control of the height of the laminated photospacer. An object of the present invention is to provide a photosensitive coloring composition. A photosensitive coloring composition comprising a coloring agent (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), wherein the polymerizable compound (C) contains an aliphatic urethane (meth)acrylate (C1), and the photopolymerization initiator (D) contains an oxime-based photopolymerization initiator (D2b) containing two oxime groups in one molecule. Composition. [Selection drawing] Fig. 1

Description

The present invention relates to a photosensitive coloring composition used for color filters and the like.

Color filters, which are one type of optical filters used in image display devices, solid-state imaging devices, etc., are usually patterned on a film formed from a photosensitive coloring composition by a process such as photolithography. .

In a liquid crystal display (LCD), a TFT substrate and a color filter substrate are arranged facing each other with a predetermined gap, and liquid crystal is filled in the gap. If this interval is not maintained accurately, a difference in the thickness of the liquid crystal layer will occur, resulting in display defects. Therefore, Patent Literature 1 proposes a forming method. Patent Document 1 discloses a method of forming columnar protrusions called spacers having a diameter of 10 μm to 50 μm on a substrate of a color filter by photolithography.

As a photosensitive coloring composition for forming a spacer, Patent Document 2 discloses: A photosensitive coloring composition containing an extender pigment and a special monomer is disclosed. Patent Document 3 discloses a photosensitive coloring composition containing an epoxy curing agent. Patent Document 4 discloses a photosensitive coloring composition whose solvent composition is adjusted to improve leveling properties.

JP 2013-101234 A JP 2013-97235 A JP 2020-095194 A JP 2019-133144 A

However, conventional compositions have the problem of narrowing the pixel width when the exposure dose during development is reduced in order to shorten the process time, the problem of wrinkles on the pixel surface, and the problem of insufficient heat resistance. Moreover, it was difficult to control the height of the laminated photospacer with conventional compositions.

The present invention is a photosensitive coloring that can obtain the desired pixel width even with a low exposure amount during development, suppresses wrinkles on the pixel surface, has heat resistance in the pixel, and is easy to control the height of the laminated photospacer. It is intended to provide a composition.

The present invention is a photosensitive coloring composition comprising a coloring agent (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D),
The polymerizable compound (C) contains an aliphatic urethane (meth)acrylate (C1),
The photopolymerization initiator (D) relates to a photosensitive coloring composition containing an oxime photopolymerization initiator (D2b) containing two oxime groups in one molecule.

The present invention also relates to the photosensitive coloring composition, wherein the polymerizable compound (C) further contains a polymerizable compound (C2) having a viscosity of 800 mPa·S or less at 25°C.

Further, in the present invention, the content of the polymerizable compound (C2) having a viscosity at 25 ° C. of 800 mPa S or less is 5 to 50% by mass in 100% by mass of the polymerizable compound (C). It relates to a coloring composition.

The present invention also relates to the photosensitive coloring composition, wherein the coloring agent (A) contains a phthalocyanine pigment whose central metal is Al.

The present invention also relates to a color filter having a substrate and a filter segment formed from the photosensitive coloring composition.

The present invention also relates to an image display device having the color filter.

The present invention also relates to a solid-state imaging device having the color filter.

According to the present invention, the desired pixel width can be obtained even with a low exposure amount during development, wrinkles on the pixel surface can be suppressed, the pixel has heat resistance, and the height of the laminated photospacer can be controlled. It is possible to provide an easy-to-use photosensitive coloring composition. Also, the present invention can provide an optical filter, an image display device, and a solid-state imaging device.

FIG. 1 shows a schematic cross-sectional view of an image display device. FIG. 2 shows a schematic cross-sectional view of pixel and stack photospacer height evaluation.

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

The photosensitive coloring composition of the present invention contains a coloring agent (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D),
The polymerizable compound (C) contains an aliphatic urethane (meth)acrylate (C1),
The photopolymerization initiator (D) contains an oxime photopolymerization initiator (D2b) containing two oxime groups in one molecule. The photosensitive coloring composition of the present invention has a synergistic effect of the aliphatic urethane (meth) acrylate (C1) and an oxime-based photopolymerization initiator (D2b) containing two oxime groups in one molecule, resulting in low exposure during development. Even if the amount is small, the desired pixel width can be obtained, wrinkles on the pixel surface can be suppressed, the pixel has heat resistance, and the problem of easy control of the height of the laminated photospacer can be solved.
The photosensitive coloring composition of the present invention is preferably used for applications such as pixels and laminated photospacers constituting color filters such as image display devices and solid-state imaging devices.

<Colorant>
Colorants include pigments and dyes. Pigments include organic pigments and inorganic pigments. The pigment is preferably a pigment having high color developability and high heat resistance, particularly an organic pigment in terms of high heat decomposition resistance. Specific examples of organic pigments are shown below with color index numbers.

Red pigments include, for example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3,57,57:1,57:2,58:4,60,63,63:1,63:2,64,64:1,68,69,81,81:1,81:2,81: 3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255,256,257,258,259,260,262,263,264,265,266,267,268,269,270,271,272,273,274,275,276,277,278,279,280, 281,282,283,284,285,286,287,291,295,296, pigments described in JP-A-2014-134712, pigments described in Japanese Patent No. 6368844, and the like. Among these, from the viewpoint of heat resistance, light resistance and transmittance, C.I. I. Pigment Red 48: 1,122,177,224,242,269,254,291,295,296, the pigment described in JP-A-2014-134712, the pigment described in Patent No. 6368844 is preferable, C. I. Pigment Red 177, 254, 291, 295, 296, pigments described in JP-A-2014-134712, and pigments described in Japanese Patent No. 6368844 are more preferred.

Orange pigments include, for example, C.I. I. Pigment Orange 36, 38, 43, 64, 71, 73 and the like.

Yellow pigments include, for example, C.I. I. Pigment Yellow 1,2,3,4,5,6,10,12,13,14,15,16,17,18,24,31,32,34,35,35:1,36,36:1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, JP 2012-226110, JP 2017-171912, JP 2017-171913, JP 2017-171914 Examples thereof include pigments described in publications, JP-A-2017-171915, and the like. Among these, C.I. I. Pigment Yellow 138, 139, 150, 185, 231, 233 and the pigments described in JP-A-2012-226110 are preferred.

Green pigments include, for example, C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63 and the like. Among these, C.I. I. Pigment Green 36, 58, 59, 62, 63 are preferred.

Blue pigments include, for example, C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 are preferred.

Purple pigments include, for example, C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, C.I. I. Pigment Violet 19, 23 are preferred.

Black pigments include, for example, C.I. I. Pigment Black 1, 6, 7, 12, 20, 31, 32 and the like. In addition, compounds described in JP-A-2010-534726, JP-A-2012-515233, JP-A-2012-515234, JP-A-1-170601, JP-A-2-34664 and the like are also included.

The photosensitive coloring composition herein is preferably a photosensitive green composition containing a green pigment and a yellow pigment. In this case the green pigment is C.I. I. Pigment Green 58 (a phthalocyanine pigment whose central metal is Zn) and 63 (a phthalocyanine pigment whose central metal is Al) are preferred, and C.I. I. Pigment Green 63 is more preferred. A yellow pigment is C.I. I. Pigment Yellow 138 is preferred. As a result, for example, the greenest pixel with the highest brightness can be formed for LCD applications using white LEDs as backlights.

Inorganic pigments other than the above include titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, Prussian blue, chromium oxide green, cobalt green, and amber. , synthetic iron black, and the like.

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

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

Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, sodium sulfate and the like. Among these, sodium chloride (table salt) is preferable from the point of price. The amount of the water-soluble inorganic salt to be used is preferably 50 to 2000 parts by mass, more preferably 300 to 1000 parts by mass, based on 100 parts by mass of the pigment, from the viewpoint of both processing efficiency and production efficiency.

The water-soluble organic solvent wets the pigment and the water-soluble inorganic salt. A water-soluble organic solvent is a compound that dissolves (miscible in) water and does not substantially dissolve water-soluble inorganic salts. The water-soluble organic solvent is preferably a high boiling point solvent having a boiling point of 120° C. or higher because it is difficult to volatilize due to the temperature rise during salt milling. Water-soluble organic solvents include, for example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. mentioned. The amount of the water-soluble organic solvent used is preferably 5 to 1000 parts by mass, more preferably 50 to 500 parts by mass, based on 100 parts by mass of the pigment.

A resin can be added as needed during the salt milling process. Resins include, for example, natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. The resin is solid at room temperature, preferably water-insoluble, and more preferably partially soluble in water-soluble organic solvents. The amount of the resin used is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the pigment.

<Removal of metal>
If a large amount of the specific metal element exists in the coloring composition as an impurity other than the constituent components of the pigment, the dispersion stability over time is hindered, and the heat resistance may be lowered, or the sensitivity may be lowered. In addition, a color filter produced using this may have foreign matter, which tends to result in a decrease in brightness. The total content of Li, Na, K, Mg, Ca, Fe, Al, and Cr (hereinafter also referred to as specific metal elements) contained in the photosensitive coloring composition is preferably 500 mass ppm or less.

The total amount of specific metal elements contained in the photosensitive coloring composition is more preferably 300 mass ppm or less, particularly preferably 200 mass ppm or less. The lower limit of the total amount of the specific metal elements is not particularly limited, but is preferably 1 ppm by mass or more, more preferably 5 ppm by mass or more. If it is within the above range, it is possible to obtain a photosensitive coloring composition capable of suppressing the cost, excellent in storage stability, and capable of forming a color filter with little generation of foreign matter and reduction in brightness. The content of the specific metal element can be measured by inductively coupled plasma emission spectrometry (ICP).

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

In addition, metals such as Ni, Zn, Cu, Al, Fe, Fe, Co, and Co that make up the pigment should also contain few impurities that do not function effectively. I can. Further, it is preferable that the concentrations of Mn, Cs, Ti, Co, Si, Pd, etc. mixed with materials (for example, catalysts) used in the manufacturing process of various raw materials of the photosensitive coloring composition are also low.

As a method for removing the colorant (A) or the mixed metal from the equipment in the manufacturing process, JP-A-2010-83997, JP-A-2018-36521, JP-A-7-198928, JP-A-8- Examples include the method of washing with water as described in JP-A-333521 and JP-A-2009-7432, and the method of removing magnetic foreign matter using a magnet as described in JP-A-2011-48736.

<Dye>
Dyes include, for example, acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. In addition, dye derivatives and lake pigments obtained by converting dyes into lakes are also included.

The acid dye preferably has an acidic group such as sulfonic acid or carboxylic acid. Salt-forming compounds, which are salts of acid dyes and nitrogen-containing compounds such as quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, or primary amine compounds, are also preferred. A salt-forming compound, which is a salt of a resin component having these functional groups and an acid dye, is also preferred. Moreover, the salt-forming compound is sulfonamidated to be modified into a sulfonic acid amide compound, thereby easily obtaining a photosensitive coloring composition having excellent resistance (light resistance and solvent resistance).
A salt-forming compound of an acid dye and a compound having an onium base is also preferable because of its excellent resistance (light resistance and solvent resistance). The compound having an onium base is preferably a resin having a cationic group.

Although the basic dye can be used as it is, a salt-forming compound that forms a salt with an organic acid, perchloric acid, or a metal salt thereof is preferred. Salt-forming compounds of basic dyes are preferable because they have excellent resistance (light resistance and solvent resistance) and affinity with pigments. In salt-forming compounds of basic dyes, anion components that act as counter ions include organic sulfonic acids, organic sulfuric acids, fluorine group-containing phosphorus anion compounds, fluorine group-containing boron anion compounds, cyano group-containing nitrogen anion compounds, and halogenated carbonization compounds. A salt-forming compound obtained by salt-forming an anion compound having a conjugate base of an organic acid having a hydrogen group and an acid dye is preferred. It should be noted that the resistance of the salt-forming compound is further improved when it contains a polymerizable unsaturated group in the molecule.

Chemical structures of dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, etc.). dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes , polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and the like; Among these, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, Quinophthalone dyes, phthalocyanine dyes and subphthalocyanine dyes are preferred, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes and phthalocyanine dyes are more preferred.

Colorant (A) can be used alone or in combination of two or more.

The content of the coloring agent (A) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, based on 100% by mass of the non-volatile matter of the photosensitive coloring composition.

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

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

A dye derivative can be used individually or in mixture of 2 or more types.

The amount of the dye derivative used is preferably 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, and even more preferably 5 to 50 parts by mass, based on 100 parts by mass of the organic pigment.

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

<Resin Dispersant>
The photosensitive coloring composition of the present invention can contain a dispersing resin (G). The dispersing resin (G) has a colorant-affinity site that adsorbs to the colorant (A) and a relaxation site that has a high affinity with components other than the colorant and causes steric repulsion between dispersed particles.
The dispersing resin (G) is, for example, a urethane-based dispersant such as polyurethane, a polycarboxylic acid ester such as polyacrylate, an unsaturated polyamide, a polycarboxylic acid, a polycarboxylic acid (partial) amine salt, a polycarboxylic acid ammonium salt, a poly Carboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof; amides and salts thereof; (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc.; Examples include polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, and phosphoric acid esters.
In addition, the polymer dispersion resin having a basic functional group is a nitrogen atom-containing graft copolymer, a nitrogen atom-containing Examples include acrylic block copolymers and urethane polymer dispersion resins.

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

The amount of the dispersing resin (G) used is preferably about 3 to 200% by mass, more preferably about 5 to 100% by mass, based on the colorant (A). When used in an appropriate amount, the film formability is improved.

[Alkali-soluble resin (B)]
The alkali-soluble resin (B) is a binder resin and is preferably used for patterning a film by photolithography.
Alkali-soluble resin (B) has an alkali-soluble group. Alkali-soluble groups include, for example, carboxyl groups, phosphoric acid groups, sulfonic acid groups, hydroxyl groups, and phenolic hydroxyl groups. Among these, a carboxyl group is preferred.
The alkali-soluble resin (B) can be broadly classified into a non-photosensitive alkali-soluble resin and a photosensitive alkali-soluble resin.

(Non-photosensitive alkali-soluble resin)
Non-photosensitive alkali-soluble resins include, for example, acrylic resins having acidic groups, α-olefin/(anhydride) maleic acid copolymers, styrene/styrenesulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, Alternatively, isobutylene/(anhydrous) maleic acid copolymer and the like can be mentioned. Among these, acrylic resins having acidic groups and styrene/styrenesulfonic acid copolymers are preferred.

(Photosensitive alkali-soluble resin)
A photosensitive alkali-soluble resin is an alkali-soluble resin having a polymerizable unsaturated group. The photosensitive alkali-soluble resin is preferably, for example, a resin synthesized by the method (i) or (ii) shown below. By curing with active energy rays, the resin is three-dimensionally crosslinked to improve the crosslink density and chemical resistance.

[Method (i)]
Method (i), for example, first synthesizes a polymer of an epoxy group-containing monomer and other monomers. Next, there is a method of adding a monocarboxyl group-containing monomer to the epoxy group of the polymer, and reacting the formed hydroxyl group with a polybasic acid anhydride to obtain a photosensitive alkali-soluble resin.

Epoxy group-containing monomers include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4- Epoxycyclohexyl (meth)acrylates can be mentioned. Among these, glycidyl (meth)acrylate is preferable from the viewpoint of reactivity.

Other monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t- Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate Acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethylene oxide (EO)-modified cresol acrylate, n-nonyl Phenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, EO-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, nonylphenol (Meth)acrylates such as PO-modified (meth)acrylates of
(Meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone (meth)acrylamide, or (meth)acrylamides such as acryloylmorpholine ;
styrene or styrenes such as α-methylstyrene;
vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether;
Fatty acid vinyls such as vinyl acetate or vinyl propionate;
cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedi maleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl -N-substituted maleimides such as 6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine;
2-(meth)acryloyloxyethyl acid phosphate, a phosphate group-containing unit such as a compound obtained by reacting a hydroxyl group of a hydroxyl group-containing monomer described later with a phosphorylating agent such as phosphorus pentoxide or polyphosphoric acid mers.

Monocarboxyl group-containing monomers are, for example, (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth)acrylic acid, alkoxyl, halogen, nitro, cyano-substituted and monocarboxylic acids such as monocarboxylic acids.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. In addition, if necessary, a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic anhydride can be used to hydrolyze the remaining anhydride groups.

As a method similar to method (i), for example, a polymer of a carboxyl group-containing monomer and other monomers is synthesized. Next, there is a method of adding an epoxy group-containing monomer to a part of the carboxyl groups of the polymer to obtain a photosensitive alkali-soluble resin.

[Method (ii)]
Method (ii) synthesizes polymers of, for example, hydroxyl group-containing monomers, monocarboxyl group-containing monomers, and other monomers. Next, a method of reacting the hydroxyl group of the polymer with the isocyanate group of the isocyanate group-containing monomer can be mentioned.

Hydroxyl group-containing monomers, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylates or hydroxyalkyl methacrylates such as cyclohexanedimethanol mono(meth)acrylate; In addition, polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to hydroxyalkyl (meth)acrylate, poly γ-valerolactone, poly ε-caprolactone, and/or poly Polyester mono(meth)acrylates to which 12-hydroxystearic acid or the like is added are also included. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred because foreign substances are less likely to form in the coating. In terms of photosensitivity, glycerol mono(meth)acrylate is preferred.

Isocyanate group-containing monomers include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis[methacryloyloxy]ethyl isocyanate, and the like.

As the monocarboxyl group-containing monomer and other monomers, the monomers already exemplified can be used.

The raw materials used for synthesizing the photosensitive alkali-soluble resin can be used alone or in combination of two or more.

The photosensitive alkali-soluble resin may also be a resin obtained by adding a polymerizable unsaturated group to the non-photosensitive alkali-soluble resin described above.

The weight average molecular weight (Mw) of the alkali-soluble resin (B) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, even more preferably 4,000 to 20,000. Also, the value of Mw/Mn is preferably 10 or less. Adhesion to substrates and alkali developability are improved by an appropriate Mw.

The acid value of the alkali-soluble resin (B) is preferably from 50 to 200 mgKOH/g, more preferably from 70 to 180 mgKOH/g, even more preferably from 90 to 170 mgKOH/g, in order to impart solubility in alkali development. An appropriate acid value improves the solubility in alkaline development and suppresses the formation of residues. Improves pattern linearity.

The content of the alkali-soluble resin (B) is preferably 5 to 60% by mass, more preferably 10 to 40% by mass, in the non-volatile content of the photosensitive coloring composition from the viewpoint of developer solubility.

In this specification, a thermoplastic resin can be used together as a binder resin other than the alkali-soluble resin.

<Thermoplastic resin>
Thermoplastic resins include, for example, acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, Examples include polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

<Polymerizable compound (C)>
The polymerizable compound (C) includes monomers and oligomers having a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include a vinyl group having an ethylenically unsaturated double bond, a (meth)allyl group, and a (meth)acryloyl group. In addition, an oligomer is a compound with a molecular weight of 1000 or more.
The polymerizable compound (C) includes an aliphatic urethane (meth)acrylate (C1), a polymerizable compound (C2) having a viscosity at 25°C of 800 mPa S or less, a polymerizable compound having an acid group (C3), and others. A polymerizable compound (C4) is mentioned. Among these, the aliphatic urethane (meth)acrylate (C1) and the polymerizable compound (C2) having a viscosity at 25°C of 800 mPa·S or less are preferable, and the aliphatic urethane (meth)acrylate (C1) is more preferable.

(Aliphatic urethane (meth)acrylate (C1))
Aliphatic urethane (meth)acrylate (C1) is a (meth)acrylate having no aromatic moiety but an aliphatic moiety and a urethane bond in the molecule. Examples of aliphatic moieties include chain hydrocarbon groups and saturated cyclic hydrocarbon groups. When aliphatic urethane (meth)acrylate (C1) is used, both improvement in heat resistance and suppression of pixel wrinkles can be achieved. In addition, since the aliphatic urethane (meth)acrylate (C1) has a relatively low viscosity, it contributes to controlling the height of the laminated photospacer.

Aliphatic urethane (meth)acrylate (C1) is not limited as long as it has the above site, and examples thereof include reaction products of aliphatic diisocyanate and hydroxyl group-containing (meth)acrylate. In particular, the aliphatic urethane (meth)acrylate (C1) in which a linear aliphatic diisocyanate is used as a reactant has improved heat resistance.

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

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

Commercial products of aliphatic urethane (meth)acrylate (C1) include UA-306H, UA-306I, UA-510H manufactured by Kyoeisha Chemical Co., Ltd., and the like.

The content of the aliphatic urethane (meth)acrylate (C1) is preferably 5 to 95% by mass, more preferably 5 to 80% by mass, based on 100% by mass of the polymerizable compound (C).

(Polymerizable compound (C2) having a viscosity of 800 mPa S or less at 25°C)
If the photosensitive coloring composition contains a polymerizable compound (C2) (hereinafter referred to as a polymerizable compound (C2)) having a viscosity of 800 mPa S or less at 25°C, the film will flow when the solvent evaporates in the drying process. This makes it easier to adjust the height of the laminated photospacer. Although the height can be adjusted by changing the type of solvent, it is not preferable because the residual solvent may have an adverse effect.

The polymerizable compound (C2) is, for example, tricyclodecanedimethylol di(meth)acrylate, bisphenol FEO-modified di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, trimethylolpropane tri (Meth)acrylates, trimethylolpropane PO-modified tri(meth)acrylates, trimethylolpropane EO-modified tri(meth)acrylates, pentaerythritol tri(and tetra)(meth)acrylates, and the like. Examples of commercially available products include M-309, M-310 and M-450 manufactured by Toagosei Co., Ltd., A-DCP manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and the like.

The content of the polymerizable compound (C2) is preferably 5 to 50% by mass, more preferably 5 to 30% by mass, based on 100% by mass of the polymerizable compound (C).

The number of polymerizable unsaturated groups in the polymerizable compound (C2) is preferably 2 or more, more preferably 3 or more. This makes it easy to achieve both line width sensitivity and overlay rate control at a low exposure dose.

(Polymerizable compound (C3) having an acid group)
The acid group of the polymerizable compound (C3) having an acid group includes, for example, a sulfonic acid group, a carboxyl group, and a phosphoric acid group.

The polymerizable monomer having an acid group (C3) is, for example, an esterified product of a free hydroxyl group-containing poly(meth)acrylate of polyhydric alcohol and (meth)acrylic acid, and a dicarboxylic acid; , esters with monohydroxyalkyl (meth)acrylates, and the like. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. , malonic acid, succinic acid, glutaric acid, free carboxyl group-containing monoesters with dicarboxylic acids such as phthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4- Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2-hydroxy Monohydroxy monoacrylates such as ethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, or free carboxyl group-containing oligoesters with monohydroxy monomethacrylates, and the like can be mentioned.

Other polymerizable compounds (C4) include, for example, dipentaerythritol penta (and hexa) (meth) acrylate, ethoxylated bisphenol A diacrylate, bis and tris-(2-acryloxyethyl) isocyanurate, 9,9-bis[ 4-(2-hydroxyethoxy)phenyl]fluorenediacrylate, neopentylglycol hydroxypivalate diacrylate, UA-306H manufactured by Kyoeisha Chemical Co., Ltd., and the like.

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

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

<Photoinitiator (D)>
The photopolymerization initiator (D) contains an oxime-based photopolymerization initiator (D2b) containing two oxime groups in one molecule, and can be used in combination with other photopolymerization initiators, if necessary.

(Oxime-based photopolymerization initiator (D2))
In oxime ester-based compounds, the absorption of ultraviolet light causes cleavage of the NO bond of the oxime to produce iminyl radicals and alkyloxy radicals. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure. When the colorant concentration of the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may be low and the degree of curing of the coating film may be low. However, oxime ester compounds are preferably used because they have high quantum efficiency. be.
The oxime photopolymerization initiator (D2) includes a compound (D2a) containing one oxime group in one molecule and a compound (D2b) containing two oxime groups in one molecule. The compound (D2b) containing two oxime groups in one molecule is more preferable because of its good line width sensitivity.

[Compound (D2b) Containing Two Oxime Groups in One Molecule]
Oxime-based photopolymerization initiators (D2b) containing two oxime groups in one molecule are, for example, JP-A-2005-215378, JP-A-2011-105713, JP-A-2017-523465, JP-A-2017-523465, Examples thereof include compounds described in JP-A-2021-011486 and the like. Among them, a compound represented by the following general formula (7) is preferable.

general formula (7)

In general formula (7), X ₁ and X ₂ each independently represent a carbonyl bond (--CO--) or a single bond. _X3 represents a single bond or a sulfur atom. R ₁ represents an alkyl group having 1 to 20 carbon atoms, R ₂ and R ₃ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a heterocyclic ring having 2 to 30 carbon atoms, It represents an aryl group of 30 or an arylalkyl group of 7 to 30 carbon atoms. R ₄ and R ₅ each independently represents an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. show.

In general formula (7), X ₁ and X ₂ each independently represent a carbonyl bond (--CO--) or a single bond. Above all, from the viewpoint of solubility in organic solvents, at least one of X ₁ and X ₂ is preferably a carbonyl bond (--CO--), and X ₁ and X ₂ are more preferably a carbonyl bond (--CO--).

In general formula (7), _X3 is a single bond or a sulfur atom, preferably a single bond.

In general formula (7), R ₁ represents an alkyl group having 1 to 20 carbon atoms.
The alkyl group having 1 to 20 carbon atoms may be linear, branched, cyclic, or a combination thereof. may be a base. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group , nonyl group, decyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylmethyl group and the like. Among these, an ethyl group, a propyl group and an isopropyl group are preferred.

In general formula (7), R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a heterocyclic ring having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a carbon atom. represents an arylalkyl group of numbers 7 to 30;
The alkyl group having 1 to 20 carbon atoms is the same as above. Among them, a pentyl group, a hexyl group, a heptyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, and a cyclohexylmethyl group are preferable.
Examples of the heterocyclic group having 2 to 30 carbon atoms include pyridyl group, pyrimidyl group, furyl group, tetrahydrofuryl group, dioxolanyl group, imidazolidyl group, oxazolidyl group, piperidyl group and morpholinyl group.
Examples of the aryl group having 6 to 30 carbon atoms include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group and anthryl group. The aryl group may be a group substituted with a halogen atom, an amino group, a nitro group, or the like.
Examples of arylalkyl groups having 7 to 30 carbon atoms include benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, phenylethyl group and the like. An arylalkyl group may be a group substituted with a halogen atom, an amino group, a nitro group, or the like.

Among these, from the viewpoint of solubility in organic solvents, at least one of R ₂ and R ₃ is preferably a linear alkyl group having 1 to 20 carbon atoms. From the viewpoint of suppressing , a straight-chain alkyl group having 1 to 20 carbon atoms and a cyclic alkyl group having 1 to 20 carbon atoms are more preferable.

In general formula (7), R ₄ and R ₅ each independently represent an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or 7 carbon atoms. represents an arylalkyl group of ∼30.
The alkyl group having 1 to 20 carbon atoms is the same as above. Among them, a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferable from the viewpoint of reactivity.
The heterocyclic group having 2 to 30 carbon atoms is the same as described above.
The aryl group having 6 to 30 carbon atoms is the same as above. Among them, a phenyl group is preferable from the viewpoint of reactivity.
The arylalkyl group having 7 to 30 carbon atoms is the same as above.

Among these, R ₄ and R ₅ are preferably a methyl group, an ethyl group, or a phenyl group, more preferably a methyl group or an ethyl group, from the viewpoint of reactivity.

The method for producing the compound represented by formula (7) is not particularly limited, and known methods can be used. For example, the methods described in JP-A-2017-523465, JP-A-2021-011486, etc. can be used.

Specific examples of the compound (D2b) containing two oxime groups in one molecule are shown below. In addition, this invention is not limited to these.

chemical formula (10)

chemical formula (11)

Among chemical formulas (8) to (11), the compound of chemical formula (8) is preferable from the viewpoint of suppression of water stains.

[Compound (D2a) containing one oxime group in one molecule]
Commercial products of the compound (D2a) containing one oxime group in one molecule include, for example, IRGACURE OXE-01, 02, 03 manufactured by BASF Japan, and Adeka Arcles N-1919 and NCI-831 manufactured by ADEKA. , 930, TRONLY TR-PBG-301, 304, 305, 309, 314, 358, 380, 365, 610, 3054, 3057 manufactured by Changzhou Tenryu New Materials Co., Ltd., OMNIRAD 1312, 1314, 1316 manufactured by IGM Resins, Samyang Corporation SPI-02, 03, 04, 06, 07 manufactured by Co., Ltd., and DFI-020 and EOX-01 manufactured by Daito Chemix Co., Ltd.

Specific examples of the compound (D2a) containing one oxime group in one molecule include the following. In addition, this invention is not limited to these.

Methods for producing compounds of chemical formulas (3) to (6) include, for example, JP-A-2004-534797, JP-A-2008-80068, JP-A-2012-526185, International Publication No. 2015/036910, International Examples include methods described in Japanese Unexamined Patent Publication No. 2015/152153, Japanese Patent Publication No. 2016-504270, Japanese Patent Publication No. 2017-512886, and the like.

The compound (D2a) containing one oxime group in one molecule can be used alone or in combination of two or more.

(Photopolymerization initiator (D1) represented by general formula (1))

General formula (1)

(In general formula (1), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ₃ represents a hydrogen atom or a monovalent substituent. show.)

R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
The alkyl group having 1 to 8 carbon atoms may be linear, branched, cyclic, or a combination thereof, such as methyl, ethyl, propyl, isopropyl, butyl. group, isobutyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylmethyl group and the like. be done. Among them, straight-chain alkyl groups having 3 to 8 carbon atoms are preferred, and straight-chain alkyl groups having 4 to 6 carbon atoms are more preferred, from the viewpoints of water stain suppression and pattern shape.

R ₃ represents a hydrogen atom or any monovalent substituent.
Examples of monovalent substituents include alkyl groups having 1 to 20 carbon atoms such as methyl group and ethyl group; alkoxy groups having 1 to 20 carbon atoms such as methoxy group and ethoxy group; F, Cl, Br, I and the like. a halogen atom; an acyl group having 1 to 20 carbon atoms; an alkyl ester group having 1 to 20 carbon atoms; an alkoxycarbonyl group having 1 to 20 carbon atoms; a halogenated alkyl group having 1 to 20 carbon atoms; Aromatic ring group having 4 to 20 numbers; Amino group; Aminoalkyl group having 1 to 20 carbon atoms; Hydroxyl group; Nitro group; Cyano group; and the like. Examples of the substituent which the benzoyl group or thenoyl group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, and the like. . Among them, a hydrogen atom and a nitro group are preferred, and a hydrogen atom is more preferred, from the viewpoint of radical generation efficiency.

Examples of the method for producing the compound (D1) represented by the general formula (1) include the methods described in JP-T-2019-507108, JP-T-2019-528331, and the like.

Specific examples of the compound (D1) represented by formula (1) are shown below. In addition, this invention is not limited to these.

chemical formula (2)

Other photopolymerization initiators include, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl ]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, etc. acetophenone compounds; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated Benzophenone compounds such as benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methyl Thioxanthone compounds such as thioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl) -s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6- Bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6 -triazine or triazine compounds such as 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl- , 2-(O-benzoyloxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) Oxime ester compounds; phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; 9,10-phenanthrenequinone, camphorquinone , ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; Among these, oxime ester compounds are preferred.

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

The content of the photopolymerization initiator (D) is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the colorant (A). When blended in an appropriate amount, the photocurability and photolithographic properties are further improved.

<Sensitizer>
The photosensitive coloring composition of the present invention can contain a sensitizer.
Examples of sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone. derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives , azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4' -tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone and the like. Among these, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferred. Specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis( dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N - Ethylcarbazole and the like are more preferred.

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

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

<Thermosetting compound>
The photosensitive coloring composition of the invention can contain a thermosetting compound. As a result, the thermosetting compound reacts in the heating step, increasing the crosslink density and improving the heat resistance.

The thermosetting compound may be a low molecular weight compound or a high molecular weight compound such as a resin. Thermosetting compounds include, for example, epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenolic compounds. Among these, epoxy compounds and oxetane compounds are preferred.

The content of the thermosetting compound is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition.

<Thiol chain transfer agent>
The photosensitive coloring composition can contain a chain transfer agent. The chain transfer agent is preferably a thiol chain transfer agent. A thiol-based chain transfer agent, when used in combination with a photopolymerization initiator, generates thiyl radicals that are less likely to be inhibited by oxygen during radical polymerization after photoirradiation, improving the sensitivity of the photosensitive coloring composition.

The thiol-based chain transfer agent is preferably a polyfunctional thiol having two or more thiol groups (SH groups). The thiol-based chain transfer agent more preferably has 4 or more SH groups. As the number of functional groups increases, photocuring from the surface to the deepest part of the film becomes easier.

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

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

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

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

Polymerization inhibitors include, for example, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propyl catechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert Alkylcatechol compounds such as -butylcatechol and 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol , 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, alkylresorcinol compounds such as 4-tert-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2 ,5-di-tert-butylhydroquinone and other alkylhydroquinone compounds; tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine and other phosphine compounds; Phosphine oxide compounds, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol, phloroglucine and the like.

The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass in the non-volatile content of the photosensitive coloring composition. If it is contained in an appropriate amount, it becomes easy to obtain a good pattern shape.

<Ultraviolet absorber>
The photosensitive coloring composition can contain an ultraviolet absorber. Examples of ultraviolet absorbers include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, and salicylate compounds. In addition, the ultraviolet absorber may be an oligomer or polymer.

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

Moreover, the total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the non-volatile matter of the photosensitive coloring composition. When contained in an appropriate amount, the adhesion between the substrate and the film is further improved, and good resolution can be obtained.

Benzotriazole compounds include 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5 -bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy- 5′-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethyl ethyl)-4-hydroxy, a mixture of C7-9 side chain and linear alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-( 2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction product, 2-(2H-benzotriazol-2-yl)-4-(1,1 ,3,3-tetramethylbutyl)phenol, 2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2 -(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-(3,5 -di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert- Butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro- 2H-benzotriazol-2-yl)phenyl]propionate.

Triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6 -bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxyphenyl )-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidate ester reaction product, 2,4-bis "2-hydroxy-4- butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyl oxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine and the like.

Benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2 , 2′,4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone and the like.

Salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tertbutylphenyl salicylate.

The content of the ultraviolet absorber is preferably 5 to 70% by weight based on the total 100% by weight of the photopolymerization initiator and the ultraviolet absorber. A good pattern shape can be easily obtained when it is contained in an appropriate amount. In addition, suppose that content of a sensitizer is included in content of a photoinitiator when a photosensitive coloring composition contains a sensitizer.

<Antioxidant>
The photosensitive coloring composition can contain an antioxidant. Antioxidants prevent the coating formed from the photosensitive coloring composition from yellowing due to oxidation during thermal curing and ITO annealing, and can suppress decrease in transmittance of the coating. Especially when the concentration of the coloring agent in the photosensitive coloring composition is high, the content of the photopolymerizable compound (D) is relatively reduced. is prone to yellowing. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating process, and to suppress a decrease in the transmittance of the coating.

Antioxidants are compounds with radical-scavenging or peroxide-decomposing functions. Antioxidants include hindered phenol compounds, hindered amine compounds, phosphorus compounds, sulfur compounds, hydroxylamine compounds, and the like. The antioxidant is preferably a compound containing no halogen atoms.

The antioxidant (L) can be used alone or in combination of two or more.

The content of the antioxidant (L) is preferably 0.5 to 5.0% by mass based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When contained in an appropriate amount, transmittance, spectral characteristics, and sensitivity are improved.

<Leveling agent>
The photosensitive coloring composition can contain a leveling agent. This further improves the wettability with respect to the transparent substrate and the drying property of the coating when the coating is formed. Examples of leveling agents include silicone surfactants, fluorosurfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.

Examples of silicone-based surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers in which organic groups are introduced into side chains or terminals.

Commercially available products are, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377 manufactured by BYK Chemie, 378, 3455, UV3510, 3570, Toray Dow Corning FZ-7002, 2110, 2122, 2123, 2191, 5609, Shin-Etsu Chemical Co., Ltd. X-22-4952, X-22-4272, X- 22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341 and the like.

Fluorosurfactants include, for example, surfactants or leveling agents having fluorocarbon chains.

Commercially available products are, for example, Surflon S-242, 243, 420, 611, 651, 386 manufactured by AGC Seimi Chemical Co., Ltd., and Megafac F-253, 477, 551, 552, 555, 558, 560, 570 manufactured by DIC Corporation. , 575, 576, R-40-LM, R-41, RS-72-K, DS-21, Sumitomo 3M FC-4430, 4432, Mitsubishi Materials Electronic Chemicals EF-PP31N09, EF-PP33G1 , EF-PP32C1, and Ftergent 602A manufactured by Neos.

Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrister ether, polyoxyethylene octyl Dodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Alkyl ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan mono Laurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxytetraoleic acid Ethylene sorbitol, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamides, alkylimidazolines, and the like.

Commercially available products are, for example, Kao Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430 , 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90 , B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, Rhodol SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V , SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60 (K), Amit 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, Adeka Pluronic (registered trademark) L-23, 31 manufactured by ADEKA, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, Kyoeisha Chemical Co., Ltd. (meth)acrylic acid-based (co)polymer Polyflow-No. 75, No. 90, No. 95 and the like.

Examples of cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride and cetyltrimethylammonium chloride, and their ethylene oxide adducts.

Commercially available products include, for example, Acetamine 24, Kotamine 24P, 60W, 86P conch manufactured by Kao Corporation.

Anionic surfactants include, for example, polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonates, sodium alkyldiphenylether disulfonates, and monoethanol lauryl sulfate. amine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate, and the like.

Commercially available products include, for example, Futergent 100 and 150 manufactured by Neos, Adeka Hope YES-25, Adekacol TS-230E, PS-440E and EC-8600 manufactured by ADEKA.

Amphoteric surfactants include, for example, lauramidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, alkylbetaines such as alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.

Commercially available products include Amphithol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, 20N manufactured by Kao Corporation.

A leveling agent (M) can be used individually or in combination of 2 or more types.

The content of the leveling agent (M) is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on 100% by mass of non-volatile matter in the photosensitive coloring composition. Within this range, the balance between applicability and adhesion of the photosensitive coloring composition is further improved.

<Storage stabilizer>
The photosensitive coloring composition can contain storage stabilizers to stabilize the viscosity of the composition over time. Storage stabilizers include, for example, quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine; organic acids such as lactic acid and oxalic acid and their methyl ethers; phosphine, phosphite and the like.

The content of the storage stabilizer is preferably 0.1 to 10% by mass with respect to 100 parts by mass of the colorant (A).

<Adhesion improver>
The photosensitive coloring composition can contain an adhesion improver. This further improves the adhesion between the coating and the substrate. In addition, it becomes easier to form a narrow pattern by photolithography. Adhesion improvers include, for example, silane coupling agents.

Examples of silane coupling agents include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, (Meth)acrylsilanes such as 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxysilanes, N-2-(aminoethyl)-3-aminopropyl methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3- dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, aminosilanes such as hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyl mercaptos such as methyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureides such as 3-ureidopropyltriethoxysilane; Examples include sulfides and isocyanates such as 3-isocyanatopropyltriethoxysilane.

The content of the adhesion improver is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the colorant (A). When contained in an appropriate amount, the photosensitivity of the photosensitive coloring composition is improved, the adhesion of the coating is further improved, and the resolution of the pattern is also further improved.

<Solvent>
The photosensitive coloring composition can contain a solvent. This facilitates the adjustment of the viscosity of the photosensitive coloring composition, making it easier to form a film with a smooth surface. The solvent may be appropriately selected according to the purpose of use and contained in an appropriate amount.

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

Among the above solvents, it is preferable to include an organic solvent having a boiling point of 120° C. or higher and 180° C. or lower at 1 atm from the viewpoint of coating properties and drying properties. Among these, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl- 2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone and the like are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and the like are more preferred.

<Method for producing a photosensitive coloring composition>
The photosensitive coloring composition is subjected to a dispersion treatment using, for example, the coloring agent (A), a dye derivative and/or a dispersing resin, to prepare a coloring agent dispersion. Then, the colorant dispersion, the alkali-soluble resin (B), the polymerizable compound (C), the photopolymerization initiator (D), etc. can be blended and mixed. The materials to be blended and the timing of blending are arbitrary. Moreover, a dispersion|distribution process can also be performed in multiple times.

For the dispersion treatment, for example, a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor can be used.

<Removal of coarse particles>
In this specification, it is preferable to remove coarse particles contained after preparing the colorant (A) dispersion stage or the photosensitive coloring composition. As a result, foreign matter can be removed from the film, making it easier to form a fine pattern.
The removal is preferably carried out by a method such as centrifugal separation, sintered filter, membrane filter, or the like. As a result, foreign substances such as coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more can be removed. Thus, the photosensitive coloring composition preferably does not substantially contain particles of 0.5 μm or more, and preferably does not contain particles of 0.3 μm or less.

<Water content in photosensitive coloring composition>
The content of water contained in the photosensitive coloring composition of the present invention is preferably 2% by mass or less. When the water content is within the above range, the photosensitive coloring composition is excellent in dispersion stability and sensitivity after storage over time. In addition, 1.8 mass % or less is preferable and, as for content of water, 1.6 mass % or less is more preferable.

A method for controlling the water content is not particularly limited, and a known method can be used. Examples thereof include a method of producing a photosensitive colored composition while blowing in a dry inert gas, and a method of adding molecular sieves and dehydrating after production. Among them, the method of adjusting while blowing dry inert gas is preferable.

The water content can be measured by a known method such as the Karl Fischer method.

<Color filter>
The color filter herein comprises a substrate (also referred to as a transparent substrate) and filter segments formed from a photosensitive coloring composition. The color filter segment (hereinafter also referred to as filter segment) preferably has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of coloring agent (A) used. In addition, the color filter may have a magenta filter segment, a cyan filter segment, and a yellow filter segment of complementary colors instead of these color filter segments. A reflective substrate can be used instead of the transparent substrate. Examples of transparent substrates include glass substrates. Examples of the reflective substrate include a substrate using an aluminum electrode or a metal thin film as a reflective surface.

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

Filter segments can be formed by, for example, a printing method, an electrodeposition method, a transfer method, an inkjet method, a photolithography method, or the like. The most preferred photolithographic methods are described herein.

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

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

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

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

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

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

<Liquid crystal display device>
The image display device of this specification includes a color filter. The image display device preferably further includes a light source. A liquid crystal display device will be described as an example of the image display device.
A liquid crystal display device includes a color filter and a light source. Examples of the light source include a cold cathode fluorescent lamp (CCFL) and a white LED. In the present invention, it is preferable to use a white LED in terms of widening the reproduction range of red. FIG. 1 is a schematic cross-sectional view of a liquid crystal display device 10 having a color filter of the present invention. The device 10 shown in FIG. 1 comprises a pair of transparent substrates 11 and 21 spaced and opposed to each other, with a liquid crystal LC sealed between them.

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

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

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

A polarizing plate 25 is formed on the outer surface of the transparent substrate 21 . A backlight unit 30 is provided below the polarizing plate 15 .

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

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

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

The following examples illustrate the invention. However, the present invention is not limited to these. In addition, "part" is "mass part" and "%" is "mass%".

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

(Average molecular weight of resin)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as the apparatus, two separation columns were connected in series, and "TSK-GEL SUPER HZM-N" was used as both packing materials, and the oven temperature was 40 ° C. , using a tetrahydrofuran (THF) solution as an eluent and measuring at a flow rate of 0.35 ml/min. The sample was dissolved in a solvent consisting of 1% by weight of the above eluent and injected at 20 microliters. A molecular weight is a polystyrene conversion value.

(Acid value of resin)
Add 80 ml of acetone and 10 ml of water to 0.5 to 1 g of the resin solution and stir to dissolve uniformly. (manufactured) to measure the acid value (mgKOH/g). Then, the acid value per nonvolatile content of the resin was calculated from the acid value of the resin solution and the concentration of the nonvolatile content of the resin solution.

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

(Ammonium salt value (mgKOH/g))
The ammonium salt value is determined by titration with a 0.1N aqueous solution of silver nitrate using a 5% aqueous solution of potassium chromate as an indicator, and then converted into the equivalent weight of potassium hydroxide.

<Production of colorant (A)>
(Refined red pigment (A-1))
C. I. Pigment Red 254 (100 parts), sodium chloride (1,200 parts) and diethylene glycol (120 parts) were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 6 hours. Next, the kneaded mixture is put into hot water, heated to about 80°C and stirred with a high-speed mixer for 1 hour to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, and then heated to 80°C. It was dried for a whole day and night and pulverized to obtain a finely divided red pigment (A-1).

(Refined red pigment (A-2))
C. I. Pigment Red 177 (100 parts), sodium chloride (1,200 parts) and diethylene glycol (120 parts) were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 6 hours. Next, the kneaded mixture is put into hot water, heated to about 80°C and stirred with a high-speed mixer for 1 hour to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, and then heated to 80°C. It was dried for a whole day and night and pulverized to obtain a finely divided red pigment (A-2).

(Micronized blue pigment (A-3))
C. I. Pigment Blue 15:6 (100 parts), sodium chloride (1,000 parts) and diethylene glycol (100 parts) were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50° C. for 12 hours. This mixture is poured into 3,000 parts of hot water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. was dried for 24 hours and pulverized to obtain a finely divided blue pigment (A-3).

(Micronized purple pigment (A-4))
C. I. Pigment Violet 23 (100 parts), sodium chloride (1,200 parts) and diethylene glycol (100 parts) were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80° C. for 6 hours. Next, this kneaded product was put into 8,000 parts of hot water, stirred for 2 hours with a high-speed mixer while heating to 80° C. to form a slurry, and repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. After that, it was dried at 85° C. for 24 hours and pulverized to obtain a finely divided purple pigment (A-4).

(Micronized green pigment (A-5))
C. I. 100 parts of Pigment Green 58, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 6 hours. This kneaded product is put into 3000 parts of hot water, stirred for 1 hour with a high-speed mixer while heating to 70° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then kept at 80° C. for a day and night. A fine green pigment (A-5) was obtained by drying and pulverizing.

(Micronized green pigment (A-6)
A green pigment (A-6) of the following chemical formula (12) was obtained according to the example of JP-A-2017-111398. 100 parts of green pigment (A-6), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 6 hours. This kneaded product is put into 3000 parts of hot water, stirred for 1 hour with a high-speed mixer while heating to 70° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then kept at 80° C. for a day and night. A fine green pigment (A-6) was obtained by drying and pulverizing.
chemical formula (12)

(Micronized yellow pigment (A-7))
C. I. Pigment Yellow 150 (100 parts), sodium chloride (700 parts) and diethylene glycol (180 parts) were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80° C. for 6 hours. This mixture is poured into 2,000 parts of hot water, stirred for 1 hour with a high-speed mixer while heating to 80°C to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then kept at 80°C for a day and night. A fine yellow pigment (A-7) was obtained by drying and pulverizing.

(Micronized yellow pigment (A-8))
C. I. Pigment Yellow 138 (100 parts), pulverized sodium chloride (800 parts) and diethylene glycol (100 parts) were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 12 hours. This mixture is poured into 3000 parts of hot water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then kept at 80°C for a day and night. A fine yellow pigment (A-8) was obtained by drying and pulverizing.

(Micronized yellow pigment (A-9))
C. I. 100 parts of Pigment Yellow 185 (“Palitol Yellow D1155” manufactured by BASF Japan), 700 parts of pulverized sodium chloride, and 180 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. . Next, this kneaded product is put into 8 liters of hot water, stirred with a high-speed mixer for 2 hours while heating to 80°C to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then heated to 85°C. It was dried overnight at room temperature and pulverized to obtain a finely divided yellow pigment (A-9).

(Micronized yellow pigment (A-10)
A yellow pigment (A-10) of the following chemical formula (13) was obtained according to the example of JP-A-2012-226110. 100 parts of yellow pigment (A-10), 700 parts of pulverized sodium chloride, and 180 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80° C. for 6 hours. Next, this kneaded product is put into 8 liters of hot water, stirred with a high-speed mixer for 2 hours while heating to 80°C to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then heated to 85°C. The mixture was dried overnight and pulverized to obtain a finely divided yellow pigment (A-10).
chemical formula (13)

The average primary particle size of the finely divided pigment was in the range of 5 to 120 nm.

(Dye (A-11))
The C.I. I. A dye (A-11), which is a salt-forming compound consisting of Acid Red 52 and Resin 1 having a cationic group in the side chain, was produced.
A four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser was charged with 67.3 parts of methyl ethyl ketone and heated to 75°C under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2'-azobis(2,4-dimethylvaleronitrile ) and 25.1 parts of methyl ethyl ketone were homogenized, charged into a dropping funnel, attached to a four-necked separable flask, and added dropwise over 2 hours. After 2 hours from the completion of dropping, it was confirmed that the polymerization yield was 98% or more from the non-volatile matter and the weight average molecular weight (Mw) was 6,830, and the mixture was cooled to 50°C. 3.2 parts of methyl chloride and 22.0 parts of ethanol were added thereto, and the mixture was reacted at 50° C. for 2 hours, then heated to 80° C. over 1 hour, and further reacted for 2 hours. Thus, Resin 1 having a cationic group in a side chain containing 47% by mass of ammonium group as a resin component was obtained. The ammonium salt value of the obtained resin was 34 mgKOH/g.
Next, to 2,000 parts of water, 30 parts of Resin 1 having a cationic group on a side chain was added in terms of non-volatile content, and the mixture was sufficiently stirred and mixed, and then heated to 60°C. On the other hand, 10 parts of C.I. I. An aqueous solution in which Acid Red 52 was dissolved was prepared, and was added dropwise to the previous resin solution. After dropping, the mixture was stirred at 60° C. for 120 minutes to sufficiently react. To confirm the end point of the reaction, the reaction solution was added dropwise to a filter paper, and the point at which no bleeding occurred was regarded as the end point, and it was determined that a salt-forming compound was obtained. After allowing to cool to room temperature while stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer. I. A dye (A-11), which is a salt-forming compound of Acid Red 52 and Resin 1 having a cationic group in the side chain, was obtained. At this time, C.I. I. The content of components derived from Acid Red 52 was 25% by mass.

<Production of alkali-soluble resin (B)>
(Alkali-soluble resin (B1-1) solution)
270.0 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) was placed in a reaction vessel equipped with a separable 4-necked flask, a thermometer, a condenser, a nitrogen gas introduction tube, and a stirring device, and 120 parts of nitrogen gas was introduced into the vessel. ℃, and at the same temperature, 80.0 parts of glycidyl methacrylate (hereinafter, GMA), 75.0 parts of dicyclopentanyl methacrylate (hereinafter, DCPMA), 29.0 parts of styrene, and a polymerization initiator were added from a dropping tube. A mixture of 19.0 parts of certain t-butylperoxy-2-ethylhexanoate and PGMAc was added dropwise over 2.5 hours.
After the dropwise addition was completed, the mixture was further stirred at 120° C. for 2 hours to obtain a precursor. After that, the inside of the flask was replaced with air, and 40.6 parts of acrylic acid (hereinafter referred to as AA) as a modified compound, and 0.6 parts of triphenylphosphine and 0.2 parts of methylhydroquinone as catalysts were added. It was made to react for 10 hours. As a result, a monomer unit (hereinafter referred to as GMA+AA) was obtained by reacting the epoxy group of GMA with the carboxyl group of AA, and a polymerizable unsaturated group-containing monomer unit was introduced.
Then, 93.0 parts of succinic anhydride (hereinafter referred to as SHA) was added as a modifying compound, and the mixture was reacted at 110° C. for 4 hours. As a result, some of the hydroxyl groups of GMA+AA were reacted with SHA. After that, PGMAc was added so that the non-volatile content was 20% by mass to prepare an alkali-soluble resin (B1-1) solution. The alkali-soluble resin (B1-1) had an acid value of 79 mgKOH/g and a weight average molecular weight of 6,000.

(Alkali-soluble resin (B1-2) to (B1-3) solution)
Alkali-soluble resins (B1-2) to (B1-3) were synthesized in the same manner as the alkali-soluble resin (B1-1) by changing the compounding type and amount so that the composition ratio shown in Table 1 was obtained. , and PGMAc were added to adjust the non-volatile content to 20% by mass.

MAA+GMA described in Table 1 represents a polymerizable unsaturated group-containing monomer unit obtained by adding an epoxy group of GMA to a carboxyl group derived from methacrylic acid (hereinafter referred to as MAA) in the precursor. GMA+AA+THPA represents a polymerizable unsaturated group-containing monomer unit obtained by reacting part of the hydroxyl groups at the reaction site of GMA+AA with tetrahydrophthalic anhydride (THPA).

(Alkali-soluble resin (B2) solution)
196 parts of cyclohexanone was charged into a reaction vessel equipped with a separable 4-necked flask, a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80°C, and after replacing the inside of the reaction vessel with nitrogen, the mixture was added dropwise. From the tube, 25.1 parts of benzyl methacrylate, 23.0 parts of n-butyl methacrylate, 14.3 parts of 2-hydroxyethyl methacrylate, 13.4 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (manufactured by Toagosei Co., Ltd. "Aronix M110") 24.1 parts and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 more hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution is sampled and dried by heating at 180° C. for 20 minutes to measure the nonvolatile content, and PGMAc is added to the previously synthesized resin solution so that the nonvolatile content is 20% by mass. Then, an alkali-soluble resin (B2) solution was prepared. It had an acid value of 87 mgKOH/g and a weight average molecular weight of 25,000.

<Production of polymerizable compound (C)>
(Aliphatic urethane (meth) acrylate (C1-3))
400 parts of dipentaerythritol pentaacrylate, 100 parts of propylene glycol monomethyl ether acetate, and 0.5 parts of N,N dimethylbenzylamine were placed in a 5-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer and dropping tube. was charged, the temperature was raised to 70° C., and a mixture of 64 parts of hexamethylene diisocyanate and 64 parts of propylene glycol monomethyl ether acetate was dropped from the dropping tube over 2 hours. After dropping, reaction was carried out at a temperature of 5070° C. for 8 hours, and disappearance of absorption of isocyanate at 2180 cm 1 was confirmed by IR. The solvent was distilled off to obtain an aliphatic urethane acrylate (C1-3) having 10 polymerizable unsaturated groups.

(Polymerizable compound having an acid group (C3-2))
400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine were charged into a 5-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube. C., and a mixture of 66 parts of toluene diisocyanate and 66 parts of PGMAc was dropped from the dropping tube over 2 hours. After dropping, reaction was carried out at a temperature of 50 to 70° C. for 8 hours, and disappearance of absorption of isocyanate at 2180 cm −1 was confirmed by IR. Then, 35 parts of mercaptoacetic acid and 0.6 parts of 4-methoxyphenol were charged and reacted at a temperature of 50-60° C. for 6 hours. The solvent was distilled off to obtain a polymerizable compound (C3-2) having an acid group.

<Production of dispersion resin (G)>
(Dispersion resin (G-1) solution)
10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate and 50 parts of PGMAc were introduced into a reaction vessel equipped with a gas inlet tube, a temperature control, a condenser and a stirrer, and the atmosphere was purged with nitrogen gas. The inside of the reaction vessel was heated to 50° C. with stirring, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90° C., and the mixture was reacted for 7 hours while adding a solution of 0.1 part of 2,2′-azobisisobutyronitrile to 90 parts of PGMAc. It was confirmed by measuring the non-volatile content that 95% had reacted. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and reacted at 100° C. for 7 hours. . After confirming that 98% or more of the acid anhydride is half-esterified by acid value measurement, the reaction is terminated, and PGMAc is added to dilute so that the nonvolatile content is 30% by nonvolatile content measurement, and the acid value is 70 mgKOH / g. , and a dispersion resin (G-1) solution having a weight average molecular weight of 8,500 was obtained.

(Dispersion resin (G-2) solution)
108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst were charged into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer. After substitution, reaction was carried out at 120° C. for 5 hours (first step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step in terms of non-volatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate Parts, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged, the inside of the reaction vessel was heated to 80° C., 1.2 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) was added, and the mixture was reacted for 12 hours. (Second step). It was confirmed by measuring the non-volatile content that 95% had reacted. Finally, 500 parts of a diluted PGMAc solution with a non-volatile content of 50% of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 part of hydroquinone were charged, and the isocyanate was measured by IR. The reaction was carried out until the disappearance of the peak at 2270 cm −1 based on the group was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the non-volatile content was adjusted with PGMAc to obtain a dispersion resin (G-2) solution with a non-volatile content of 30%. The resulting dispersion resin (G-2) had an acid value of 68 mgKOH/g, an unsaturated double bond equivalent of 1,593, and a weight average molecular weight of 13,000.

(Dispersion resin (G-3) solution)
3 parts of trimellitic anhydride, 1 part of 3-mercapto-1,2-propanediol, 50 parts of methoxypropyl acetate, 0.5 parts of dimethylbenzylamine were added to a reactor equipped with a gas inlet tube, a condenser, a stirring blade and a thermometer. I ordered one part. After purging with nitrogen gas, the inside of the reaction vessel was heated to 120° C. and reacted for 4 hours, and then reacted at 80° C. for 2 hours. Further, 30 parts of tertiary butyl acrylate, 20 parts of ETERNACOLL OXMA (3-ethyl-3-oxetanyl) methyl methacrylate, manufactured by Ube Industries, Ltd.), 5 parts of methacrylic acid, 40 parts of ethyl acrylate, and 10 parts of methoxypropyl acetate were added to the reaction vessel. While maintaining the inside at 80° C., 0.2 part of 2,2′-azobisisobutyronitrile was added in 15 portions every 30 minutes. A non-volatiles measurement was taken one hour after the final addition and confirmed that 95% of the monomer had reacted. After a final dilution with methoxypropyl acetate, the reaction was completed by cooling. A dispersant (G-3) having a nonvolatile content of 30%, an acid value per nonvolatile content of 51 mgKOH/g, and a weight average molecular weight (Mw) of 24,000 was obtained.

(Dispersion resin (G-4) solution)
30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reaction apparatus equipped with a gas inlet tube, condenser, stirring blade, and thermometer, and nitrogen was flowed. While stirring at 50° C. for 1 hour, the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110° C. under a nitrogen stream to initiate polymerization of the first block (B block). After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., Fancryl FA-711MM) as a second block (A block) monomer were added to the reactor. The reaction was continued by stirring while maintaining the temperature at 110° C. under a nitrogen atmosphere. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled and the nonvolatile content was measured. % or more, the reaction solution was cooled to room temperature to terminate the polymerization. PGMAc was added to dilute the nonvolatile content to 30% by nonvolatile measurement to obtain a dispersion resin (G-4) solution having an amine value per nonvolatile content of 57 mgKOH/g and a number average molecular weight of 4,500 (Mn). .

(Dispersion resin (G-5) solution)
250 parts by mass of tetrahydrofuran (THF) and 5.81 parts by mass of dimethylketenemethyltrimethylsilyl acetal as an initiator were placed in a 500 mL four-neck separable flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a stirrer, and a digital thermometer. was added through the addition funnel, and nitrogen substitution was sufficiently performed. 0.5 parts by mass of a 1 mol/L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst was injected using a syringe, and 19.7 parts by mass of 2-hydroxyethyl methacrylate as a block monomer having solvent affinity. , 7.5 parts by mass of 2-ethylhexyl methacrylate, 12.9 parts by mass of n-butyl methacrylate, 10.7 parts by mass of benzyl methacrylate, and 30.9 parts by mass of methyl methacrylate were added for 60 minutes using an addition funnel. dripped over. The temperature was kept below 40° C. by cooling the flask with an ice bath. After 1 hour, 18.3 parts by mass of dimethylaminopropyl methacrylamide, which is a monomer for colorant adsorption functional block, was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to terminate the reaction. The resulting block copolymer THF solution was reprecipitated in hexane, filtered and vacuum dried for purification.
Subsequently, 15.0 parts by mass of the resulting block copolymer was dissolved in 35 parts by mass of PGMAc in a 100 mL round-bottomed flask, and 1.1 parts by mass of phenylphosphinic acid (dimethylaminopropyl methacrylamide), which is a salt-forming component, was dissolved. 0.5 molar equivalent) was added, stirred at a reaction temperature of 30° C. for 20 hours, and adjusted by adding PGMAc to obtain a dispersion resin (G-5) solution having a nonvolatile content of 30%.

<Production of dispersion>
(Dispersion 1)
Using zirconia beads with a diameter of 0.5 mm, after dispersing for 3 hours with an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.), it was filtered through a filter with a pore size of 1.0 μm. Dispersion 1 was produced. Organic solvent (P-1) is PGMAc.
Micronized blue pigment (A-3): 9.05 parts by mass Micronized purple pigment (A-4): 0.31 parts by mass Dye (A-11): 4.16 parts by mass Dye derivative (F-1 ): 1.04 parts by mass Dispersion resin (G-1) solution: 3.47 parts by mass Alkali-soluble resin ( B2 ) solution: 10.0 parts by mass Organic solvent (P-1): 71.97 parts by mass

ただしｎは１～４の整数である。 Dye derivative (F-1): the following structure

However, n is an integer of 1-4.

Dispersions 2 to 9 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts shown in Table 3 were changed.

Dye derivative (F-2) in Table 3: the following structure

Dye derivative (F-3) in Table 3: the following structure

Dye derivative (F-4): the following structure

Dye derivative (F-5): the following structure

<Production of photosensitive coloring composition>
[Example 1]
(Photosensitive coloring composition 1)
The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition 1.
Dispersion 3: 31.74 parts by mass Dispersion 5: 27.44 parts by mass Alkali-soluble resin (B1-1) solution: 2.90 parts by mass Polymerizable compound (C1-1): 2.12 parts by mass Polymerizable compound (C2-1): 1.20 parts by mass Polymerizable compound (C4-1): 1.70 parts by mass Oxime photopolymerization initiator (D2b-1): 0.44 parts by mass Thermosetting compound (H1-1 ): 0.08 parts by mass Polymerization inhibitor (J): 0.0015 parts by mass Leveling agent (M): 0.50 parts by mass Organic solvent (P): 31.89 parts by mass

[Examples 2-31, Comparative Examples 1-2]
Examples 2 to 21 in the same manner as in Example 1, except that the photosensitive coloring composition 1 of Example 1 was changed to the raw materials and amounts described in Tables 4-1 to 4-2, and Comparative Examples 1 to No. 2 photosensitive coloring composition was prepared. Examples 5, 6 and 10-12 herein are reference examples.

The raw materials listed in Tables 4-1 and 4-2 are as follows.

[Polymerizable compound (C)]
(Aliphatic urethane acrylate (C1))
C1-1: UA-306H (manufactured by Kyoeisha Chemical Co., Ltd.)
C1-2: UA-306I (manufactured by Kyoeisha Chemical Co., Ltd.)

(Polymerizable compound (C2) having a viscosity of 800 mPa S or less at 25°C)
The number of functional groups of the polymerizable unsaturated group and the viscosity at 25°C are described in parentheses.
C2-1: M-309 (manufactured by Toagosei Co., Ltd.: trifunctional, 60-150 mPa s)
C2-2: M-310 (manufactured by Toagosei Co., Ltd.: trifunctional, 60-110 mPa s)
C2-3: M-450 (manufactured by Toagosei Co., Ltd.: tetrafunctional, 400-650 mPa s)
C2-4: A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.: bifunctional, 135 mPa s)

(Polymerizable compound (C3) having an acid group)
C3-1: Aronix M-520 (manufactured by Toagosei Co., Ltd., polybasic acid-modified acrylic oligomer acid group: carboxyl group)

(Other polymerizable compounds (C4))
C4-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
C4-2: UA-306T (manufactured by Kyoeisha Chemical Co., Ltd., aromatic urethane acrylate modified tolylene diisocyanate)

[Photoinitiator (D)]
[Compound (D2b) Containing Two Oxime Groups in One Molecule]
D2b-1: compound of the above chemical formula (8) D2b-2: compound of the above chemical formula (11)

[Compound (D2a) containing one oxime group in one molecule]
D2a-1: TRONLY TR-PBG-3057 (manufactured by Changzhou Tenryu New Materials Co., Ltd., a compound containing one oxime group in one molecule)
D2a-2: compound of chemical formula (3) above D2a-3: compound of chemical formula (4) above D2a-4: compound of chemical formula (5) above D2a-5: compound of chemical formula (6) above

(Photopolymerization initiator (D1) represented by general formula (1))
D1-1: the compound of the above chemical formula (2)

(Other photoinitiators (D3))
D3-1: Omnirad 907 (manufactured by IGM Resins, acetophenone compound)
D3-2: Omnirad 369 (manufactured by IGM Resins, acetophenone compound)

[Sensitizer (E)]
(Thioxanthone-based compound (E1))
D1-1: 2,4-diethylthioxanthone (benzophenone compound (E2))
D2-1: 4,4'-bis(diethylamino)benzophenone

[Thermosetting compound]
(Epoxy compound (H1))
H1-1: EHPE-3150 (manufactured by Daicel)

[Polymerization inhibitor (J)]
J-1: 4-methylcatechol J-2: methylhydroquinone J-3: t-butylhydroquinone Above, (J-1) to (J-3) are mixed in the same amount, respectively, polymerization inhibitor (J) and

[Leveling agent (M)]
M-1: BYK-330 (manufactured by BYK-Chemie)
M-2: Megafac F-551 (manufactured by DIC)
1 part of each of (M-1) and (M-2) above was mixed and dissolved in 98 parts of PGMAc to prepare a mixed solution as a leveling agent (M).

[Organic solvent (P)]
P-1: 30 parts of propylene glycol monomethyl ether acetate P-2: 30 parts of cyclohexanone P-3: 10 parts of ethyl 3-ethoxypropionate P-4: 10 parts of propylene glycol monomethyl ether P-5: 10 parts of cyclohexanol acetate P -6: 10 parts of dipropylene glycol methyl ether acetate Above, (P-1) to (P-6) were mixed in the above parts by mass to obtain an organic solvent (P).

<Evaluation of photosensitive coloring composition>
The photosensitive coloring compositions of Examples 1 to 21 and Comparative Examples 1 and 2 were evaluated for heat resistance, overriding ratio, line width sensitivity, luminance (only green pixels were evaluated) and wrinkles by the following methods. Table 5 shows the evaluation results.

[Heat resistance evaluation]
The obtained photosensitive coloring composition was coated on a 0.7 mm glass substrate (Eagle 2000 manufactured by Corning) by spin coating so that the film thickness after drying was 2.5 μm. and dried in a vacuum dryer. Then, exposure was performed using a high-pressure mercury lamp at illuminance of 30 mW/cm ² and 25 mJ/cm ² . After that, it was spray-developed with an aqueous solution of sodium carbonate at 23° C. for 40 seconds, washed with deionized water, air-dried, and heated in a clean oven at 230° C. for 30 minutes.
Chromaticity ([L ^* , (1), a ^* (1), b ^* (1)]) of the resulting coating film under C light source was measured with a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). was measured using Furthermore, after that, as heat resistance evaluation, it is heated at 230 ° C. for 1 hour, and the chromaticity with C light source ([L ^* , (2), a ^* (2), b ^* (2)]) is measured, and the following calculation formula The color difference ΔEab* was obtained by The evaluation criteria are as follows, and 3 or more is regarded as practical.
ΔEab ^* = ((L ^* (2)-L ^* (1)) ² +(a ^* (2)-a ^* (1)) ² +(b ^* (2)-b ^* (1)) ² )1 /2
5: ΔEab ^* is less than 1 4: ΔEab ^* is 1 or more and less than 2 3: ΔEab ^* is 2 or more and less than 3 2: ΔEab ^* is 3 or more and less than 5 1: ΔEab ^* is 5 or more

[Evaluation of run-on rate]
The height control of the laminated photospacer was evaluated by the overriding ratio. The obtained photosensitive coloring composition was spin-coated onto a 0.7 mm glass substrate (Eagle 2000 manufactured by Corning Co., Ltd.) of 100 mm long x 100 mm wide on which a black matrix was arranged so that the film thickness after drying was 2.5 μm. and dried in a vacuum dryer. Then, exposure was performed using a high-pressure mercury lamp at an illuminance of 30 mW/cm ² and 25 mJ/cm ² . After that, it was spray-developed with an aqueous solution of sodium carbonate at 23° C. for 40 seconds, washed with deionized water, air-dried, and heated in a clean oven at 230° C. for 30 minutes.
Next, the pixel film thickness (A) and the film thickness (B) of the laminated portion on the black matrix shown in the cross-sectional view of the color filter (FIG. 2) were measured with a contact-type film thickness meter, and the overriding ratio (B ÷ A × 100) was calculated. The results are shown in Table 5. Practical use is possible with 3 or more.
5: Run-on rate is 75 or more and less than 80 4: Run-on rate is 80 or more and less than 82.5 3: Run-on rate is 82.5 or more and less than 85 2: Run-on rate is 85 or more and less than 90 1: Run-on rate is 90 or more

[Line width sensitivity]
Pixel width control at low exposure was evaluated by line width sensitivity. The obtained photosensitive coloring composition is coated on a 0.7 mm glass substrate (Eagle 2000 manufactured by Corning) by spin coating so that the film thickness after drying is 2.5 μm. and dried in a vacuum dryer. Then, pattern exposure using a photomask was performed using a high-pressure mercury lamp at an illumination intensity of 30 mW/cm ² and 25 mJ/cm ² . Note that the distance between the substrate and the photomask was set to 150 μm. After that, it was spray-developed with an aqueous solution of sodium carbonate at 23° C. for 40 seconds, washed with deionized water, air-dried, and heated in a clean oven at 230° C. for 30 minutes.
The resulting photolithographic pattern pixel width was measured with an optical microscope ("BX-51" manufactured by Olympus Optical Co., magnification: 500) and image processing software (ImagePro). 3 or more is made practical.
5: The value of (pixel width - photomask opening width) is 10 μm or more 4: The value of (pixel width - photomask opening width) is 8 μm or more and less than 10 μm 3: The value of (pixel width - photomask opening width) is 6 μm or more Less than 8 μm 2: The value of (pixel width - photomask opening width) is 2 μm or more and less than 6 μm 1: The value of (pixel width - photomask opening width) is less than 2 μm

[Luminance]
The obtained photosensitive coloring composition was coated on a 0.7 mm glass substrate (Eagle 2000 manufactured by Corning) by spin coating so that the film thickness after drying was 2.5 μm. and dried in a vacuum dryer. Then, pattern exposure using a photomask was performed using a high-pressure mercury lamp at an illumination intensity of 30 mW/cm ² and 25 mJ/cm ² . Note that the distance between the substrate and the photomask was set to 150 μm. After that, it was spray-developed with a sodium carbonate solution at 23° C. for 40 seconds, washed with deionized water, air-dried, and heated in a clean oven at 230° C. for 30 minutes.
A coated substrate was obtained such that x=0.298 and y=0.593 in white LED2. The brightness (Y) of the resulting substrate was measured with a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). 3 or more is made practical.
Luminance is evaluated with the green colored composition, and not evaluated otherwise.
5: 60.4 or more 4: 59.9 or more and less than 60.4 3: 59.4 or more and less than 59.9 2: 57.4 or more and less than 59.4 1: less than 57.4

[Wrinkle]
The pattern surface of the pattern formability evaluation substrate was observed using an optical microscope ("BX-51" manufactured by Olympus Optical Co., Ltd., magnification: 200). 3 or more is made practical.
5: No wrinkles are observed on the surface of the pattern.
4: A very slight wrinkle is observed on the surface of the pattern.
3: Slight wrinkles are observed on the surface of the pattern.
2: Wrinkles are observed on the surface of the pattern.
1: Severe wrinkles are observed on the surface of the pattern.

10 liquid crystal display device 11 transparent substrate 12 TFT array 13 transparent electrode layer 14 alignment layer 15 polarizing plate 21 transparent substrate 22 color filter 23 transparent electrode layer 24 alignment layer 25 polarizing plate 30 backlight unit 31 white LED light source LC liquid crystal 32 black matrix 33 Pixel 34 Laminated photospacer 35 Transparent substrate

Claims (7)

A photosensitive coloring composition containing a coloring agent (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D),
The polymerizable compound (C) contains an aliphatic urethane (meth)acrylate (C1) having no aromatic moiety,
A photosensitive coloring composition in which the photopolymerization initiator (D) contains an oxime ester photopolymerization initiator (D2b) containing two oxime ester groups in one molecule represented by the following general formula (7).
general formula (7)

(In general formula (7), X ₁ and X ₂ each independently represent a carbonyl bond (—CO—) or a single bond. X ₃ represents a single bond. R ₁ has 1 to 20 alkyl groups, R ₂ and R ₃ each independently represent an alkyl group having 1 to 20 carbon atoms , at least one of which is a linear alkyl group, R ₄ and R ₅ each represent Each independently represents an alkyl group having 1 to 20 carbon atoms. The photosensitive coloring composition according to claim 1, wherein the polymerizable compound (C) further contains a polymerizable compound (C2) having a viscosity at 25°C of 800 mPa·S or less. The content of the polymerizable compound (C2) having a viscosity of 800 mPa S or less at 25° C. is 5 to 50% by mass in 100% by mass of the polymerizable compound (C). Photosensitivity according to claim 2 coloring composition. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the coloring agent (A) contains a phthalocyanine pigment whose central metal is Al. A color filter comprising a substrate and a filter segment formed from the photosensitive coloring composition according to any one of claims 1 to 4. An image display device comprising the color filter according to claim 5 . A solid-state imaging device comprising the color filter according to claim 5 .

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