JP7707879B2 - Photosensitive coloring composition, cured film using the same, color filter, image display device, and solid-state imaging device - Google Patents

Description

The present invention relates to a photosensitive coloring composition that can be used in a low-temperature heating process at 150°C or less.

The film or fine pattern of the color filter used in image display devices such as liquid crystal display devices and organic EL display devices, and solid-state imaging devices, is required to have optical properties such as transparency, but is also required to have chemical resistance when performing post-processing such as forming and assembling other components. For this reason, it is known to form a film or fine pattern with excellent chemical resistance by adding a thermal crosslinking agent to the photosensitive coloring composition in advance and performing photocuring and thermal curing. (For example, Patent Documents 1 and 2)

JP 2013-195956 A JP 2011-93955 A

However, as image display devices become more flexible and wearable, there is an increasing need to produce elements using flexible substrates instead of the rigid glass substrates that have been used traditionally. Many flexible substrates are made of organic materials and have lower heat resistance than glass substrates, so it is necessary to lower the heat curing temperature. For example, in the manufacture of color filters, heat curing has been carried out at about 200 to 230°C, but when using a flexible plastic substrate, it is necessary to lower the heat curing temperature to 150°C or less due to the heat resistance issue. However, with conventional compositions, heat curing does not proceed sufficiently, so by using a large amount of highly sensitive photocurable material, the degree of film crosslinking can be increased to obtain the desired heat resistance, but on the other hand, there is a problem that it becomes difficult to form fine patterns.

The present invention aims to provide a photosensitive coloring composition that has excellent chemical resistance and can form fine patterns even when heated at a low temperature of 150°C or less.

The photosensitive coloring composition of the present invention is a photosensitive coloring composition used for forming a pattern of a color filter by a photolithography method in which the pattern is cured by a heating step of 150 ° C. or less after development,
The composition contains a pigment (A), a resin (B), a photopolymerization initiator (C), and a polymerizable compound (D), and is characterized in that the resin (B) contains a resin (B1) that contains a blocked isocyanate group-containing structural unit, and a resin (B2) that contains a (meth)acryloyl group-containing vinyl polymer moiety.

The present invention described above can provide a photosensitive coloring composition that has excellent chemical resistance and can form fine patterns even when heated at a low temperature of 150°C or less. The present invention can also provide a color filter, a liquid crystal display device, an image display device such as an organic EL display device, and a solid-state imaging device based on the photosensitive coloring composition.

The terms used in this specification are defined below. When "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" is used, it means "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide", respectively, unless otherwise specified. In this specification, "C.I." means Color Index (C.I.).
The photolithography method is a manufacturing method in which a coating is exposed to ultraviolet light through a photomask, and then the unexposed parts are removed by development to form a pattern. In the manufacture of color filters, a heating step (also called post-baking) is generally performed after the pattern formation.

The photosensitive coloring composition of the present invention is a photosensitive coloring composition used for forming a pattern of a color filter by a photolithography method in which the pattern is cured by a heating step of 150 ° C. or less after development,
The composition contains a pigment (A), a resin (B), a photopolymerization initiator (C), and a polymerizable compound (D), and is characterized in that the resin (B) contains a resin (B1) that contains a blocked isocyanate group-containing structural unit, and a resin (B2) that contains a (meth)acryloyl group-containing vinyl polymer moiety.
The photosensitive coloring composition of the present invention is preferably used for forming a cured film, a color filter, etc. The cured film and the color filter are preferably used for applications such as image display devices such as liquid crystal display devices and organic EL display devices, and solid-state imaging devices.

The photosensitive coloring composition of the present invention contains a resin (B1) containing a block isocyanate group-containing structural unit as resin (B), and a resin (B2) containing a (meth)acryloyl group-containing vinyl polymer moiety. The reason for this is that if excessive photocuring is performed with resin (B2) containing a vinyl polymer moiety having a (meth)acryloyl group in an attempt to obtain sufficient chemical resistance, the line width of the pattern after development increases and the resolution decreases, making it difficult to form a fine pattern. However, by combining it with resin (B1) containing a block isocyanate group-containing structural unit, the desired curing property can be obtained even in a low-temperature heating process of 150°C or less while maintaining appropriate photocuring property, thereby improving chemical resistance. Therefore, the photosensitive coloring composition has improved chemical resistance, low-temperature curing property, and fine pattern formation.

<Pigment (A)>
The photosensitive coloring composition of the present invention contains a pigment (A) as a colorant.
Examples of the pigment (A) include organic pigments and inorganic pigments. The pigment is preferably a pigment having high color development and high heat resistance, particularly a pigment having high thermal decomposition resistance, and an organic pigment is usually used. Specific examples of organic pigments are shown below with color index numbers.

Red pigments include, for example, C.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, 1 84, 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, and pigments described in Japanese Patent No. 6368844. Among these, from the viewpoints of heat resistance, light resistance, and transmittance, C.I. C.I. Pigment Red 48: 1,122,177,224,242,269,254,291,295,296, the pigments described in JP-A-2014-134712, and the pigments described in Japanese Patent No. 6368844 are preferred, and C.I. Pigment Red 177,254,269,291,295,296, the pigments described in JP-A-2014-134712, and the pigments described in Japanese Patent No. 6368844 are more preferred.

Examples of orange pigments include C.I. Pigment Orange 36, 38, 43, 64, 71, and 73.

Yellow pigments include, for example, C.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 A, JP 2017-171912 A, JP 2017-171913 A, JP 2017-171914 A, JP 2017-171915 A, and the like. Among these, C.I. Pigment Yellow 138, 139, 150, 185, 231, 233, and the pigments described in JP-A-2012-226110 are preferred.

Examples of green pigments include C.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, and 63. Of these, C.I. Pigment Green 36, 58, 59, 62, and 63 are preferred.

Examples of blue pigments include C.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, and 79. Among these, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are preferred.

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

Examples of black pigments include C.I. Pigment Black 1, 6, 7, 12, 20, 31, and 32. Other examples include compounds described in JP-T-2010-534726, JP-T-2012-515233, JP-T-2012-515234, JP-A-1-170601, and JP-A-2-34664. The black pigment includes an inorganic pigment.

Examples of inorganic pigments include titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, amber, and synthetic iron black.

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

<Minification of pigment>
It is preferable that the organic pigment is mixed with other raw materials after the micronization treatment. Examples of the method of the micronization treatment include wet grinding, dry grinding, and dissolution precipitation. Among these, salt milling treatment using a kneader method, which is a type of wet grinding, is preferable. The average primary particle size of the organic pigment after the micronization treatment is preferably 10 to 80 nm, more preferably 15 to 70 nm. A moderate particle size further improves dispersibility and the contrast ratio of the coating. The average primary particle size is the average value of about 20 particles arbitrarily selected from an enlarged image of a TEM (transmission electron microscope). When the particle has a vertical axis length and a horizontal axis length, the vertical axis length is used.

During the salt milling process, a resin can be added as necessary. Examples of the resin include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. The resin is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in water-soluble organic solvents. The amount of resin used is preferably 5 to 200 parts by mass per 100 parts by mass of the pigment.

<Metal Removal>
If a specific metal element is present in a large amount in the coloring composition as an impurity other than the pigment component, it inhibits dispersion stability over time. In addition, it may cause a decrease in heat resistance or a decrease in sensitivity. In addition, a color filter made using this may have foreign matter, which may 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 the specific metal elements is more preferably 300 ppm by mass or less, and particularly preferably 200 ppm by mass 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, and more preferably 5 ppm by mass or more. Within the above range, a photosensitive coloring composition can be obtained that can form a color filter that is cost-effective, has excellent storage stability, and has little generation of foreign matter and little decrease in brightness.

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

In addition, it is better to have fewer impurities that are not constituent components of the pigment, such as metals such as Ni, Zn, Cu, Al, Fe, Fe, Co, and Co, and these can be removed in the same way as specific metal elements by the following method. Furthermore, since Mn, Cs, Ti, Co, Si, Pd, etc. may be mixed in from materials (e.g. catalysts) used in the manufacturing process of various raw materials for the photosensitive coloring composition, it is preferable to remove them as much as possible.

Methods for removing metals that have been mixed in from pigment (A) or from equipment during the manufacturing process include the water washing methods described in JP-A-2010-83997, JP-A-2018-36521, JP-A-7-198928, JP-A-8-333521, and JP-A-2009-7432, and the method for removing magnetic foreign matter using a magnet described in JP-A-2011-48736.

The content of specific metal elements can be measured by inductively coupled plasma optical emission spectrometry (ICP).

<Dye>
The photosensitive coloring composition may contain a dye as a colorant other than the pigment (A). Examples of the dye include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. In addition, examples of the dye include dye derivatives and lake pigments obtained by converting dyes into lakes.

The dye is preferably used as a salt-forming compound. Examples of salt-forming compounds include salt-forming compounds of an acid dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound; salt-forming compounds of a resin component having an amino group and an acid dye, etc.; salt-forming compounds of an acid dye and a compound having an onium base; salt-forming compounds of a basic dye and an organic acid, perchloric acid, or a metal salt thereof. Among these, salt-forming compounds of basic dyes are preferred because they have excellent resistance to various types of substances and compatibility with pigments. The compound having an onium base is preferably a resin having a cationic group on the side chain.

The chemical structure of dyes includes, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, etc.), dyes, thiazine dyes, etc.), azine dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, etc. Among these, from the viewpoint of color properties such as hue, color separation, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferred.

<Dye derivatives>
The photosensitive coloring composition can use a dye derivative as necessary. The dye derivative is a compound having an acidic group, a basic group, a neutral group, etc. in an organic dye residue. Examples of the dye derivative include compounds having an acidic substituent such as a sulfo group, a carboxy group, or a phosphoric acid group, as well as amine salts thereof, compounds having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal, and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group.

The dye derivative is preferably a basic pigment derivative, which can be used alone or in combination with two or more other dye derivatives. As the basic pigment derivative used in the present invention, a known dye derivative having a basic group in the organic dye residue can be used. For example, a compound having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal can be used. The basic pigment derivative shown in the present invention is a derivative having at least one basic group.
Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, azo pigments such as azo, disazo, and polyazo, and the like.

Specific examples of diketopyrrolopyrrole-based basic pigment derivatives include those described in JP 2001-220520 A, WO 2009/081930 B, WO 2011/052617 B, WO 2012/102399 B, and JP 2017-156397 A; examples of phthalocyanine-based basic pigment derivatives include those described in JP 2007-226161 A, WO 2016/163351 B, JP 2017-165820 B, and Japanese Patent No. 5753266 A; and examples of anthraquinone-based basic pigment derivatives include those described in JP 2007-226161 A, WO 2016/163351 B, JP 2017-165820 B, and Japanese Patent No. 5753266 A. Examples of basic pigment derivatives include those in JP-A-63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, and WO2009/025325. Examples of basic pigment derivatives include those in JP-A-48-54128, JP-A-03-9961, and JP-A-2000-273383. Examples of basic pigment derivatives include those in JP-A-2011-162662. Examples of basic pigment derivatives include those in JP-A-2011-162662. Examples of basic pigment derivatives include those in JP-A-2011-162662. As triazine-based basic pigment derivatives, see JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, and JP-A-2007-314681; as benzoisoindole-based basic pigment derivatives, see JP-A-2009-57478; as quinophthalone-based basic pigment derivatives, see JP-A-2003-167112, JP-A-2006-291194, JP-A-2007-314681; Examples of naphthol-based basic pigment derivatives include those described in JP-A-2012-208329 and JP-A-2014-5439, examples of azo-based basic pigment derivatives include those described in JP-A-2001-172520 and JP-A-2012-172092, and examples of basic substituents include those described in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, and JP-A-2005-213404.

The content of the dye derivative 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, per 100 parts by mass of pigment (A).

By adding a dye derivative to the pigment and carrying out pigmentation processes such as acid pasting, acid slurry, dry milling, salt milling, and solvent salt milling, the dye derivative is adsorbed onto the pigment surface, making it possible to make the primary pigment particles finer than when the dye derivative is not added.

<Resin (B)>
Resin (B) corresponds to any of resins having a function of dispersing a pigment, resins having a function of binding, and resins having both functions to approximately the same extent. Resin (B) contains resin (B1) containing a structural unit containing a blocked isocyanate group, and resin (B2) containing a vinyl polymer moiety containing a (meth)acryloyl group.

<Resin (B1) Containing Blocked Isocyanate Group-Containing Structural Unit>
Resin (B) includes a resin (B1) containing a block isocyanate group-containing structural unit, which is heat cured and has a binder function. If the resin (B1) further contains a carboxyl group-containing structural unit, it becomes an alkali-soluble resin having a binder function, which is preferable. The carboxyl group-containing structural unit is introduced, for example, by copolymerizing (meth)acrylic acid.

(Blocked isocyanate group-containing structural unit)
The blocked isocyanate group-containing structural unit contained in the resin (B1) having a blocked isocyanate group-containing structural unit is a structural unit derived from a blocked isocyanate group-containing monomer. The monomer is a reaction product of an isocyanate group-containing monomer and a blocking agent. In the blocking reaction, it is preferable to use an organic metal salt such as zinc or lead, or a tertiary amine, as a catalyst. The reaction temperature is generally about -20 to 150°C, and preferably 0 to 100°C. In addition, a solvent can be used during the reaction, if necessary. Examples of the isocyanate group-containing monomer include compounds represented by the following formula (1).

Formula (1)

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

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

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

Examples of blocking agents include lactam-based agents such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; alcohol-based agents such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, and cyclohexanol; phenol-based agents such as phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, o-isopropylphenol, and butylphenols such as p-tert-butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, thymol, p-naphthol, p-nitrophenol, and p-chlorophenol; and active methylene-based agents such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone.
Mercaptans such as butyl mercaptan, thiophenol, and tert-dodecyl mercaptan;
Amines such as diphenylamine, phenylnaphthylamine, aniline, and carbazole; acid amides such as acetanilide, acetanisidide, acetic acid amide, and benzamide;
Acid imides such as succinimide and maleimide;
Imidazoles such as imidazole, 2-methylimidazole, and 2-ethylimidazole;
Pyrazoles such as pyrazole and 3,5-dimethylpyrazole;
Urea-based compounds such as urea, thiourea, and ethyleneurea;
Carbamate-based compounds such as N-phenylcarbamate phenyl and 2-oxazolidone; imine-based compounds such as ethyleneimine and polyethyleneimine;
Oximes such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, and cyclohexanone oxime;
Examples of the bisulfites include sodium bisulfite, potassium bisulfite, and the like.

When the blocked isocyanate group is heated, the blocking agent dissociates and the isocyanate group is regenerated. In the present invention, the isocyanate group reacts with reactive functional groups, such as acid groups and optionally hydroxyl groups and amino groups, to form a cured product with high crosslink density.

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

The blocked isocyanate group-containing structural unit preferably used in the photosensitive coloring composition of the present invention is a blocked isocyanate group-containing (meth)acrylate. It is preferable to use a blocked isocyanate group-containing (meth)acrylate in which the dissociation rate of the blocked isocyanate group when heat-treated at 100°C for 30 minutes is preferably 5 to 99% by mass, more preferably 8 to 97% by mass, and most preferably 10 to 95% by mass. The dissociation rate of the blocked isocyanate group of the blocked isocyanate group-containing (meth)acrylate is determined by preparing an n-octanol solution containing the blocked isocyanate group-containing (meth)acrylate at a concentration of 20% by mass, adding 1% by mass of dibutyltin laurate and 3% by mass of phenothiazine (polymerization inhibitor) to the solution, and then heating the solution for 30 minutes at 100° C., and measuring the mass loss rate of the blocked isocyanate group-containing (meth)acrylate by HPLC analysis. By using a blocked isocyanate group-containing (meth)acrylate having a dissociation rate within the above range, it is possible to sufficiently ensure the stability of the copolymer during synthesis, and it is possible to sufficiently lower the baking temperature during the production of a cured coating film, thereby ensuring sufficient solvent resistance of the cured coating film. Examples of blocking agents for blocked isocyanate group-containing (meth)acrylates having such a dissociation rate include γ-butyrolactam, 1-methoxy-2-propanol, 2,6-dimethylphenol, diisopropylamine, methyl ethyl ketoxime, 3,5-dimethylpyrazole, and diethyl malonate. Among these blocking agents, diethyl malonate, 3,5-dimethylpyrazole, and methyl ethyl ketoxime are more preferred from the viewpoint of low-temperature curing properties.

It is also preferable to use a blocked isocyanate group-containing (meth)acrylate in which the dissociation temperature of the blocked isocyanate group is 80°C or higher. By using a blocked isocyanate group-containing (meth)acrylate with a dissociation temperature of 80°C or higher, the stability of the copolymer during synthesis can be sufficiently ensured, and unintended crosslinking reactions can be reduced during the modification reaction described below. On the other hand, if the dissociation temperature of the blocked isocyanate group is 150°C or lower, the baking temperature can be sufficiently lowered, and the solvent resistance of the cured coating film can be sufficiently ensured. The dissociation temperature of the blocked isocyanate group of the blocked isocyanate group-containing (meth)acrylate is determined by preparing an n-octanol solution containing the blocked isocyanate group-containing (meth)acrylate at a concentration of 20% by mass, adding 1% by mass of dibutyltin laurate and 3% by mass of phenothiazine (polymerization inhibitor) to the solution, heating the solution at a predetermined temperature, and measuring the mass loss rate of the blocked isocyanate group-containing (meth)acrylate after 30 minutes by HPLC analysis. The temperature at which the mass loss rate is 80% by mass or more is determined to be the dissociation temperature of the blocked isocyanate group.

Examples of the blocked isocyanate group-containing (meth)acrylate include methacrylates such as Karenz (registered trademark) MOI-DEM (a reaction product of methacryloyloxyethyl isocyanate and diethyl malonate, manufactured by Showa Denko K.K., dissociation temperature of blocked isocyanate group: 90°C, dissociation rate: 90% by mass) represented by the following formula (2), Karenz MOI-BP (a reaction product of methacryloyloxyethyl isocyanate and 3,5-dimethylpyrazole, manufactured by Showa Denko K.K., dissociation temperature of blocked isocyanate group: 110°C, dissociation rate: 70% by mass) represented by the following formula (3), and Karenz MOI-BM (a reaction product of methacryloyloxyethyl isocyanate and methyl ethyl ketoxime, manufactured by Showa Denko K.K., dissociation temperature of blocked isocyanate group: 130°C, dissociation rate: 18% by mass) represented by the following formula (4), and the corresponding acrylates. These blocked isocyanate group-containing (meth)acrylates may be used alone or in combination of two or more.

Formula (4)

The resin (B1) containing a structural unit containing a blocked isocyanate group may be, for example, a resin having a dispersing function as described in JP-A-2009-155406. The resin (B1) containing a structural unit containing a blocked isocyanate group may have monomer units derived from the other monomers described below.

Other monomers include, for example, (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate, or (meth)acrylic (meth)acrylamides such as styrene, α-methylstyrene, and the like; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; oxetane group-containing (meth)acrylates such as (3-methyl-3-oxetanyl)methyl (meth)acrylate, (3-ethyl-3-oxetanyl)methyl (meth)acrylate, (3-butyl-3-oxetanyl)methyl (meth)acrylate, and (3-hexyltyl-3-oxetanyl)methyl (meth)acrylate; vinyl acetate; and vinyl fatty acid vinyls such as vinyl propionate.

The proportion of the blocked isocyanate group-containing structural units contained is preferably 1 to 40 mol %, more preferably 2 to 30 mol %, and even more preferably 3 to 25 mol % of all structural units of resin (B1). When the proportion of the blocked isocyanate group-containing structural units is 1 to 40 mol %, the crosslinking density of the cured coating film increases and the solvent resistance improves. In addition, the storage stability of resin (B1) does not decrease.

<Resin (B2) Containing a (Meth)acryloyl Group-Containing Vinyl Polymer Moiety>
The resin (B2) containing a (meth)acryloyl group-containing vinyl polymer moiety is a resin that has both binder function and dispersibility, in which the vinyl polymer moiety acts as a steric repulsion moiety to enhance dispersibility, and the (meth)acryloyl group acts as a photocrosslinking moiety.

The resin (B2) is more preferably a resin further having an aromatic carboxylic acid moiety. The aromatic carboxylic acid moiety has a high affinity with the pigment surface. Therefore, the resin (B2) efficiently encapsulates the pigment, suppressing the exposed surface of the pigment and making it difficult for the substrate and the pigment to come into direct contact with each other, thereby improving adhesion.

The aromatic carboxylic acid moiety is derived from one or more acid anhydrides selected from, for example, tetracarboxylic acid anhydrides or tricarboxylic acid anhydrides.

Resins having aromatic carboxylic acid moieties derived from tetracarboxylic anhydrides can be synthesized, for example, by adding hydroxyl groups in a vinyl polymer having two hydroxyl groups at one end to tetracarboxylic anhydrides. Examples of the tetracarboxylic anhydrides that are the raw materials for comb-shaped resin-type dispersants and the raw materials for vinyl polymers that are part of the structure include the resins described in WO 2008/007776.

These may be used alone or in combination. The aromatic tetracarboxylic dianhydride is preferably used in the present invention from the viewpoint of reducing the viscosity of the photosensitive coloring composition. For example, pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, ethylene glycol ditrimellitic anhydride ester, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 3,3',4,4'-biphenyl sulfone tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, and 3,3',4,4'-biphenyl tetracarboxylic dianhydride are preferred. Among these, pyromellitic anhydride is preferred.

For example, a resin having an aromatic carboxylic acid moiety derived from a tricarboxylic anhydride can be synthesized by adding a hydroxyl group in a vinyl polymer having two hydroxyl groups at one end to a tricarboxylic anhydride to synthesize a straight-chain resin-type dispersant having a carboxyl group. Examples include the compounds described in JP-A-2009-251481, JP-A-2007-23195, and JP-A-1996-143651.

Examples of tricarboxylic anhydrides include benzenetricarboxylic anhydride (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], etc.), naphthalenetricarboxylic anhydride (1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride, etc.), 3,4,4'-benzophenonetricarboxylic anhydride, 3,4,4'-biphenylethertricarboxylic anhydride, 3,4,4'-biphenyltricarboxylic anhydride, 2,3,2'-biphenyltricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride, and 3,4,4'-biphenylsulfonetricarboxylic anhydride. Among these, trimellitic anhydride is preferred.

The weight average molecular weight of the vinyl polymer portion of resin (B2) is preferably 500 to 30,000, more preferably 5,000 to 20,000, and even more preferably 7,000 to 10,000.

The number average molecular weight of the vinyl polymer portion of resin (B2) is preferably 2,000 to 6,000.

The photosensitive coloring composition contains a resin (B1) containing a structural unit containing a blocked isocyanate group, and a resin (B2) containing a vinyl polymer moiety containing a (meth)acryloyl group as the resin (B). The reason for this is that if sufficient chemical resistance is to be achieved with the resin (B2) containing a vinyl polymer moiety having a (meth)acryloyl group, excessive photocuring occurs, and the line width of the pattern after development increases and the resolution decreases, making it difficult to form a fine pattern. However, by combining it with the resin (B1) containing a structural unit containing a blocked isocyanate group, the desired curing property can be obtained even in a heating process at a low temperature of 150°C or less while maintaining appropriate photocuring property, thereby improving chemical resistance. Therefore, the photosensitive coloring composition has improved chemical resistance, low-temperature curing property, and fine pattern formation.

The total amount of resin (B1) and resin (B2) is preferably 80 mass% or more of the total amount of resin (B).

The acid value of the resin (B1) containing a structural unit containing a blocked isocyanate group and the resin (B2) containing a vinyl polymer moiety having a meth)acryloyl group is preferably 10 to 250 mgKOH/g, more preferably 40 to 200 mgKOH/g, and even more preferably 50 to 160 mgKOH/g, calculated as non-volatile content. A moderate acid value improves storage stability.

<Other resins>
Other resins that can be used in combination with the resin (B1) and the resin (B2) include resins having a dispersing function and resins having a binder function.
Examples of resins having a dispersing function include those described in WO2008/007776, JP2008-029901A, JP2009-155406A, JP2010-185934A, JP2011-157416A, JP2009-251481A, JP2007-23195A, JP1996-143651A, and JP2007-140487A.

The resin having a binder function is preferably a resin having a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm when a coating having a thickness of 2 μm is formed. The transmittance is preferably 95% or more. The resin having a binder function is preferably a thermoplastic resin or a photosensitive resin. In addition, the resin having a binder function is preferably alkali-soluble. This allows the coating formed from the photosensitive coloring composition to be patterned by a photolithography method. The photosensitive resin not having alkali solubility and the alkali-soluble resin can have a thermosetting group. Examples of the thermosetting group include an epoxy group and an oxetanyl group.

Resins with binder function can be used alone or in combination of two or more types.

The content of the resin having a binder function is preferably 20 to 400 parts by mass, and more preferably 50 to 250 parts by mass, per 100 parts by mass of pigment (A). When an appropriate amount is contained, a coating can be easily formed and good color characteristics can be easily obtained.

Examples of alkali-soluble resins include resins having acidic groups such as carboxyl groups and sulfonic groups. Examples of alkali-soluble thermoplastic resins include acrylic resins having acidic groups, α-olefin/maleic acid (anhydride) copolymers, styrene/styrene sulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, and isobutylene/maleic acid (anhydride) copolymers. Among these, acrylic resins having acidic groups and styrene/styrene sulfonic acid copolymers are preferred in terms of improving developability, heat resistance, and transparency.

<Thermoplastic resin>
The thermoplastic resin is not alkali-soluble. Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin.

<Alkali-soluble photosensitive resin>
The alkali-soluble photosensitive resin has photosensitivity because it has a polymerizable unsaturated group. The alkali-soluble photosensitive resin may be any known resin as long as it is alkali-soluble and photosensitive, but a resin synthesized by the following method (i) or (ii) is preferred. When the alkali-soluble photosensitive resin is used, it is three-dimensionally crosslinked by light irradiation to increase the crosslink density, improving the chemical resistance of the coating.

[Method (i)]
Method (i) is, for example, a method in which a polymer of an epoxy group-containing monomer and other monomers is first synthesized. Next, a monocarboxyl group-containing monomer is added to the epoxy group of the polymer, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to obtain an alkali-soluble photosensitive resin. The monocarboxyl group-containing monomer is a monomer having one carboxyl group.

Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

Examples of monocarboxyl group-containing monomers include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. Note that polybasic acid anhydrides may have a carboxyl group that does not form an acid anhydride.

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, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene Examples of such compounds include (meth)acrylates such as polyethylene glycol (meth)acrylate or ethoxy polyethylene glycol (meth)acrylate, (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, or acryloylmorpholine, styrenes such as styrene or α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, and vinyl acetate or vinyl propionate, and other fatty acid vinyl compounds.

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

Method (ii) is, for example, a method in which a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers are synthesized to produce a polymer. Then, the hydroxyl group of the polymer is reacted with an isocyanate group of an isocyanate group-containing monomer to synthesize an alkali-soluble photosensitive resin.

Examples of the hydroxyl group-containing monomer include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. Other examples include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to hydroxyalkyl (meth)acrylates, and polyester mono(meth)acrylates obtained by addition of poly(γ-valerolactone), poly(ε-caprolactone, and/or poly(12-hydroxystearic acid). Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred, and glycerol mono(meth)acrylate is more preferred.

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

Monomers that can be used other than the above monomers include the other monomers exemplified in method (i) above, as well as phosphate ester group-containing monomers, etc.

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

The above-mentioned raw materials for the resin having a binder function can be used alone or in combination of two or more types. Also, the resin having a binder function can be used alone or in combination of two or more types.

<Thermosetting compound>
The photosensitive coloring composition can contain a thermosetting compound. When a color filter is produced using the photosensitive coloring composition, the thermosetting compound is thermally cured in the post-baking process to increase the crosslink density of the coating, thereby improving heat resistance. This suppresses pigment aggregation in the post-baking process, improving the contrast ratio.

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

Epoxy compounds include, for example, polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenols, aromatic-substituted phenols, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, di Examples of such epoxy resins include polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzene dimethanol, α,α,α',α'-benzene dimethanol, biphenyl dimethanol, α,α,α',α'-biphenyl dimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethyl biphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidyl amine epoxy resins, and glycidyl ester epoxy resins.

(Oxetane Compounds)
The oxetane compound is a compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher functional oxetane compounds.

Examples of monofunctional oxetane compounds include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane.

Examples of bifunctional oxetane compounds include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether-3-ethyl-3-hydroxymethyloxetane, 3 -ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycose bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl -3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified Examples include bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether, etc.

Examples of oxetane groups with three or more functional groups include pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, and caprolactone-modified dipentaerythritol. Examples include dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (such as the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30.

The content of the thermosetting compound is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass. If an appropriate amount is included, the solvent resistance of the coating is further improved.

(Basic resin type dispersant)
The photosensitive coloring composition can contain a basic resin type dispersant. Examples of the basic resin type dispersant include a nitrogen atom-containing graft copolymer, a nitrogen atom-containing acrylic block copolymer having a functional group including a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocycle, etc., in a side chain, and a urethane-based polymer dispersant.

The number average molecular weight of the basic resin-type dispersant used in the present invention is preferably 500 to 50,000, and more preferably 3,000 to 30,000. If the number average molecular weight is less than 500, the effect of steric repulsion due to the pigment affinity group, the effect of compatibility with the pigment carrier, and the effect of compatibility with the pigment carrier and solvent when a solvent is used are small, making it difficult to prevent pigment aggregation and causing the viscosity of the dispersion to increase. Furthermore, if the number average molecular weight is 50,000 or more, the amount of resin required for dispersion increases, which may lead to a decrease in the pigment concentration in the coating film.

The amine value of the basic resin-type dispersant is preferably 35 to 100 mgKOH/g. More preferably, it is 50 to 75 mgKOH/g. If the amine value is less than 35 mgKOH/g, it may not be sufficiently adsorbed to the pigment, resulting in poor dispersion. If it exceeds 100 mgKOH/g, it may not be adsorbed efficiently to the pigment due to adsorption or reaction with the acidic components in the pigment carrier, resulting in poor dispersion.

Various types of resins such as vinyl, urethane, polyester, polyether, or polyamide can be used as basic resin-type dispersants, but vinyl monomer copolymer types are preferred because they are easy to design and have excellent resistance to various factors. Specifically, copolymer resins of N,N-disubstituted amino group-containing vinyl monomer units, alkyl (meth)acrylate monomer units, and other vinyl monomer units are preferred.

Examples of N,N-disubstituted amino group-containing vinyl monomer units include, but are not limited to, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, and N,N-diethylaminoethyl (meth)acrylamide. These monomer units are adsorbed to the pigment as basic group-containing monomer units.

Examples of alkyl (meth)acrylate monomer units include, but are not limited to, (meth)acrylic esters obtained by reacting unsaturated monocarboxylic acids such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, or lauryl (meth)acrylate with alkyl alcohols having 1 to 18 carbon atoms. These monomer units act as pigment carrier affinity groups.

Other vinyl monomer units include nitro group-containing vinyl monomers such as (meth)acrylonitrile, vinyl aromatic monomers such as styrene, α-methylstyrene, and benzyl (meth)acrylate, hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and polyethylene glycol (meth)acrylate, amide group-containing vinyl monomers such as (meth)acrylamide, N,N-dimethylacrylamide, N-isopropylacrylamide, and diacetone acrylamide, N-methylol (meth)acrylamide, and dimethylol (meth)acrylamide, and Examples of suitable vinyl monomers include vinyl monomers such as acrylamides, alkoxymethyl group-containing vinyl monomers such as N-methoxymethyl(meth)acrylamide and N-butoxymethyl(meth)acrylamide, olefins such as ethylene, propylene, and isoprene, dienes such as chloroprene and butadiene, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether, and vinyl fatty acids such as vinyl acetate and vinyl propionate. These are used appropriately according to the purpose, but are not necessarily limited to these.

Other examples include basic resin-type dispersants having comb-shaped basic substituents, which are prepared by modifying a polymer having a primary amino group-containing monomer unit such as allylamine, or polyethyleneimine, polyethylenepolyamine, polyxylylenepoly(hydroxypropylene)polyamine, or poly(aminomethylated)epoxy resin with a polyester resin, an acrylic resin, or a polyether resin.

Commercially available basic resin-type dispersants include, for example, DISPERBYK161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919, 21116 from BYK Japan, and SOLSPERSE11200, 13240, 13650, 13940, 21200, 2124 ... Examples include 4000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 71000, EFKA4300, 4330, 4046, 4060, 4080 from BASF, and Ajisper PA111, PB711, PB821, PB822, PB824 from Ajinomoto Fine-Techno Co., Ltd.

The content of the basic resin-type dispersant is preferably about 3 to 200% by mass, and more preferably about 5 to 100% by mass, relative to the pigment (A). When an appropriate amount is included, the film-forming properties are further improved.

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

<Polymerizable compound (D)>
The polymerizable compound (D) is a monomer or oligomer containing a polymerizable unsaturated group. The polymerizable compound (D) contributes to the formation of a film of the photosensitive coloring composition. The polymerizable compound (D) may be, for example, an acid group-containing monomer, a urethane bond-containing monomer, or other monomer. The polymerizable unsaturated group may be, for example, a vinyl group, a (meth)acryloyl group, or a (meth)allyl group. The oligomer is a compound having a molecular weight of 1000 or more.

The acid group of the acid group-containing monomer may be a sulfonic acid group, a carboxyl group, a phosphoric acid group, etc.

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

(Urethane bond-containing monomer)
Examples of the urethane bond-containing monomer include polyfunctional urethane acrylates obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and polyfunctional urethane acrylates obtained by reacting an alcohol with a polyfunctional isocyanate and further reacting the alcohol with a (meth)acrylate having a hydroxyl group.

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

Examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate, etc.

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

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

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

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

The photopolymerization initiator (C) can be used alone or in combination of two or more types.

(Oxime ester compounds)
In the oxime ester compound, the N-O bond of the oxime is cleaved by absorbing ultraviolet light, generating an iminyl radical and an alkyloxy radical. These radicals further decompose to generate highly active radicals, so that a pattern can be formed with a small amount of exposure. When the colorant concentration of the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may decrease, and the degree of curing of the coating film may decrease, but the oxime ester compound has a high quantum efficiency and is therefore preferably used.

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

The content of the photopolymerization initiator (C) is preferably 2 to 50 parts by mass, and more preferably 2 to 30 parts by mass, per 100 parts by mass of the pigment (A). When an appropriate amount is added, the photocurability and developability are further improved.

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

Sensitizers can be used alone or in combination of two or more types.

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

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

<Thiol-based chain transfer agent>
The photosensitive coloring composition can contain a chain transfer agent. The chain transfer agent is preferably a thiol-based chain transfer agent. When the thiol-based chain transfer agent is used in combination with a photopolymerization initiator, it generates a thiyl radical that is not easily inhibited by oxygen during radical polymerization after irradiation with light, improving the sensitivity of the photosensitive coloring composition. The thiol-based chain transfer agent can be classified into a monofunctional thiol having one thiol group and a multifunctional thiol having two or more thiol groups.

Examples of monofunctional thiols include 1-hexanethiol, 1-octanethiol, 2-ethylhexyl-3-mercaptopropionate, 3-methoxybutyl-3-mercaptopropionate, tridecyl-3-mercaptopropionate, 2-methyl-1-butanethiol, 2-methyl-2-butanethiol, aryl mercaptan, cyclohexyl mercaptan, thiophenol, phenethyl mercaptan, 2-ethylthiophenol, 4-methoxybenzothiophenol, 2-naphthalenethiol, mercaptoimidazole, mercaptooxazole, mercaptothiazole, mercaptotriazole, mercaptothiadiazole, mercaptooxadiazole, mercaptobenzimidazole, mercaptobenzoxazole, mercaptobenzothiazole, and derivatives thereof.

Polyfunctional thiols include, for example, hexanedithiol and 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, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, etc. are preferably used, and ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate are preferably used.

During the exposure process in the pattern formation process, the exposure of the deeper parts of the film that are in close contact with the substrate may be insufficient compared to the surface parts, which can result in the parts that are in close contact with the substrate after development becoming thinner. Conventionally, to address this issue, polyfunctional thiol compounds have often been used as chain transfer agents that move radicals generated at the surface parts to the deeper parts of the film, but the use of monofunctional thiol compounds makes it possible to more effectively suppress the occurrence of thinning in the parts that are in close contact with the substrate after development, and to form finer patterns with a higher degree of rectangularity.

Thiol-based chain transfer agents can be used alone or in combination of two or more types.

The content of the thiol chain transfer agent is preferably 30 to 200 parts by mass, more preferably 50 to 150 parts by mass, relative to 100 parts by mass of the photopolymerization initiator (C). In addition, the content is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, relative to 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is contained, the photosensitivity and taper shape are improved, and wrinkles are less likely to occur on the coating surface.

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

Polymerization inhibitors include, for example, alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, and 3,5-di-tert-butylcatechol; 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, and 2-n-butylcatechol. Examples of such compounds include alkyl resorcinol compounds such as n-butyl resorcinol, 4-n-butyl resorcinol, 2-tert-butyl resorcinol, and 4-tert-butyl resorcinol; alkyl hydroquinone compounds such as methyl hydroquinone, ethyl hydroquinone, propyl hydroquinone, tert-butyl hydroquinone, and 2,5-di-tert-butyl hydroquinone; phosphine compounds such as tributyl phosphine, trioctyl phosphine, tricyclohexyl phosphine, triphenyl phosphine, and tribenzyl phosphine; phosphine oxide compounds such as trioctyl phosphine oxide and triphenyl phosphine oxide; phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite; pyrogallol; and phloroglucin.

The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass based on 100% by mass of the non-volatile content of the photosensitive coloring composition. If an appropriate amount is included, it becomes easier to obtain a good pattern shape.

<Ultraviolet absorbing agent>
The photosensitive coloring composition may contain an ultraviolet absorbing agent. Examples of the ultraviolet absorbing agent include benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, salicylic acid ester-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds. The ultraviolet absorbing agent may be an oligomer or a polymer.

The content of the UV absorber is preferably 5 to 70% by mass, out of a total of 100% by mass of the photopolymerization initiator and UV absorber. If an appropriate amount is included, the resolution after development will be further improved.

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

Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α, α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, mixture of 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side and straight chain 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 products, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t- Butyl-4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate.

Examples of triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester. Examples of such compounds include 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-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

Examples of salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

<Antioxidants>
The photosensitive coloring composition can contain an antioxidant. The antioxidant can prevent the coating film formed from the photosensitive coloring composition from yellowing due to oxidation during the thermal process of heat curing or ITO annealing, and suppress the decrease in the transmittance of the coating film. In particular, when the pigment concentration of the photosensitive coloring composition is high, the content of the polymerizable compound (D) is relatively reduced, so that the coating film is likely to yellow when the amount of the photopolymerization initiator is increased or a thermosetting compound is blended. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and the decrease in the transmittance of the coating film can be suppressed.

Antioxidants are compounds that have a radical scavenging function or a peroxide decomposition function. Examples of antioxidants include hindered phenol compounds, hindered amine compounds, phosphorus compounds, sulfur compounds, and hydroxylamine compounds. It is preferable that the antioxidant is a compound that does not contain a halogen atom.

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

Antioxidants can be used alone or in combination of two or more types.

The content of the antioxidant is preferably 0.5 to 5.0% by mass based on 100% by mass of the non-volatile content of the photosensitive coloring composition. This further improves the transmittance, spectral characteristics, and sensitivity.

<Leveling Agent>
The photosensitive coloring composition can contain a leveling agent. This improves the wettability of the transparent substrate during film formation and the drying property of the film. Examples of the leveling agent include silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.

The content of the leveling agent is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, of the non-volatile content of the photosensitive coloring composition. By being within this range, the balance between the coatability of the photosensitive coloring composition, the pattern adhesion, and the transmittance is further improved.

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

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

<Adhesion improver>
The adhesion improver may, for example, be a silane coupling agent.
Examples of the silane coupling agent include vinyl silanes such as vinyl trimethoxy silane and vinyl triethoxy silane; (meth)acrylic silanes such as 3-methacryloxypropyl methyl dimethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyl diethoxy silane, 3-methacryloxypropyl triethoxy silane and 3-acryloxypropyl trimethoxy silane; epoxy silanes such as 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyl methyl dimethoxy silane, 3-glycidoxypropyl trimethoxy silane, 3-glycidoxypropyl methyl diethoxy silane and 3-glycidoxypropyl triethoxy silane; N-2-(aminoethyl)-3-aminopropyl methyl dimethoxy silane, N-2-( aminosilanes such as N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride; mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureidos such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatepropyltriethoxysilane.

The content of the adhesion improver is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of pigment (A). When an appropriate amount is contained, 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 makes it easier to adjust the viscosity of the photosensitive coloring composition, making it easier to form a coating with a smooth surface. The solvent may be appropriately selected according to the purpose of use, and may be contained in an appropriate amount.

Examples of the solvent include ester solvents (solvents that contain -COO- in the molecule and do not contain -O-), ether solvents (solvents that contain -O- in the molecule and do not contain -COO-), ether ester solvents (solvents that contain -COO- and -O- in the molecule), ketone solvents (solvents that contain -CO- in the molecule and do not contain -COO-), alcohol solvents (solvents that contain OH in the molecule and do not contain -O-, -CO-, or -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc.

Among these, solvents with a boiling point of 120°C or more and 180°C or less at 1 atm are preferred in terms of coatability and drying properties. For example, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc. are more preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are even more preferred.

Solvents can be used alone or in combination of two or more types.

<Production of Photosensitive Coloring Composition>
The photosensitive coloring composition is prepared by dispersing the pigment (A), a resin-type dispersant, a solvent, etc. to prepare a pigment dispersion. The pigment dispersion, a resin having a binder function, a polymerizable compound (D), and a photopolymerization initiator (C) are then mixed together to prepare the photosensitive coloring composition. The timing of mixing each material is arbitrary. The dispersion process can also be carried out multiple times.

The dispersion process can be carried out using a dispersion device such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor.

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

<Water content in photosensitive coloring composition>
The photosensitive coloring composition of the present invention preferably has a water content of 2% by mass or less.

When the water content is set to the above range, the photosensitive coloring composition has excellent dispersion stability and sensitivity even after storage over time.

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

There are no particular limitations on the method for controlling the water content, and known methods can be used. For example, a method of producing a photosensitive coloring composition while blowing in a dry inert gas, or a method of adding molecular sieves after production and dehydrating the composition, etc., can be mentioned. Among these, the method of producing the composition while blowing in a dry inert gas is preferred.

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

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

<Cured film, which is a cured product of the photosensitive coloring composition>
The cured film, which is a cured product of the photosensitive coloring composition, means a filter segment, and can be formed by, for example, a printing method, an electrodeposition method, a transfer method, an inkjet method, a photolithography method, etc. In this specification, the most preferred photolithography method will be described.

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

Examples of coating devices include spray coaters, spin coaters, slit coaters, and roll coaters. A drying process can be carried out during coating. Examples of drying devices include hot air ovens and infrared heaters.

In the exposure step, the colored layer is exposed to a specific pattern through a mask using an exposure device such as a stepper. This results in a cured film. For exposure, ultraviolet rays such as g-line, h-line, or i-line are preferably used.

The developer may be an alkaline developer, for example, an inorganic alkali such as sodium carbonate or sodium hydroxide; or an organic alkali such as dimethylbenzylamine or triethanolamine. In addition, a defoamer or a surfactant may be added to the developer.

<Color filter>
The color filter of the present specification has a filter segment formed from a photosensitive coloring composition. The color filter preferably has a base material (also referred to as a transparent substrate). The filter segment preferably has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of pigment (A) used. The filter segment may have a magenta filter segment, a cyan filter segment, and a yellow filter segment instead of these. A reflective substrate may be used instead of the transparent substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective substrate include a substrate using an aluminum electrode or a metal thin film as a reflective surface.

<Color Filter Manufacturing Method>
It is preferable that the color filter is formed by first forming a black matrix on a substrate and then forming filter segments. It is also possible to form thin film transistors (TFTs) on the substrate before forming the black matrix.
Examples of the black matrix include a multilayer film of chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, and a resin film in which a light-shielding agent is dispersed.

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

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

<Solid-state imaging element>
The solid-state imaging device of the present invention includes the above-mentioned color filter of the present invention. The solid-state imaging device is not particularly limited, but examples thereof include the following configurations.

The solid-state imaging element has, on a support, a plurality of photodiodes constituting a light receiving area thereof and a transfer electrode made of polysilicon or the like; a light-shielding film made of tungsten or the like is provided on the photodiodes and the transfer electrode, with only the light receiving portions of the photodiodes being opened; a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the light receiving portions of the photodiodes; and a cured film of the present invention is provided on the device protection film.
Furthermore, the device protective film may have a configuration in which a focusing means (e.g., a microlens, etc.; the same applies below) is provided below the cured film of the present invention (on the side closer to the support), or a configuration in which a focusing means is provided on the cured film of the present invention.
In addition, in the solid-state imaging device, the color filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned by partition walls, for example in a lattice shape. In this case, it is preferable that the partition walls have a low refractive index with respect to each color pixel.

<Liquid crystal display device>
The liquid crystal display device of the present invention includes a color filter.
The liquid crystal display device of the present invention includes the color filter of the present invention 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 because it has a wider red reproduction range.

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

Examples of LED1 include NSSW306D-HG-V1 (manufactured by Nichia Chemicals) and NSSW304D-HG-V1 (manufactured by Nichia Chemicals).

Examples of LED2 include NSSW440 (manufactured by Nichia Chemicals) and NSSW304D (manufactured by Nichia Chemicals).

The present invention will be described below with reference to examples. It goes without saying that the present invention is not limited to these examples. In the examples, "parts" means "parts by mass" and "%" means "% by mass".
It should be noted that Examples 25 to 27 and Examples 39 to 41 are reference examples.

Before going into the examples, we will explain how to calculate the average molecular weight of the resin and how to measure the acid value of the resin.

<Average primary particle size of pigment>
The average primary particle size of the pigment was measured by a general method of directly measuring the size of the primary particles from a transmission electron microscope (TEM) photograph. Specifically, the minor axis diameter and major axis diameter of each pigment primary particle were measured, and the average was taken as the particle size of the pigment particle. Next, the volume (weight) of each particle of 100 or more pigment particles was calculated by approximating it to a rectangular parallelepiped of the calculated particle size, and the volume average particle size was taken as the average primary particle size.

(Dispersed particle size measurement)
Using Nikkiso Microtrac UPA-EX150, which employs dynamic light scattering (FFT power spectrum method), particle permeability was set to absorption mode, particle shape was set to non-spherical, and D50 was set to average diameter. The solvents used for the dispersions were used as dilution solvents for the measurements, and the samples treated with ultrasonic waves were measured immediately after sample preparation.

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

(Acid value of resin)
80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of the resin solution, and the solution was stirred to dissolve uniformly, and titrated with an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) using a 0.1 mol/L KOH aqueous solution as a titrant to measure the acid value (mg KOH/g) of the resin solution. The acid value per unit of non-volatile content of the resin was calculated from the acid value of the resin solution and the concentration of the non-volatile 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 calculated by converting the total amine value (mg KOH/g) measured in accordance with the method of ASTM D 2074 into the non-volatile content.

(Ammonium salt value (mg KOH/g))
The ammonium salt value is determined by titrating with 0.1N aqueous silver nitrate solution using a 5% aqueous potassium chromate solution as an indicator, and then converted into the potassium hydroxide equivalent, and indicates the ammonium salt value of the non-volatile content.

<Method of producing fine pigment>
(Micronized Pigment (A-1))
100 parts of C.I. Pigment Red 269 (PR269) ("Toner Magenta F8B" manufactured by Clariant), 800 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 5 hours at 70 ° C. This mixture was added to 4000 parts of hot water, heated to about 80 ° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C. for 24 hours to obtain a finely divided pigment (A-1).

(Micronized Pigment (A-2))
Anthraquinone-based red pigment C.I. Pigment Red 177 (Shinic's "Shinilex Red SR3C"): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded for 8 hours at 120 ° C. Next, this kneaded product was put into 5 liters of warm water, heated to 70 ° C. and stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for one day to obtain a fine pigment (A-2).

(Micronized Pigment (A-3))
200 parts of diketopyrrolopyrrole red pigment C.I. Pigment Red 254 (BASF Japan "B-CF"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded for 6 hours at 80 ° C. Next, this kneaded product was put into 8000 parts of warm water, heated to 80 ° C. and stirred for 2 hours to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for a day and night to obtain 190 parts of finely divided pigment (A-3).

(Micronized Pigment (A-4))
500 parts of a phthalocyanine green pigment C.I. Pigment Green 36 ("Lionol Green 6YK" manufactured by Toyo Color Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 4 hours at 120° C. Next, this kneaded product was put into 5 liters of warm water, heated to 70° C. and stirred for 1 hour to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80° C. for 24 hours to obtain 490 parts of a finely divided pigment (A-4).

(Micronized Pigment (A-5))
100 parts of phthalocyanine green pigment C.I. Pigment Green 58 (DIC Corporation "FASTGEN GREEN A110"), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 70 ° C. This kneaded product was added to 3000 parts of warm water, heated to 70 ° C. and stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for a day and night to obtain 97 parts of finely divided pigment (A-5).

(Micronized Pigment (A-6))
100 parts of C.I. Pigment Yellow 139 (BASF Japan "Irgaphor Yellow 2R-CF"), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 70 ° C. This kneaded product was added to 3000 parts of warm water, heated to 70 ° C. and stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for a day and night to obtain a fine pigment (A-6).

(Micronized Pigment (A-7))
100 parts of a metal complex yellow pigment (C.I. Pigment Yellow 150, Lanxess "Yellow Pigment E4GN"), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded for 10 hours at 60° C. Next, this mixture was poured into 3 liters of warm water, heated to about 80° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, which was filtered and washed repeatedly with water to remove sodium chloride and the solvent, and then dried at 80° C. for one day and night to obtain a finely divided yellow pigment (A-7).

(Micronized Pigment (A-8))
The azobarbituric acid precursor was prepared according to the synthesis method described in JP 2017-171915 A. (Instruction 1)
46.2 parts of diazobarbituric acid and 38.4 parts of barbituric acid were introduced into 1100 parts of distilled water at 85° C. The pH was then adjusted to about pH 5 with aqueous potassium hydroxide solution and stirring was continued for 90 minutes.
Azobarbituric acid (0.3 moles) prepared according to Instruction 1 was then mixed with 1500 parts of distilled water at 82°C. 10 parts of 30% hydrochloric acid were then added dropwise to adjust the pH to 2-2.5. 79.4 parts of melamine (0.63 moles) were then added. 0.225 moles of a mixed solution of 25% nickel chloride + 0.075 moles of 25% zinc chloride were then added dropwise. After 3 hours at 82°C, the pH was adjusted to about 5.5 using aqueous potassium hydroxide. This was followed by dilution with about 100 parts of distilled water at 90°C. 21 parts of 30% hydrochloric acid were then added dropwise and the temperature was maintained at 90°C for 12 hours. The pH was then adjusted to about 5 using aqueous potassium hydroxide. The pigment was then isolated on a suction filter, washed, dried at 80° C. in a vacuum drying cabinet, and ground for 2 minutes in a standard laboratory mill to obtain the melamine adduct of zinc/nickel azobarbituric acid, a hybrid compound having a composition of 25 mol % Zn and 75 mol % Nickel.
100 parts of the hybrid compound, 10 parts of the dye derivative (d-1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 8 hours at 70° C. This mixture was added to 2000 parts of warm water, heated to about 80° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, which was filtered and washed repeatedly with water to remove salt and the solvent, and then dried at 80° C. for 24 hours to obtain a finely-processed metal azo pigment (A-8).

(Micronized Pigment (A-9))
50 parts of C.I. Pigment Yellow 185 (BASF Japan "Paliotol Yellow L 1155"), 250 parts of sodium chloride, and 25 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 100 ° C. for 6 hours. Next, this kneaded product was put into 5 liters of warm water, heated to 70 ° C. and stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours to obtain a fine pigment (A-9). The volume average primary particle diameter of the obtained colorant was 33 nm.

(Micronized Pigment (A-10))
100 parts of blue pigment C.I. Pigment Blue 15:6 ("Lionol Blue ES" manufactured by Toyo Color Co., Ltd.), 800 parts of ground salt, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 70° C. This mixture was added to 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, filtered and washed repeatedly with water to remove salt and solvent, and then dried at 80° C. for 24 hours to obtain 98 parts of finely divided pigment (A-10).

(Micronized Pigment (A-11))
200 parts of a phthalocyanine blue pigment C.I. Pigment Blue 15:3 (PB15:3, Toyo Color Co., Ltd. "LIONOL BLUE FG-7351"), 600 parts of sodium chloride, and 600 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. Next, this kneaded mixture was added to 8,000 parts of warm water, heated to 120°C and stirred for 8 hours to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85°C for a day and a night.
A finely divided pigment (A-11) was obtained.

(Micronized Pigment (A-12))
100 parts of a purple pigment C.I. Pigment Violet 23 ("LIONOGEN VIOLET FG-6140" manufactured by Toyo Color Co., Ltd.), 800 parts of ground salt, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 70 ° C. This mixture was added to 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, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C. for 24 hours to obtain 95 parts of a finely divided pigment (A-12).

Table 1 shows the average primary particle size (nm) of each finely divided pigment.

<Dye manufacturing method>
(Resin 1 having a cationic group on the side chain)
A four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser was charged with 67.3 parts of methyl ethyl ketone and heated to 75°C under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 6.5 parts of 2,2'-azobis (2,4-dimethylvaleronitrile), and 25.1 parts of methyl ethyl ketone were homogenized, then charged in a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the end of the dropwise addition, it was confirmed from the non-volatile content that the polymerization yield was 98% or more and the weight average molecular weight (Mw) was 6830, and the mixture was cooled to 50°C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, 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. In this way, resin 1 having a cationic group on the side chain having an ammonium group and a resin component of 47% by mass was obtained. The ammonium salt value of the obtained resin was 34 mgKOH/g.

(Dye 01 (AR52-JK))
Dye 01 (AR52-JK), which is a salt-forming compound consisting of CI Acid Red 52 and Resin 1 having a cationic group on the side chain, was produced by the following procedure.
30 parts of resin 1 having a cationic group in the side chain in terms of non-volatile content was added to 2000 parts of water, thoroughly stirred and mixed, and then heated to 60 ° C. Meanwhile, an aqueous solution was prepared by dissolving 10 parts of C.I. Acid Red 52 in 90 parts of water, and the solution was gradually dropped into the resin solution. After dropping, the solution was stirred at 60 ° C for 120 minutes to thoroughly react. To confirm the end point of the reaction, the reaction solution was dropped onto a filter paper, and the end point was determined to be when no bleeding occurred, and the salt-forming compound was obtained. After cooling 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 in a dryer to obtain dye 01 (AR52-JK), which is a salt-forming compound of 32 parts of C.I. Acid Red 52 and resin 1 having a cationic group in the side chain. At this time, the C.I. The content of the active colorant component derived from Acid Red 52 was 25% by mass.

<Method of producing dye solution>
(Dye solution (DS-01))
The following mixture was stirred and mixed to a uniform consistency, and then filtered through a filter with a pore size of 5.0 μm to prepare a dye solution (DS-01).
Dye 01: 16.0 parts Propylene glycol monomethyl ether acetate: 84.0 parts

<Basic pigment derivatives>
The following basic pigment derivatives were used:

Basic pigment derivatives (1)

Basic pigment derivatives (2)

Basic pigment derivatives (3)

(Production of Resin (B1-1))
A flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube was charged with 149.3 parts of propylene glycol monomethyl ether, which was then stirred while replacing with nitrogen and heated to 78° C. Next, a monomer mixture consisting of 16.1 parts of 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylate (KarenzMOI-BP, manufactured by Showa Denko KK), 6.7 parts of styrene, 28.2 parts of dicyclopentanyl methacrylate, 11.0 parts of methacrylic acid, 25.3 parts of 2-ethylhexyl methacrylate, and 12.8 parts of methyl methacrylate, and 11.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) dissolved in 62.8 parts of propylene glycol monomethyl ether acetate were each dropped into the flask from the dropping funnel. After the dropwise addition was completed, the mixture was stirred at 78°C for 3 hours to carry out a copolymerization reaction, thereby producing a copolymer. Thereafter, propylene glycol monomethyl ether acetate was added so that the non-volatile content became 20%, thereby obtaining a resin (B1-1) having a constitutional unit containing a blocked isocyanate group. The weight average molecular weight of the copolymer in the obtained polymer composition was 8,100, and the acid value was 80 KOHmg/g.

(Production of Resins (B1-2 to B1-4))
Copolymerization reaction was carried out under the same conditions as for the alkali-soluble binder resin solution (B1-1) having a constitutional unit containing a blocked isocyanate group, except that the raw materials shown in Table 2 were used, to obtain alkali-soluble binder resin solutions (B2-2 to B2-4) having a constitutional unit containing a blocked isocyanate group. The weight average molecular weight and acid value of the copolymer in the obtained polymer composition are shown in Table 1-2. In Table 1, 2-[O-(1'-methylproplideneamino)carboxyamino]ethyl methacrylate is Karenz MOI-BM, manufactured by Showa Denko K.K., and 2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl malonate is Karenz MOI-DEM, manufactured by Showa Denko K.K.

(Production of Resin (B1-5))
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 160 parts of n-butyl acrylate, 40 parts of Karenz MOI-BM (manufactured by Showa Denko KK), 50 parts of propylene glycol monomethyl ether acetate, and 50 parts of cyclohexanone were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80°C, 12 parts of 3-mercapto-1,2-propanediol were added, and the reaction was carried out for 12 hours. It was confirmed that 95% had reacted by measuring the non-volatile content. Next, 19 parts of pyromellitic dianhydride, 231 parts of cyclohexanone, and 0.40 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100°C for 7 hours. It was confirmed that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, and the reaction was terminated. The nonvolatile content was adjusted to 20% with propylene glycol monomethyl ether acetate, and a resin (B1-5) having an acid value of 42 mgKOH/g and a weight average molecular weight of 9,000 was obtained.

(Production of Resin (B2-1))
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc (methoxypropyl acetate), and 0.2 parts of monobutyltin oxide as a catalyst were charged, and after replacing with nitrogen gas, the mixture was reacted at 120° C. for 5 hours (first step). It was confirmed by measuring the acid value 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, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged, and the inside of the reaction vessel was heated to 80 ° C., and 1.2 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) were added, and the reaction was carried out for 12 hours (second step). It was confirmed that 95% had reacted by measuring the non-volatile content. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 parts of hydroquinone were charged, and the reaction was carried out until the disappearance of the peak at 2270 cm-1 based on the isocyanate group was confirmed by IR (third step). After the disappearance of the peak was confirmed, the reaction solution was cooled and the non-volatile content was adjusted with PGMAc to obtain a resin (B2-1) solution with a non-volatile content of 20%. The acid value of the obtained resin was 68, the unsaturated double bond equivalent was 1593, and the weight average molecular weight was 13000.

(Production of Resin (B2-2))
A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer. 207 parts of cyclohexanone was charged into the reaction vessel, which was then heated to 80°C and substituted with nitrogen in the reaction vessel. From the dropping tube, a mixture of 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the total amount of the copolymer solution obtained was stirred while stopping the nitrogen gas and injecting dry air for 1 hour, and then cooled to room temperature, and a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko K.K.), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70 ° C. for 3 hours. After completion of the dropwise addition, the reaction was continued for another 1 hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the resin solution previously synthesized so that the non-volatile content was 20% to prepare resin (B2-2). The weight average molecular weight (Mw) was 18,000.

(Production of Resin (B2-3))
A separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer was charged with 370 parts of cyclohexanone, and the temperature was raised to 80 ° C., and the inside of the flask was replaced with nitrogen, and then a mixture of 18 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile was dropped over 2 hours from the dropping tube. After the dropping, the mixture was further reacted at 100 ° C. for 3 hours, and then a solution of 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was continued at 100 ° C. for 1 hour. Next, the inside of the vessel was replaced with air, and 9.3 parts of acrylic acid (100% of glycidyl groups), 0.5 parts of trisdimethylaminophenol, and 0.1 parts of hydroquinone were added to the vessel, and the reaction was continued for 6 hours at 120° C., and the reaction was terminated when the non-volatile acid value reached 0.5, to obtain an acrylic resin solution. Furthermore, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added, and the reaction was continued for 3.5 hours at 120° C., to obtain an acrylic resin solution.
After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content, and PGMAc was added to the previously synthesized resin solution so that the non-volatile content was 20 mass% to prepare a resin (B2-3) solution. The weight average molecular weight (Mw) was 19,000.

<Production Example of Other Resin (B3)>
A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer, and 196 parts of cyclohexanone was charged in the reaction vessel, which was then heated to 80°C. The atmosphere in the reaction vessel was replaced with nitrogen, and then a mixture of 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), and 1.1 parts of 2,2'-azobisisobutyronitrile was dripped over 2 hours from the dropping tube. After dripping was completed, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried at 180°C for 20 minutes to measure the nonvolatile content, and PGMAc was added to the resin solution previously synthesized so that the nonvolatile content was 20% to prepare a binder function other resin (B3) liquid. The weight average molecular weight (Mw) was 26,000.

(Production of Basic Resin-Type Dispersant (Bb-1))
In a reaction apparatus equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride as a catalyst, 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 nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content. Next, 61 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 10 parts of methacryloyloxyethylbenzyldimethylammonium chloride were charged into the reaction apparatus, and the mixture was stirred while maintaining 110°C under a nitrogen atmosphere, and the reaction was continued. Two hours after the addition, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more calculated from the nonvolatile content. The reaction solution was cooled to room temperature to stop the polymerization. As a result of GPC measurement, the mass average molecular weight of the polymer was 20,000, the molecular weight distribution Mw/Mn was 1.4, and the reaction conversion rate was 98.5%. In this way, a basic resin type dispersant (Bb-1) having an amine value of 169.8 mgKOH/g per nonvolatile content was obtained. After cooling to room temperature, about 2 g of the resin type dispersant solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content, and PGMAc was added to the previously synthesized basic resin type dispersant (Bb-1) so that the nonvolatile content was 20 mass%, to prepare a basic resin type dispersant (Bb-1) solution having an amino group, which is an A-B-A block polymer.

(Production of Basic Resin-Type Dispersant (Bb-2))
A reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 133 parts of PGMAc, and the temperature was raised to 110 ° C. while replacing with nitrogen. A dropping vessel was charged with 177 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate, 3 parts of methyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, 61 parts of PGMAc, and 6 parts of 2,2'-azobis (2,4-dimethylvaleronitrile), and after stirring until uniform, the mixture was dropped into the reaction vessel over 2 hours, and the reaction was continued for 3 hours at the same temperature. In this way, a basic resin-type dispersant (Bb-2) having an amine value of 201 mg KOH / g per nonvolatile content and a number average molecular weight of 3,800 (Mn) was obtained. In the same manner as in the case of the basic resin type dispersant (Bb-2) solution, the solution was diluted so that the nonvolatile content became 20% by mass, to prepare a basic resin type dispersant (Bb-2) solution having an amino group, which is a random polymer.

<Method of producing colored composition>
[Production Example 1]
(Preparation of Colored Composition (R-1))
The mixture below was stirred and mixed to be uniform, and then dispersed for 3 hours using zirconia beads having a diameter of 0.5 mm in an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.), and then filtered through a filter having a pore size of 5.0 μm to prepare a colored composition (R-1).
Pigment (A-1): 20.5 parts Resin (B1-1: 20% non-volatile liquid): 2.0 parts Resin (B2-1: 20% non-volatile liquid): 16.0 parts Solvent (P): 61.5 parts

[Production Examples 2 to 35]
(Preparation of Colored Compositions (R-2 to R-35))
Colored compositions (R-2 to R-35) were prepared in the same manner as in Production Example 1, except that the material types and masses were changed as shown in Table 3. The dispersed particle diameters of the respective pigments are shown in Table 3.

<Method for producing photosensitive coloring composition>
[Example 1]
(Photosensitive coloring composition (X-1))
The following raw materials were mixed and stirred, and then filtered through a filter having a pore size of 1.0 μm to obtain a photosensitive colored composition (Y-1).
Coloring composition (R-1: non-volatile content 20%): 70.0 parts Resin (B1-1: non-volatile content 20%): 10.0 parts Thermosetting compound (E-1): 0.2 parts Thermosetting compound (E-2): 0.3 parts Polymerizable monomer (F): 3.0 parts Photopolymerization initiator (G): 1.8 parts Sensitizer (H): 0.2 parts Thiol-based chain transfer agent (I): 0.4 parts Polymerization inhibitor (J): 0.1 parts Ultraviolet absorber (K): 0.1 parts Antioxidant (L): 0.1 parts Leveling agent (M: non-volatile content 3%): 1.0 parts Storage stabilizer (N): 0.1 parts Silane coupling agent (O): 0.2 parts Solvent (P): 12.5 parts

[Examples 2 to 53, Comparative Examples 1 to 3]
(Preparation of Photosensitive Coloring Compositions (X-2 to 56))
Except for changing the coloring composition and the type of the resin solution having a binder function of Example 1 as shown in Table 4, the same procedure as in Example 1 was carried out to prepare photosensitive coloring compositions (X-2 to 56).
The details of each raw material are as follows:

<Thermosetting compound (E)>
Epoxy compound (E-1)
(E-1-1) 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2'-bis(hydroxymethyl)-1-butanol [EHPE-3150 (manufactured by Daicel Corporation)],
(E-1-2) Glycidyl etherified epoxy compound of sorbitol [Denacol EX611 (manufactured by Nagase Chemtex Corporation)],
(E-1-3) Triglycidyl isocyanurate (E-1-1) to (E-1-3) were mixed in equal amounts to obtain an epoxy compound (E-1).
Oxetane compound (E-2):
3-Ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane [Aronoxetane OXT-221 (manufactured by Toagosei)]

<Polymerizable compound (F)>
(F-1) Trimethylolpropane triacrylate [Aronix M309 (manufactured by Toagosei Co., Ltd.)]
(F-2) Dipentaerythritol penta- and hexaacrylate [ARONIX M402 (manufactured by Toagosei)]
(F-3) Polybasic acidic acrylic oligomer [ARONIX M520 (manufactured by Toagosei Co., Ltd.)]
(F-4) Caprolactone-modified dipentaerythritol hexaacrylate [KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)]

(F-5) Multifunctional urethane acrylate as described below: Pentaerythritol triacrylate (432 g) and hexamethylene diisocyanate (84 g) were charged into a 1-liter five-necked reaction vessel and reacted at 60°C for 8 hours to obtain a product containing a (meth)acryloyl group-containing multifunctional urethane acrylate (F-5). The proportion of the multifunctional urethane acrylate (F-5) in the product was 70 mass%, with the remainder being other photopolymerizable monomers. It was confirmed by IR analysis that no isocyanate groups were present in the reaction product.

(F-6) Bifunctional bisphenol A (meth)acrylate [ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
(F-7) Ethoxylated isocyanuric acid triacrylate [A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
(F-8) Trimethylolpropane EO modified triacrylate [Aronix M350 (manufactured by Toagosei)]
(F-9) EO modified (12) Dipentaerythritol hexaacrylate [KAYARAD DPEA-12 (manufactured by Nippon Kayaku)]
The above (F-1) to (F-9) were mixed in equal amounts to prepare a photopolymerizable monomer (E).

<Photopolymerization initiator (G)>
(G-1) 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one [Irgacure 907 (manufactured by BASF Japan)]
(G-2) 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [Irgacure 379 (BASF Japan)]
(G-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [Lucirin TPO (IGM Resins)]
(G-4) 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole [biimidazole (manufactured by Kurogane Chemical Industry Co., Ltd.)]
(G-5) p-Dimethylaminoacetophenone [DMA (manufactured by Daikifine Co., Ltd.)]
(G-6) Ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyloxime)
[Irgacure OXE02 (manufactured by BASF Japan)]
(G-7) 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one [Irgacure 2959 (BASF Japan)]
(G-8) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide [Irgacure 819 (manufactured by BASF Japan)]

(G-9) 100.0 parts of the photopolymerization initiator N-benzophenoylcarbazole obtained by the following synthesis method was dissolved in 1000 parts of chloroform, and 85.0 parts of aluminum chloride was added and stirred at 0°C, and a solution of 32.0 parts of propionyl chloride dissolved in 500 parts of chloroform was dropped over 2 hours. After the dropwise addition, the mixture was stirred at 25°C for 4 hours. The reaction liquid was poured into 2000 parts of ice water and extracted with 2000 parts of chloroform. The organic layer was dried over magnesium sulfate, and the desiccant was filtered off, and the residue was recrystallized with chloroform/methanol to obtain 113.0 parts of intermediate compound (a1). Next, 100.0 parts of compound (a1) was dissolved in a mixed solution of 1000 parts of tetrahydrofuran and 500 parts of concentrated hydrochloric acid, and 38.4 parts of tert-butyl nitrite was dropped over 1 hour under stirring at room temperature. After the dropwise addition, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 parts of ice water and extracted with 1600 parts of chloroform. The organic layer was washed with water (500 parts x 3 times), dried with magnesium sulfate, filtered to remove the desiccant, and the solvent was distilled off. The residue was washed with n-hexane to obtain 99.8 parts of precursor compound (b1). Next, 30.0 parts of compound (b1) was stirred in 300 parts of ethyl acetate, to which 6.3 parts of acetic anhydride and 10.6 parts of sodium acetate were added and heated under reflux for 3 hours. Thereafter, the reaction solution was poured into 500 parts of ice water, and the product was extracted with ethyl acetate. The organic layer was washed with water (300 parts x 3 times), dried with magnesium sulfate, filtered to remove the desiccant, and the solvent was distilled off. The residue was recrystallized with ethyl acetate-hexane to obtain 31.4 g of oxime ester photopolymerization initiator (G-9).

Photopolymerization initiator (G-9)

(G-10) Photopolymerization initiator obtained by the following synthesis method 100.0 parts of N-benzophenoylcarbazole was dissolved in 1000 parts of chloroform, and 84.0 parts of aluminum chloride was added. A solution of 36.8 parts of butanoyl chloride dissolved in 500 parts of chloroform was dropped over 2 hours while stirring at 0°C. After the dropwise addition, the mixture was stirred at 25°C for 4 hours. The reaction liquid was poured into 2000 parts of ice water and extracted with 2000 parts of chloroform. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was recrystallized with chloroform/methanol to obtain 109.3 parts of intermediate compound (a2). Next, 100.0 parts of compound (a2) was dissolved in a mixed solution of 1000 parts of tetrahydrofuran and 500 parts of concentrated hydrochloric acid, and 43.1 parts of tert-butyl nitrite was dropped over 1 hour while stirring at room temperature. After the dropwise addition, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 parts of ice water and extracted with 1600 parts of chloroform. The organic layer was washed with water (500 parts x 3 times), dried with magnesium sulfate, filtered to remove the desiccant, and the solvent was distilled off. The residue was washed with n-hexane to obtain 89.3 parts of precursor compound (b2). Next, 30.0 parts of compound (b2) was stirred in 300 parts of ethyl acetate, to which 6.1 parts of acetic anhydride and 10.3 parts of sodium acetate were added and heated under reflux for 3 hours. Thereafter, the reaction solution was poured into 500 parts of ice water, and the product was extracted with ethyl acetate. The organic layer was washed with water (300 parts x 3 times), dried with magnesium sulfate, filtered to remove the desiccant, and the solvent was distilled off. The residue was recrystallized with ethyl acetate-hexane to obtain 30.0 parts of oxime ester photopolymerization initiator (G-10).

Photopolymerization initiator (G-10)

(G-11) Photopolymerization initiator obtained by the following synthesis method 100.0 parts of N-(p-nitrophenyl)carbazole was dissolved in 1000 parts of chloroform, and 101.8 parts of aluminum chloride was added and stirred at 0°C, and a solution of 44.3 parts of butanoyl chloride dissolved in 500 parts of chloroform was dropped over 2 hours. After the dropwise addition, the mixture was stirred at 25°C for 4 hours. The reaction liquid was poured into 2000 parts of ice water and extracted with 2000 parts of chloroform. The organic layer was dried over magnesium sulfate, and the desiccant was filtered off, and the residue was recrystallized with chloroform/methanol to obtain 113.6 parts of intermediate compound (a3). Next, 100.0 parts of compound (a3) was dissolved in a mixed solution of 1000 parts of tetrahydrofuran and 500 parts of concentrated hydrochloric acid, and 43.1 parts of tert-butyl nitrite was dropped over 1 hour under stirring at room temperature. After the dropwise addition, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 parts of ice water and extracted with 1500 parts of chloroform. The organic layer was washed with water (500 parts x 3 times), dried with magnesium sulfate, filtered to remove the desiccant, and the solvent was distilled off. The residue was washed with n-hexane to obtain 107.2 parts of precursor compound (b3). Next, 50.0 parts of compound (b3) was stirred in 500 parts of ethyl acetate, to which 19.9 parts of acetic anhydride and 11.7 parts of sodium acetate were added and heated under reflux for 3 hours. Thereafter, the reaction solution was poured into 500 parts of ice water, the product was extracted with ethyl acetate, the organic layer was washed with water (500 parts x 3 times), and dried with magnesium sulfate. The desiccant was filtered, and the solvent was distilled off. The residue was recrystallized with ethyl acetate-hexane to obtain 57.6 parts of oxime ester photopolymerization initiator (G-11).

Photopolymerization initiator (G-11)

(G-12) Photopolymerization initiator obtained by the following synthesis method 100.0 parts of N-benzophenoyl-1,3-dimethyl-carbazole was dissolved in 1000 parts of chloroform, and 78.6 parts of aluminum chloride was added and stirred at 0°C, and a solution of 29.6 parts of propionyl chloride dissolved in 500 parts of chloroform was dropped over 2 hours. After the dropwise addition, the mixture was stirred at 25°C for 4 hours. The reaction liquid was poured into 2000 parts of ice water and extracted with 2000 parts of chloroform. The organic layer was dried over magnesium sulfate, and the desiccant was filtered off, and the residue was recrystallized with chloroform/methanol to obtain 111.8 parts of intermediate compound (a4). Next, 100.0 parts of compound (a4) was dissolved in a mixed solution of 1000 parts of tetrahydrofuran and 500 parts of concentrated hydrochloric acid, and 35.7 parts of tert-butyl nitrite was dropped over 1 hour under stirring at room temperature. After the dropwise addition, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 parts of ice water and extracted with 1600 parts of chloroform. The organic layer was washed with water (500 parts x 3 times), dried with magnesium sulfate, filtered to remove the desiccant, and the solvent was distilled off. The residue was washed with n-hexane to obtain 98.3 parts of precursor compound (b4). Next, 30.0 parts of compound (b4) was stirred in 300 parts of ethyl acetate, to which 5.9 parts of acetic anhydride and 10.0 parts of sodium acetate were added and heated under reflux for 3 hours. Thereafter, the reaction solution was poured into 500 parts of ice water, the product was extracted with ethyl acetate, the organic layer was washed with water (300 parts x 3 times), and dried with magnesium sulfate. The desiccant was filtered to remove the solvent, and the residue was recrystallized with ethyl acetate-hexane to obtain 31.2 parts of oxime ester photopolymerization initiator (G-12).

Photopolymerization initiator (G-12)

The above (G-1) to (G-12) were mixed in equal amounts to prepare a photopolymerization initiator (G).

<Sensitizer (H)>
(H-1) 2,4-Diethylthioxanthone [Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)]
(H-2) 4,4'-bis(diethylamino)benzophenone [CHEMARK DEABP (manufactured by Chemark Chemical Co.)]
The above (H-1) and (H-2) were mixed in equal amounts to prepare a sensitizer (H).

<Thiol-Based Chain Transfer Agent (I)>
(I-1) 2-Ethylhexyl-3-mercaptopropionate [BMPA-2EH (manufactured by Yodo Chemical Co., Ltd.)]
(I-2) Trimethylolethane tris(3-mercaptobutyrate)
[TEMB (Showa Denko)]
(I-3) Trimethylolpropane tris(3-mercaptobutyrate)
[TPMB (Showa Denko Co., Ltd.)]
(I-4) Pentaerythritol tetrakis(3-mercaptopropionate)
[PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(I-5) Trimethylolpropane tris(3-mercaptopropionate)
[TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(I-6) Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate [TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)]
As described above, (I-1) was used alone, or (I-2) to (I-6) were mixed in equal amounts and used as a thiol-based chain transfer agent (IM).

<Polymerization inhibitor (J)>
(J-1) 3-methylcatechol (J-2) methylhydroquinone (J-3) tert-butylhydroquinone The above (J-1) to (J-3) were mixed in equal amounts to prepare a polymerization inhibitor (J).

<Ultraviolet absorber (K)>
(K-1) 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine [TINUVIN 400 (manufactured by BASF Japan)]
(K-2) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol [TINUVIN 900 (manufactured by BASF Japan)]
The above (K-1) and (K-2) were mixed in equal amounts to prepare an ultraviolet absorber (K).

<Antioxidant (L)>
(L-1) pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (L-2) dioctadecyl 3,3'-thiodipropanoate (L-3) tris[2,4-di-(tert)-butylphenyl]phosphine (L-4) bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (L-5) p-octylphenyl salicylate. The above (L-1) to (L-5) were mixed in equal amounts to give antioxidant (L).

<Leveling Agent (M)>
1 copy of BYK-330 manufactured by BYK-Chemie,
1 copy of DIC "Megafac F-551"
A mixed solution in which 1 part of Kao Corporation's "Emulgen 103" was dissolved in 97 parts of PGMAc.

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

<Adhesion improver (O)>
(O-1) 3-glycidoxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-2) 3-methacryloxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-3) N-2-(aminoethyl)-3-aminopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-4) 3-mercaptopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
The above (O-1) to (O-4) were mixed in equal amounts to prepare a silane coupling agent (O).

<Solvent (P)>
(P-1) PGMAc 30 parts (P-2) Cyclohexanone 30 parts (P-3) Ethyl 3-ethoxypropionate 10 parts (P-4) Propylene glycol monomethyl ether 10 parts (P-5) Cyclohexanol acetate 10 parts (P-6) Dipropylene glycol methyl ether acetate 10 parts The above (P-1) to (P-6) were mixed in the above parts by mass to obtain solvent (P).

<Evaluation of Photosensitive Coloring Composition>
The photosensitive coloring compositions (X-1 to X-56) were subjected to the following tests. The test results are shown in the table below.
The evaluation criteria are as follows:
◎: Particularly good level.
◯: Good level.
△: Practical level.
×: Impractical level.

<Evaluation of fine pattern formability>
The formability of a fine pattern was evaluated in terms of linearity and pattern shape as described below.
[Creating an evaluation board]
The obtained photosensitive coloring composition was applied to a glass substrate of 10 cm length x 10 cm width by spin coating, and then heated in a clean oven at 70 ° C for 15 minutes to remove the solvent, obtaining a coating film of about 1 μm. Next, after cooling the substrate to room temperature, the substrate was exposed to 600 mJ / cm ² ultraviolet light through a photomask of 100 μm width (pitch 200 μm) and 25 μm width (pitch 50 μm) stripe pattern using an ultra-high pressure mercury lamp. Then, the substrate was spray-developed using an aqueous sodium carbonate solution at 23 ° C, washed with ion-exchanged water, air-dried, and heated in a clean oven at 100 ° C for 30 minutes. The spray development was performed for each coating film of the photosensitive coloring composition in the shortest time possible to form a pattern without development residue, and this was determined as the appropriate development time. The thickness of the coating film was measured using Dektak 3030 (manufactured by Japan Vacuum Technology Co., Ltd.).

[Linearity evaluation]
The pattern of the 100 μm wide photomask portion of the filter segment formed by the above method was observed under an optical microscope and evaluated. The evaluation was ranked as follows:
○: Good linearity △: Partially poor linearity ×: Poor linearity

[Pattern shape evaluation]
The cross section of the pattern in the 100 μm photomask portion of the filter segment formed by the above method was observed and evaluated using an electron microscope. The pattern cross section had a good forward taper. The evaluation ranks were as follows:
◎: Cross section has a gentle forward taper shape ○: Cross section has a forward taper shape ×: Cross section has a reverse taper shape

(Chemical resistance)
The obtained photosensitive coloring composition was spin-coated on a glass substrate using a spin coater so that the dry film thickness was 0.9 μm, and dried at 70 ° C. for 20 minutes. Next, the dried coating film was exposed to 600 mJ / cm ² with an ultra-high pressure mercury lamp having an i-line illuminance of 30 mW / cm ² through a photomask in which a 6 μm square pattern mask pattern was arranged. The pattern-exposed coating film was developed in the unexposed area using a 2 mass % potassium hydroxide aqueous solution, and then washed with pure water. Thereafter, the water droplets were blown off with high pressure air, the substrate was naturally dried, and the substrate was post-baked on a hot plate at 120 ° C. for 10 minutes to form a pattern on the glass substrate. The spectral transmittance of the pattern-formed portion of the glass substrate was measured using a microspectrophotometer (Olympus Optical Co., Ltd. "OSP-SP100"). Thereafter, the film was immersed in an aqueous solution of 1.0% by weight of TMAH (tetramethylammonium hydroxide) dissolved in water, and the spectral transmittance was measured again. The change in transmittance at 400 nm before and after immersion in the TMAH aqueous solution was evaluated. The evaluation was ranked as follows:
◎: The change in transmittance is less than 0.5%. ○: The change in transmittance is 0.5% or more but less than 1.0%. △: The change in transmittance is 1.0% or more but less than 5.0%. ×: The change in transmittance is 5.0% or more.

<Viscosity characteristics>
The viscosity of the obtained photosensitive coloring composition was measured at a rotation speed of 20 rpm using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.).
The evaluation ranking is as follows:
◯: Viscosity 2.0 or more and less than 10.0: Good level ×: Viscosity 10.0 or more: Unusable level

<Storage stability>
The storage stability was evaluated by the following method.
The initial viscosity on the day after the photosensitive coloring composition was prepared and the viscosity over time after aging at 40° C. for one week were measured using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) at 25° C. and a rotation speed of 50 rpm. From the initial viscosity and the viscosity over time, the viscosity change rate over time was calculated using the following formula, and the storage stability was evaluated in two stages.
[Change rate of viscosity over time] = |([initial viscosity] - [viscosity over time]) / [initial viscosity] | x 100
○: The rate of change is less than 10% ×: The rate of change is 10% or more

Claims (8)

A photosensitive coloring composition used for forming a pattern of a color filter by a photolithography method in which the pattern is cured by a heating step of 150° C. or less after development,
The composition contains a pigment (A), a resin (B), a photopolymerization initiator (C), and a polymerizable compound (D), in which the resin (B) contains a resin (B1) that contains a blocked isocyanate group-containing structural unit, and a resin (B2) that contains a (meth)acryloyl group-containing vinyl polymer moiety ,
The resin (B2) further has an aromatic carboxylic acid moiety,
The content of the pigment (A) is 45% by mass to 70% by mass of the total nonvolatile content,
A photosensitive coloring composition, characterized in that the acid values of both the resin (B1) and the resin (B2) are 50 to 160 (mgKOH/g) . The photosensitive coloring composition according to claim 1, characterized in that the resin (B1) further has a carboxy group-containing structural unit. 3. The photosensitive coloring composition according to claim 1, wherein the total amount of the resin (B1) and the resin (B2) is 80 mass % or more based on the total amount of the resin (B). 4. The photosensitive coloring composition according to claim 1, further comprising at least one of a basic pigment derivative and a basic resin-type dispersant. A cured film which is a cured product of the photosensitive coloring composition according to any one of claims 1 to 4 . A color filter comprising the cured film according to claim 5 . A solid-state imaging device comprising the color filter according to claim 6 . An image display device comprising the color filter according to claim 6 .