Curable composition, inkjet ink using same, cured film, color filter, solid-state imaging element, and image display device

Abstract

Provided are: a curable composition which exhibits excellent characteristics such as low particle diameter change rate over time, high storage stability, excellent ejection properties, and low foreign matter generation rate; an inkjet ink, a cured film, and a color filter using the curable composition; and a solid-state imaging element and an image display device which include the color filter. The problem is solved by a curable composition comprising a colorant (A), a pigment derivative (B1) represented by general formula (1), a pigment derivative (B2) represented by general formula (2), a polymerizable compound (C), and a polymerization initiator (D), the content of a solvent in the curable composition being 5.0 mass% or less. General formula (1) # imgabs 0 # general formula (2) # imgabs 1 #

Description

Technical Field

[0001] The present invention relates to a curable composition, an inkjet ink using the same, a cured film, a color filter, a solid-state imaging element, and an image display device. Background Art

[0002] In recent years, solvent-free inkjet recording methods have attracted much attention. The solvent-free inkjet recording method is to apply an ink that can be cured by irradiation with ultraviolet rays or other radiation to a desired material in an image-like manner, and harden the ink applied in an image-like manner to record an image. In the curable composition used in inkjet, it is important to ensure the dispersion stability of the colorant. If there is a problem with the dispersion stability, it may cause various problems such as the precipitation of aggregated foreign matter on the film or the reduction of the ejection property of the inkjet ink.

[0003] As a method for obtaining a stable inkjet ink, for example, a composition using a pigment derivative is proposed in Patent Document 1. In addition, an inkjet ink using a quinophthalone derivative is disclosed in Patent Document 2. However, although the inkjet inks disclosed in these documents have dispersion stability, there is room for improvement in ejection stability or the rate of change of particle diameter over time.

[0004] [Prior art literature]

[0005] [Patent Document]

[0006] [Patent Document 1] Japanese Patent Publication No. 2004-18656

[0007] [Patent Document 2] Japanese Patent Application Publication No. 2006-348205 Summary of the invention

[0008] [Problems to be solved by the invention]

[0009] An object of the present invention is to provide a curable composition, an inkjet ink, a film using the same, a color filter, a solid-state imaging element including the color filter, and an image display device, which have a small change rate of particle diameter over time and show excellent characteristics such as high storage stability, excellent ejection properties, and low foreign matter generation rate.

[0010] [Technical means to solve the problem]

[0011] The present inventors have made intensive studies to solve the above problems and have found that the above problems can be solved by including two pigment derivatives of specific structures in a curable composition having a solvent content of 5.0 mass % or less, thereby completing the present invention.

[0012] That is, the present invention relates to a curable composition comprising a colorant (A), a pigment derivative (B1) represented by the general formula (1), a pigment derivative (B2) represented by the general formula (2), a polymerizable compound (C) and a polymerization initiator (D), wherein the content of the solvent in the curable composition is 5.0% by mass or less.

[0013] Furthermore, the present invention relates to the curable composition, wherein the polymerizable compound (C) contains a difunctional (meth)acrylate.

[0014] The present invention also relates to the curable composition, wherein the colorant (A) contains at least one selected from phthalocyanine pigments, isoindoline pigments, azo metal complex pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, and anthraquinone pigments.

[0015] The present invention also relates to the curable composition, wherein the mass ratio of the pigment derivative (B1) represented by the general formula (1) to the pigment derivative (B2) represented by the general formula (2) is 99.9:0.1 to 50.0:50.0.

[0016] The present invention also relates to the curable composition, wherein the pigment derivative (B1) is in the general formula (1), R 101 ~R 108 In the general formula (2), at least one of the pigment derivatives (B2) is a halogen atom. 114 ~R 121 At least one of them is a halogen atom.

[0017] In addition, the present invention relates to an inkjet ink comprising the curable composition.

[0018] Furthermore, the present invention relates to a cured film formed from the curable composition.

[0019] Furthermore, the present invention relates to a color filter including the cured film.

[0020] Furthermore, the present invention relates to a solid-state imaging element including the color filter.

[0021] In addition, the present invention relates to an image display device comprising the color filter.

[0022] [Effects of the Invention]

[0023] According to the present invention, there can be provided a curable composition having a small rate of change in particle size over time and exhibiting excellent properties such as high storage stability, excellent ejection properties and a low rate of foreign matter generation, an inkjet ink, a film using the same, a color filter, a solid-state imaging element including the color filter, and an image display device. DETAILED DESCRIPTION

[0024] Hereinafter, the form of the curable composition for implementing the present invention will be described in detail. In addition, the present invention is not limited to the following embodiments, and can be implemented by modifying it within the range that can solve the problem.

[0025] In the present specification, "(meth)acryloyl", "(meth)acrylic acid", "(meth)acrylic acid", "(meth)acrylate", "(meth)acryloyloxy" or "(meth)acrylamide" means "acryloyl and / or methacryloyl", "acrylic acid and / or methacrylic acid", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", "acryloyloxy and / or methacryloyloxy" or "acrylamide and / or methacrylamide", unless otherwise specified. In addition, "CI" means Colour Index (CI; issued by The Society of Dyers and Colourists).

[0026] <Colorant (A)>

[0027] The curable composition of the present invention contains a colorant (A). The colorant (A) can be selected from a variety of pigments and dyes known in the art. Specific examples of the colorant (A) that can be used in the curable composition are shown below by color index number.

[0028] As the red pigment, for example, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64 、64:1、68、69、81、81:1、81:2、81:3、81:4、83、88、90:1、101、101:1、104、108、108:1、109、112、113、114、122、123、144、146、147、149、151、166、168、169、170、172、173、174、175、176、177、178、179、181、184、 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 261 2,263,264,265,266,267,268,269,270,271,272,273,274,275,276,277,278,279,280,281,282,283,284,285,286,287,291,295 or 296, the pigment described in Japanese Patent Laid-Open No. 2014-134712, the pigment described in Japanese Patent No. 6368844, etc. In addition, red dyes such as xanthene-based, azo-based, disazo-based, and anthraquinone-based dyes can also be used. Specifically, salt compounds of xanthene-based acid dyes such as CI Acid Red 52, 87, 92, 289, and 338 can be listed. Among them, CI Pigment Red 177, 254, and 291 are preferred from the viewpoint of coloring power and storage stability.

[0029] As the orange pigment, CI pigment orange 34, 36, 38, 43, 51, 55, 59, 61, 62, 64, 71, or 73 can be used.

[0030] As yellow pigments, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 124 5, 126, 127, 128, 129, 137, 138, 139, 147, 148, 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, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221, 231, 233 or 234. In addition, quinoline-based, azo-based, disazo-based, methine-based yellow dyes may also be used. Among them, CI Pigment Yellow 138, 139, 150, 185, and 231 are preferred from the viewpoint of coloring power and storage stability.

[0031] As green pigments, for example, CI Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, zinc phthalocyanine pigments described in Japanese Patent Laid-Open No. 2008-19383, Japanese Patent Laid-Open No. 2007-320986, Japanese Patent Laid-Open No. 2004-70342, International Publication No. 2015 / 118720, etc., aluminum phthalocyanine pigments described in Japanese Patent No. 4893859, etc. can also be used. Among them, CI Pigment Green 7, 36, 58, 59, 62, and 63 are preferred from the viewpoint of coloring power and storage stability.

[0032] As the blue pigment, for example, CI pigment blue 1, 1:2, 1:3, 2, 2:1, 2:2, 3, 8, 9, 10, 10:1, 11, 12, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 18, 19, 22, 24, 24:1, 53, 56, 56:1, 57, 58, 59, 60, 61, 62, 64 and the like blue pigments can be used.

[0033] Examples of the violet pigment include CI 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, but are not particularly limited thereto.

[0034] Inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, chrome yellow, zinc yellow, red iron (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, umber, synthetic iron black, etc. In order to achieve a balance between chroma and brightness while ensuring good coating properties, sensitivity, developability, etc., inorganic pigments can be used in combination with organic pigments.

[0035] From the viewpoint of storage stability, the colorant (A) preferably contains at least one selected from phthalocyanine pigments, isoindoline pigments, azo metal complex pigments, quinophthalone pigments, diketopyrrolopyrrole pigments and anthraquinone pigments, and particularly preferably phthalocyanine pigments, isoindoline pigments, azo metal complex pigments, quinophthalone pigments and anthraquinone pigments.

[0036] (Pigment micronization)

[0037] When the colorant (A) used in the curable composition of the present invention is a pigment, it is preferably used after micronization. The micronization method is not particularly limited. For example, any of wet grinding, dry grinding, and dissolution separation methods can be used. As exemplified in the present invention, a kneader method as a type of wet grinding can be used for salt milling treatment. The average primary particle size of the pigment obtained by a transmission electron microscope (TEM) is preferably in the range of 5nm to 90nm. There is a situation where if it is less than 5nm, it is difficult to disperse, and if it is greater than 90nm, the transmittance is reduced. For this reason, the more preferred average primary particle size is in the range of 10nm to 70nm.

[0038] The so-called salt milling treatment is the following treatment: using a batch or continuous kneading machine such as a kneader, a double-roll mill, a triple-roll mill, a ball mill, a grinder, a sand mill, a planetary mixer, etc., a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent is mechanically kneaded while being heated, and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and during salt milling, the high hardness of the inorganic salt is used to crush the pigment. By optimizing the conditions for salt milling the pigment, a pigment with a very fine primary particle diameter, a narrow distribution range, and a sharp particle size distribution can be obtained.

[0039] As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc. can be used. In terms of price, sodium chloride (salt) is preferably used. In terms of processing efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight, relative to 100 parts by weight of the pigment.

[0040] The water-soluble organic solvent plays a role in wetting the pigment and the water-soluble inorganic salt. If it is an organic solvent that is dissolved (mixed) in water and does not substantially dissolve the inorganic salt used, it is not particularly limited. Among them, during salt grinding, the temperature rises and the solvent becomes a state that is easy to evaporate. Therefore, in terms of safety, a high boiling point solvent with a boiling point of more than 120°C is preferably used. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. can be used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

[0041] When the pigment is subjected to salt milling treatment, a resin may be added as needed. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified from natural resins, etc. may be used. The resin used is preferably solid and water-insoluble at room temperature, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight relative to 100 parts by weight of the pigment.

[0042] <Pigment derivatives>

[0043] The curable composition of the present invention contains a pigment derivative (B1) represented by the general formula (1) and a pigment derivative (B2) represented by the general formula (2). The pigment derivative (B1) and the pigment derivative (B2) are pigment derivatives having a quinophthalone skeleton.

[0044] There is a situation where most of the pigment derivative is adsorbed on the colorant (A), but a part of it is not adsorbed and is free in the composition. Here, the pigment derivative (B1) having a sulfonic acid group and the pigment derivative (B2) having a sulfonic acid group and a carboxyl group have different acidity. It is speculated that by including two pigment derivatives (B1) and (B2) with different acidity, the pigment derivatives also interact with each other, and the free pigment derivatives are small, so a curable composition with good ejection properties and storage stability can be obtained. Furthermore, it is speculated that the pigment derivative (B1) and the pigment derivative (B2) have the same quinophthalone skeleton, so compared with the case of using two pigment derivatives with different skeletons, the interaction is strong, so the condensed foreign matter is reduced and the particle size change rate over time is also reduced.

[0045] (Pigment derivative (B1))

[0046] The pigment derivative (B1) contained in the curable composition of the present invention is represented by the following general formula (1).

[0047] General formula (1)

[0048]

[0049] [In the general formula (1), R 101 ~R 113 R each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, -SO3H or a metal salt or alkylammonium salt of -SO3H; 101 ~R 104 and / or R 105 ~R 108 The adjacent groups of may be integrated to form an aromatic ring which may have a substituent; R 101 ~R 113 At least one of them is -SO3H or a metal salt or alkylammonium salt of -SO3H]

[0050] For R in the general formula (1), 101 ~R 113 Provide explanation.

[0051] Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

[0052] In addition, examples of the alkyl group which may have a substituent include, in addition to straight-chain or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl, n-octyl, stearyl, and 2-ethylhexyl, alkyl groups having a substituent such as trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-dibromoethyl, 2,2,3,3-tetrafluoropropyl, 2-ethoxyethyl, 2-butoxyethyl, 2-nitropropyl, benzyl, 4-methylbenzyl, 4-tert-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl, and 2,4-dichlorobenzyl.

[0053] In addition, examples of the alkoxy group which may have a substituent include, in addition to straight-chain or branched alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutyloxy, tert-butyloxy, neopentyloxy, 2,3-dimethyl-3-pentyloxy, n-hexyloxy, n-octyloxy, stearyloxy, and 2-ethylhexyloxy groups, alkoxy groups having a substituent such as trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropyloxy, 2,2-di-trifluoromethylpropoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-nitropropoxy, and benzyloxy groups.

[0054] In addition, examples of the aryl group which may have a substituent include, in addition to aryl groups such as phenyl, naphthyl, and anthracenyl, p-methylphenyl, p-bromophenyl, p-nitrophenyl, p-methoxyphenyl, 2,4-dichlorophenyl, pentafluorophenyl, 2-aminophenyl, 2-methyl-4-chlorophenyl, 4-hydroxy-1-naphthyl, 6-methyl-2-naphthyl, 4,5,8-trichloro-2-naphthyl, anthraquinone, and 2-aminoanthraquinone.

[0055] R 101 ~R 113 At least one of them is -SO3H or a metal salt or alkylammonium salt of -SO3H.

[0056] As metal salts of -SO3H, salts of various metals such as sodium, potassium, calcium, barium, copper, zinc, magnesium, aluminum, nickel, cobalt, and strontium can be cited. Among these, aluminum salts not only have excellent separation properties during production and dispersibility as pigment derivatives, but also have low viscosity, flow properties, and the most excellent viscosity stability over time.

[0057] As alkylammonium salts of -SO3H, there can be mentioned: lower amines such as dimethylamine, trimethylamine, diethylamine, triethylamine, hydroxyethylamine, dihydroxyethylamine, 2-ethylhexylamine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, and N,N-dibutylaminopropylamine; long-chain alkylamines having an alkyl group with more than 12 carbon atoms such as laurylamine, oleylamine, palmitylamine, stearylamine, and dimethyllaurylamine; long-chain alkyl quaternary ammonium salts having an alkyl group with more than 12 carbon atoms such as lauryltrimethylammonium, dilauryldimethylammonium, stearyltrimethylammonium, and distearyldimethylammonium. Among these, the effect is the highest when long-chain alkylamines having an alkyl group with more than 12 carbon atoms such as laurylammonium and stearylammonium are used.

[0058] The pigment derivative (B1) may have any structure as long as it is represented by the general formula (1), but preferably has a halogen atom as R 101 ~R 108 structure.

[0059] Examples of the pigment derivative (B1) include the compounds shown below, but the present invention is not limited to these.

[0060]

[0061] (Pigment derivative (B2))

[0062] The pigment derivative (B2) contained in the curable composition of the present invention is represented by the following general formula (2).

[0063] General formula (2)

[0064]

[0065] [In general formula (2), R 114 ~R 126 R each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, -SO3H or a metal salt or alkylammonium salt of -SO3H; 114 ~R 117 and / or R 118 ~R 121 The adjacent groups of may be integrated to form an aromatic ring which may have a substituent; R 114 ~R 126 At least one of them is -SO3H or a metal salt or alkylammonium salt of -SO3H]

[0066] As R 114 ~R 126 The alkyl group which may have a substituent, the alkoxy group which may have a substituent, and the aryl group which may have a substituent and R101 ~R 113 The records are the same.

[0067] The pigment derivative (B2) may have any structure as long as it is represented by the general formula (2), but preferably has a halogen atom as R 114 ~R 121 structure.

[0068] Examples of the pigment derivative (B2) include the compounds shown below, but the present invention is not limited to these.

[0069]

[0070] The mass ratio of the pigment derivative (B1) to the pigment derivative (B2) is preferably 99.9:0.1 to 50.0:50.0, and more preferably 99.5:0.5 to 70.0:30.0 from the viewpoint of storage stability and aggregated foreign matter.

[0071] The total content of the pigment derivative (B1) and the pigment derivative (B2) is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the colorant (A).

[0072] The curable composition of the present invention may contain a pigment derivative other than the pigment derivative (B1) and the pigment derivative (B2).

[0073] Pigment derivatives other than the pigment derivatives (B1) and the pigment derivatives (B2) are compounds having an acidic group, a basic group, a neutral group, etc. in the organic pigment residue. Examples of the pigment derivatives include compounds having an acidic substituent such as a sulfonic group, a carboxyl group, or a phosphoric acid group, and amine salts thereof, compounds having a basic substituent such as a sulfonamide group or a terminal tertiary amino group, and compounds having a neutral substituent such as a phenyl group or a phthalimide alkyl group.

[0074] Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments (excluding pigment derivatives (B1) and pigment derivatives (B2)), naphthol pigments, reduced pigments, phthalocyanine pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

[0075] <Polymerizable compound (C)>

[0076] The curable composition of the present invention contains a polymerizable compound (C). The polymerizable compound (C) is not particularly limited, and conventionally known monofunctional, difunctional, and trifunctional or higher polyfunctional monomers and oligomers can be used. The polymerizable compound (C) can be used alone or in combination of two or more.

[0077] As the monofunctional monomer, monofunctional acrylic monomers or monofunctional vinyl monomers can be cited. As specific examples of compounds, benzyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate (ethoxylated (or propoxylated)), dicyclopentenyl (oxyethyl) (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, 2-methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 2-ethoxyethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, methoxydipropylene glycol (meth)acrylate, dipropylene glycol (meth)acrylate, nonylphenol ethylene oxide (EO) modified acrylate, nonylphenol propylene oxide (propylene oxide) modified acrylate, oxide, PO) modified acrylate, o-phenylphenol EO modified acrylate, 2-ethylhexyl EO modified acrylate, β-carboxyethyl (meth)acrylate, trimethylolpropane formal (meth)acrylate, isopentyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 1,4-cyclohexanedimethanol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, acryloylmorpholine and N-acryloyloxyethylhexahydrophthalimide and other monofunctional acrylic monomers or N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylformamide and other monofunctional vinyl monomers, etc.

[0078] These compounds may be used alone or in combination of two or more.

[0079] The polyfunctional monomer includes a compound having two or more polymerizable functional groups in the molecule, and examples thereof include polyfunctional acrylic monomers other than 2-(2-vinyloxyethoxy)ethyl acrylate and vinyl monomers.

[0080] Specific examples of the compound include dihydroxymethyl tricyclodecane di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (ethoxylated (or propoxylated)) 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, (ethoxylated (or propoxylated)) neopentyl glycol diacrylate, di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.

[0081] As another example of a multifunctional monomer, a multifunctional vinyl monomer containing multiple vinyl groups in the molecule can be cited. As specific examples of compounds, butanediol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, trimethylolpropane divinyl ether, pentaerythritol tri(or tetra)vinyl ether, trimethylolpropane diallyl ether, pentaerythritol tri(or tetra)allyl ether, etc. can be cited. These compounds can be used alone or in combination of two or more.

[0082] Furthermore, "EO modification" means ethylene oxide modification, and "PO modification" means propylene oxide modification.

[0083] Particularly preferred are polymerizable compounds that dissolve polymer dispersants and / or pigment derivatives. Specifically, examples include: 2-phenoxyethyl acrylate, acryloyl morpholine, ethoxylated neopentyl glycol di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, isobornyl acrylate, phenoxydiethylene glycol acrylate, vinyl caprolactam, vinyl pyrrolidone, N-vinyl formamide, and 2-hydroxy-3-phenoxypropyl acrylate. Among them, from the viewpoint of storage stability, it is preferred to contain a difunctional (meth)acrylate, and dipropylene glycol diacrylate is particularly preferred.

[0084] In addition, from the viewpoint of storage stability and agglomerated foreign matter, it is preferred that a difunctional (meth)acrylate is added and attached to the surface of the pigment, pigment derivative, etc. when the pigment, pigment derivative, etc. are mixed and dispersed. It is preferred that a monofunctional (meth)acrylate is not substantially contained during the dispersion treatment.

[0085] The curable composition of the present invention preferably contains 2-(2-vinyloxyethoxy)ethyl acrylate as a polymerizable compound (C). 2-(2-vinyloxyethoxy)ethyl acrylate is commercially available as "VEEA" and "VEEA-AI" manufactured by Nippon Catalyst Co., Ltd. 2-(2-vinyloxyethoxy)ethyl acrylate has low viscosity and high reactivity. Therefore, it is excellent as a material for preparing a low-viscosity and high-sensitivity curable composition. Based on the total weight of the curable composition, the content of 2-(2-vinyloxyethoxy)ethyl acrylate is preferably 5% to 50% by mass, and more preferably 5% to 35% by mass.

[0086] <Polymerization initiator (D)>

[0087] The curable composition of the present invention contains a polymerization initiator (D). The polymerization initiator that can be used in the present invention may be a known polymerization initiator. For example, it is preferred to use a polymerization initiator of a molecular cleavage type or a dehydrogenation type that generates free radicals. In the present invention, the polymerization initiator (D) may be used alone or in combination of two or more. In addition, a polymerization initiator that generates free radicals and a polymerization initiator that generates cations may be used in combination.

[0088] Specific examples of the polymerization initiator (D) include α-hydroxyphenyl alkyl ketone compounds such as 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propane-1-one, and methyl benzoylformate; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-dimethylamino-2-(4-methyl-benzyl)-1- α-aminophenyl alkyl ketone compounds such as (4-morpholin-4-yl-phenyl)-butanone-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; acyl phosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyl oxime)] and ethyl ketone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime); benzophenone, 4-phenylbenzophenone, isophthalic acid ketone (isophthalic acid ketone) phenone), 4-benzoyl-4'-methyl-diphenyl sulfide and other benzophenone compounds; 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 -s-triazine, 2,4-bis(trichloromethyl)-6-phenylvinyl-s-triazine, 2-(naphthalene-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphthalene-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine or 2,4-trichloromethyl-(4'-methoxyphenylvinyl)-6-triazine and other triazine compounds.

[0089] Among the commercially available products, examples of α-hydroxy alkyl phenone compounds include Omnirad 127, 184, 1173, and 2959 manufactured by IGM Resins, examples of α-amino alkyl phenone compounds include Omnirad 907, 369E, and 379EG manufactured by IGM Resins, examples of acylphosphine oxide compounds include Omnirad 819 and TPO manufactured by IGM Resins, and examples of oxime ester compounds include IRGACURE OXE-01, 02, 03, 04, and 05 manufactured by BASF Japan, and Adeka Akuze manufactured by ADEKA. arkls) N-1919, NCI-730, 831E, 930, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, 3057 manufactured by Changzhou Qiangli New Materials Co., Ltd., Omnirad 1312, 1314, 1316 manufactured by IGM Resins, SPI-02, 03, 04, 05, 06, 07 manufactured by Samyang Corporation, DFI-020, 306, EOX-01 manufactured by DaitoChemix, etc.

[0090] Among these, oxime ester compounds are preferred.

[0091] (Oxime ester compound)

[0092] Oxime ester compounds absorb ultraviolet rays to generate cleavage of the NO bond of oxime, generating imino radicals and alkoxy radicals. These radicals further decompose to generate highly active radicals, so patterns can be formed using a small amount of exposure. Oxime ester compounds have high quantum efficiency, so a coating with high curability and less foreign matter can be obtained.

[0093] Examples of the oxime ester compound include oxime ester compounds described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, and International Publication No. 2021 / 175855.

[0094] The content of the polymerization initiator (D) is preferably 2% to 20% by mass, more preferably 5% to 15% by mass in the curable composition. When an appropriate amount is added, the photocurability is further improved.

[0095] <Dispersant>

[0096] The curable composition of the present invention may contain a dispersant for dispersing the colorant (A).

[0097] Regarding the dispersant, the description of known documents such as Japanese Patent Application Laid-Open No. 2011-225848 may be appropriately referred to.

[0098] Specific examples include: Lubrizol's SOLSPERSE series (for example, SOLSPERSE 16000, 21000, 32000, 33000, 41000, J180, J200, etc.), BYK-Chemie's DISPERBYK series (for example, DISPERBYK 102, 110, 111, 118, 165, 168, 190, etc.), and Evonik's TEGO Dispers series (for example, TEGO Dispers 610, 630, 651, 655, 750W, 755W, etc.).

[0099] <Solvent>

[0100] In order to improve the low viscosity of the curable composition and the wetting and spreading property on the substrate, a small amount of solvent may be contained in the curable composition. The solvent is selected in consideration of the solubility and safety of each component of the curable composition. In terms of curability, the content of the solvent in the curable composition is set to 5.0% by mass or less. In terms of ejection stability, it is preferably 0.2% to 5.0% by mass, and more preferably 0.5% to 4.0% by mass.

[0101] Among the above solvents, the boiling point of the solvent is preferably 120°C to 300°C, more preferably 140°C to 270°C. Preferred solvents include glycol compounds, monoacetates, diacetates, glycols, monoalkyl ethers, dialkyl ethers, and lactic acid esters. Among them, glycol compounds, monoacetates, monoalkyl ethers, and dialkyl ethers are preferred. More specifically, tetraethylene glycol dialkyl ether, ethylene glycol monobutyl ether acetate, and diethylene glycol diethyl ether are preferred.

[0102] <Sensitizer>

[0103] The curable composition of the present invention may contain a sensitizer.

[0104] Examples of the sensitizer include unsaturated ketones such as chalcone derivatives and dibenzalacetone; 1,2-diketone derivatives such as benzyl or camphorquinone; benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine pigments such as oxonol derivatives; acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives. compounds, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalinoporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal aromatic complexes, organic ruthenium complexes or Michler's ketone (Michler's ketone) derivatives, α-acyloxy esters, acylphosphine oxides, methyl benzoylformate, 9,10-phenanthrenequinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, etc.

[0105] Among the sensitizers, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives can be cited as particularly suitable sensitizers. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N-ethylcarbazole, etc. can be used.

[0106] More specifically, the sensitizers recorded in " Pigment Handbook " (1986, Kodansha) compiled by people such as Okawahara Shin, " Chemistry of Functional Pigments " (1981, CMC) compiled by people such as Okawahara Shin and " Special Function Materials " (1986, CMC) compiled by people such as Chisen Zhongsanlang can be enumerated, but are not limited to these. In addition, it is also possible to contain a sensitizer that demonstrates absorption for the light in the ultraviolet to near infrared region. The sensitizer can be used alone or in combination with two or more.

[0107] <Polymerization inhibitor>

[0108] In order to improve the viscosity stability over time, the ejection stability after time, and the viscosity stability in the inkjet recording device, the curable composition of the present invention can use a polymerization inhibitor. As a polymerization inhibitor, hindered phenol compounds, phenothiazine compounds, hindered amine compounds, and phosphorus compounds can be particularly suitably used. Specifically, 4-methoxyphenol, hydroquinone, methyl hydroquinone, tert-butyl hydroquinone, 2,6-di-tert-butyl-4-methylphenol, phenothiazine, aluminum salts of N-nitrosophenylhydroxylamine, etc. can be listed. In terms of maintaining curability while improving stability over time, it is preferably formulated at a ratio of 0.01% to 2% by mass relative to the entire curable composition.

[0109] <Antioxidants>

[0110] The curable composition of the present invention may contain an antioxidant. The antioxidant prevents the polymerization initiator contained in the curable composition from being oxidized and yellowing, thereby improving the transmittance of the coating film.

[0111] Examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In the present invention, the antioxidant is preferably a compound that does not contain a halogen atom.

[0112] Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred from the viewpoint of achieving a balance between transmittance and sensitivity of the coating film.

[0113] The antioxidants may be used alone or in combination of two or more.

[0114] The content of the antioxidant is more preferably 0.5% by mass to 5.0% by mass based on 100% by mass of the solid content of the curable composition, because the transmittance and spectral characteristics are good.

[0115] <Surface Conditioning Agent>

[0116] The curable composition of the present invention may contain a surface conditioner.

[0117] The surface conditioner described in this specification refers to a substance that reduces the surface tension of the curable composition by addition. Examples of the surface conditioner include silicone surface conditioners, fluorine surface conditioners, acrylic surface conditioners, acetylene glycol surface conditioners, etc. From the perspective of the ability to reduce surface tension and compatibility with polymerizable compounds, it is preferred to use a silicone surface conditioner.

[0118] As a specific silicone surface conditioner, a modified body of a dimethylsiloxane skeleton can be cited. Among them, a polyether-modified silicone surface conditioner is preferred. The so-called polyether can be, for example, polyethylene oxide and polypropylene oxide. In one embodiment of the present invention, a polyether-modified silicone surfactant that can be obtained in the form of a commercial product can be used. As an example of a representative product that can be preferably used, polyether-modified siloxanes such as BYK (registered trademark) -378, 348 and 349 of BYK Chemical Company can be cited; and polyether-modified polydimethylsiloxanes such as BYK-UV3500 and UV3510 can be cited. In addition, polyether-modified siloxane copolymers such as TEGO (registered trademark) GLIDE 450, 440, 435, 432, 410, 406, 130, 110 and 100 of Evonik Degussa can be cited. Among these, polyether-modified silicone-based surface conditioning agents such as BYK-331, 378, 348, UV3510, and TEGOGLIDE 450, 440, 432, and 410 are preferred from the viewpoint of achieving good image quality.

[0119] The content of the silicone-based surface conditioning agent is preferably in the range of 0.1% to 5.0% by mass relative to the total weight of the curable composition. By setting the content to 0.1% by mass or more, the wettability of the curable composition to the substrate can be easily improved. On the other hand, by setting the content to 5.0% by mass or less, the storage stability of the curable composition can be easily ensured.

[0120] <Storage stabilizer>

[0121] In order to stabilize the viscosity of the composition over time, the curable composition of the present invention may contain a storage stabilizer. Examples of the storage stabilizer include: benzyltrimethyl chloride; quaternary ammonium chlorides such as diethylhydroxylamine; organic acids such as lactic acid and oxalic acid and their methyl ethers; tert-butyl catechol; organic phosphines such as tetraethylphosphine and tetraphenylphosphine; phosphites, etc. The storage stabilizer can be used in an amount of 0.1% to 10% by mass based on the total amount of the colorant (A) (100% by mass).

[0122] <Other ingredients>

[0123] The curable composition of the present invention may contain other components other than those described above. Examples of other components include: binder resin, thermal crosslinking agent, curing agent, curing accelerator, acid generator, curing catalyst, chain transfer agent, silane coupling agent, near infrared absorber, etc. The content of other components can be appropriately set within the range that can solve the problem of the present invention.

[0124] <Method for preparing curable composition>

[0125] The curable composition of the present invention can be prepared by further adding a polymerizable compound (C), a polymerization initiator (D), etc. to a colorant dispersion, and diluting the colorant dispersion. The colorant dispersion is prepared by finely dispersing the colorant (A), the pigment derivative (B1), and the pigment derivative (B2) together with a dispersant, a polymerizable compound (C), and a colorant carrier such as a polymerizable compound using various dispersing means such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, a ring-shaped bead mill, or a grinder. When preparing the colorant dispersion, two or more colorants may be dispersed in the colorant carrier at the same time, or the obtained products dispersed in the colorant carriers may be mixed. In the case where the solubility of a colorant such as a dye is high, specifically, if the solubility is high in the polymerizable compound (C) used, it is dissolved by stirring, and no foreign matter is confirmed, it is not necessary to finely disperse it as described above.

[0126] <Water content>

[0127] In view of stability, the curable composition of the present invention preferably has a water content of 2.0% by mass or less.

[0128] The content of water contained in the curable composition is more preferably 1.5% by mass or less, and particularly preferably 1.0% by mass or less. The lower limit of the water content is preferably as small as possible, and is not particularly limited.

[0129] The method for controlling the water content is not particularly limited, and a known method can be used. For example, a method of reducing the amount of water contained in the components by sufficiently drying the components can be used. In addition, a method of producing a curable composition while blowing in dried air or an inert gas or a mixed gas thereof can be mentioned.

[0130] <Specific metal atoms>

[0131] The curable composition of the present invention may contain a small amount of metal components including Li, Na, Mg, K, Cs, Co, Ca, Fe, Si and Zr (hereinafter referred to as specific metal atoms) in addition to the components of the colorant (A), the pigment derivative (B1) and the pigment derivative (B2), the polymerizable compound (C) and the polymerization initiator (D). If a large amount of metal components including these specific metal atoms are present, the storage stability may be impaired, the heat resistance may be reduced, and the ejection property may be deteriorated.

[0132] In addition, a color filter produced using a curable composition containing a large amount of a metal component containing such a specific metal atom may generate foreign matter, which may result in a decrease in transmittance. The total content of the specific metal atoms in the metal component contained in the curable composition of the present invention is preferably 1 mass ppm to 1000 mass ppm relative to the entire curable composition.

[0133] <Average dispersed particle size>

[0134] The average dispersed particle size (secondary particle size) of the particles in the curable composition is preferably 10 nm to 300 nm, and more preferably 30 nm to 250 nm. If the particles have an appropriate particle size, a curable composition with high dispersion stability can be easily obtained.

[0135] About the determination method of average dispersed particle diameter (secondary particle diameter), for example, using the microtrack UPA-EX150 of Nikkiso Co., Ltd. adopting dynamic light scattering method (fast Fourier transform (FFT) power spectrum method), particle permeability is set to absorption mode, particle shape is set to non-spherical, and D50 particle diameter is set to average diameter. The diluting solvent used for determination utilizes the solvent used in dispersion respectively, and if the sample treated with ultrasound is measured just after the sample is prepared, it is easy to obtain a result with small deviation and is preferred.

[0136] <Removal of coarse particles>

[0137] The curable composition is preferably subjected to centrifugal separation, filtration using a sintered filter or a membrane filter, etc. to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably coarse particles of 0.5 μm or more, and the dust mixed therein. The curable composition of the present invention preferably does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

[0138] <Inkjet ink>

[0139] The curable composition of the present invention can be used as an inkjet ink by appropriately adjusting its composition. The use of the inkjet ink is not particularly limited, but it is preferably used as an inkjet ink for color filters.

[0140] The inkjet ink of the present invention is preferably adjusted to have a viscosity of 5 to 50 mPa·s at 25° C. When the viscosity is within the above range, excellent followability and stability of discharge are achieved.

[0141] <Printing method>

[0142] The inkjet ink of the present invention has excellent curability and can be used in a single-pass printing method. In the single-pass printing method, for example, an ink ejection mechanism including one or more inkjet heads, a mechanism for transporting a substrate with the ink at a desired speed, and a mechanism for curing the ink by irradiating active energy rays such as ultraviolet (UV) lamps or electron beams are continuously provided.

[0143] The optimum ink film thickness is preferably 2 μm to 30 μm, more preferably 3 μm to 25 μm, and still more preferably 4 μm to 20 μm. Within the above range, good color development and curability are achieved.

[0144] <Inkjet Head>

[0145] The inkjet head used in the inkjet printing method may be an on-demand method or a continuous method. In addition, as the ejection method, an electro-mechanical conversion method (e.g., a single chamber type, a dual chamber type, a vendor type, a piston type, a shared mode type, a shared wall type, etc.), an electro-thermal conversion method (e.g., a thermal inkjet type, a bubble jet (BUBBLE-JET) (registered trademark) type, etc.), an electrostatic suction method (e.g., an electric field control type, a slit jet type, etc.), a discharge method (e.g., a spark jet type, etc.) and the like may be cited as specific examples, and any ejection method may be used.

[0146] <Ink droplet size>

[0147] The volume of ink droplets ejected from the inkjet head is preferably within a range of 0.5 pL to 100 pL, and is more preferably within a range of 2 pL to 20 pL from the viewpoint of reducing coating unevenness and increasing the printing speed.

[0148] <Printing method>

[0149] There are two types of printing methods based on inkjet printing: single-pass printing and multi-pass printing. The single-pass printing method is a method in which a plurality of inkjet heads are fixedly arranged in a predetermined printing area and printing is performed in a single head scanning method. In contrast, the multi-pass printing method (also called serial printing method) is a method in which printing is performed in a predetermined printing area in multiple head scanning methods.

[0150] In the single-pass printing method, it is preferred to use a wide head with nozzles arranged in parallel over a width greater than the width of the desired coating pattern. When multiple independent coating patterns with discontinuous patterns are formed on the same substrate, it is sufficient to use a wide head at least greater than the width of each coating pattern.

[0151] The active energy rays used to cure the inkjet ink can be any energy rays that can affect the electron orbit of the irradiated body and induce polymerization reactions of free radicals, cations, anions, etc. Although not particularly limited, specific examples include electron beams, ultraviolet rays, and infrared rays. In the present invention, ultraviolet rays can be preferably used.

[0152] Specific examples that can be used as a light source for ultraviolet light include high pressure mercury lamps, metal halide lamps, low pressure mercury lamps, ultra-high pressure mercury lamps, ultraviolet lasers, light emitting diodes (LEDs), and sunlight. In terms of convenience or price, it is preferred to use high pressure mercury lamps, metal halide lamps, and LEDs. The maximum wavelength of light emission is preferably 200nm to 600nm, more preferably 300nm to 450nm, and further preferably 320nm to 420nm, and particularly preferably ultraviolet light in the range of 340nm to 400nm.

[0153] <Color filter>

[0154] The color filter of the present invention comprises a substrate and the cured film of the present invention.

[0155] The color filter of the present invention comprises: at least one red filter segment, at least one green filter segment and at least one blue filter segment. Furthermore, in addition to the filter segments of the three colors, a yellow filter segment may also be included.

[0156] <Color filter manufacturing method>

[0157] The color filter of the present invention can be produced by a printing method.

[0158] Regarding the formation of filter segments using the printing method, since patterning can be performed by printing a curable composition prepared as an inkjet ink, it is a method for manufacturing a color filter with low cost and excellent mass production. Furthermore, due to the development of printing technology, fine patterns with high dimensional accuracy and smoothness can be printed. In order to print, it is preferred to set the composition so that the ink will not dry or solidify on the printing plate or on the blanket. In addition, the control of the fluidity of the ink on the printing press is also important, and the viscosity of the ink can also be adjusted using a dispersant or a body pigment.

[0159] <Solid-state imaging device>

[0160] The solid-state imaging element of the present invention has the color filter. The form used for the solid-state imaging element is not particularly limited, and for example, it is a structure as follows: a plurality of photodiodes and a transmission electrode including polysilicon etc. constituting the light receiving area of ​​the solid-state imaging element (charge coupled device (CCD) image sensor, complementary metal oxide semiconductor (CMOS) image sensor, etc.) are provided on a substrate, a light shielding film is provided on the photodiode and the transmission electrode, and only the light receiving part of the photodiode is opened, and a device protection film including silicon nitride etc. is provided on the light shielding film so as to cover the entire surface of the light shielding film and the light receiving part of the photodiode, and a filter is provided on the device protection film. Furthermore, it may also be a structure having a focusing means (for example, a microlens, etc.; the same below) on the device protection film and below the filter (on the side close to the substrate) or a structure having a focusing means on the filter. In addition, the filter may also have a structure in which a hardened film forming each color pixel is buried in a space divided into a grid shape by a partition wall, for example. In this case, the partition wall preferably has a lower refractive index than each colored pixel.

[0161] The imaging device including the solid-state imaging element of the present invention can be used in various applications such as digital cameras, electronic devices with imaging functions (such as smartphones and tablet terminals), vehicle-mounted cameras, surveillance cameras, and optical sensors.

[0162] <Image display device>

[0163] The image display device of the present invention has the color filter. Examples of the image display device include a liquid crystal display, an organic electroluminescence (EL) display, and the like. The form used in the image display device is not particularly limited, and it can be used as a color filter, a black matrix, a light-shielding filter, an infrared cutoff filter, or an infrared transmission filter.

[0164] The form of the image display device is not particularly limited as long as it functions as an image display device. For example, the structure described in "Next Generation Liquid Crystal Display Technology (written by Tatsuo Uchida, Kogyo Shokukai Co., Ltd., published in 1994) can be cited.

[0165] The definition of an image display device or the details of each image display device are described in, for example, "Electronic Display Devices (written by Akio Sasaki, published by Kogyo Shokukai Co., Ltd. in 1990)" and "Display Devices (written by Junaki Ibuki, published by Sangyo Tosho Co., Ltd. in 1989)".

[0166] [Example]

[0167] Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited thereto. In addition, "parts" means "parts by mass" and "%" means "% by mass".

[0168] (Identification Method of Compound (Q-1) and Compound (Q-2))

[0169] In the identification of the compounds (Q-1) and (Q-2) of the present invention, matrix-assisted laser desorption / ionization time of flight mass spectrometry (MALDI TOF-MS) spectra were used. The MALDI TOF-MS spectra were obtained using a MALDI mass spectrometer, Autoflex III, manufactured by Bruker-Daltonics, and the obtained compounds were identified based on the agreement between the molecular ion peaks of the obtained mass spectrum and the mass numbers obtained by calculation.

[0170] (Identification Method of Pigment Derivatives)

[0171] The pigment derivative (B1) and the pigment derivative (B2) used in the examples of the present invention were dissolved in dimethylformamide (DMF) and analyzed using a liquid chromatography / mass spectrometry (LC / MS) analysis device manufactured by Waters, Japan. The obtained compound was identified based on the agreement between the peak of the chromatogram at 420 nm and the mass number obtained by calculation.

[0172] The measurement conditions of LC are shown below.

[0173] Device: ACQUITY UPLC H-Class manufactured by Waters Japan

[0174] Xevo TQD manufactured by Waters Japan

[0175] Column: ACQUITY UPLC BEH C18 (Waters Corporation, Japan)

[0176] Eluent:

[0177] (A) Adjust the pH to 4.5 using 0.05 mol / l CH3COONH4 aqueous solution and acetic acid

[0178] (B)DMF

[0179] Gradient conditions:

[0180] After maintaining (A): (B) = 80 / 20 (volume ratio) for 1 minute, the volume ratio was changed from (A): (B) = 80 / 20 (volume ratio) to (A): (B) = 5 / 95 (volume ratio) over 5 minutes, maintained at (A): (B) = 5 / 95 (volume ratio) for 3 minutes, and then maintained at (A): (B) = 80 / 20 (volume ratio) for 7 minutes.

[0181] Flow rate: 0.40ml / min

[0182] Flow time: 15 minutes

[0183] Injection volume: 1μl

[0184] Column temperature: 40℃

[0185] (Weight average molecular weight of dispersant (Mw))

[0186] The weight average molecular weight (Mw) of the dispersant is a polystyrene-equivalent weight average molecular weight (Mw) measured using a TSKgel column (manufactured by Tosoh Corporation) and a gel permeation chromatograph (GPC) (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with a refractive index (RI) detector, and using a 3 mM triethylamine and 10 mM LiBr N,N-dimethylformamide solution as a developing solvent.

[0187] (Amine value of dispersant)

[0188] The amine value of the dispersant is obtained by potentiometric titration using a 0.1 N hydrochloric acid aqueous solution and converted into potassium hydroxide equivalent. The amine value of the dispersant indicates the amine value of the nonvolatile component.

[0189] (Quaternary ammonium salt value of dispersant)

[0190] The quaternary ammonium salt value of the dispersant is obtained by titrating with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and then converted into potassium hydroxide equivalent. The quaternary ammonium salt value of the dispersant described below indicates the quaternary ammonium salt value of the nonvolatile component.

[0191] <Synthesis of pigment derivatives>

[0192] (Synthesis of Pigment Derivative (B1-1))

[0193] 50 parts of quinophthalone yellow pigment CI Pigment Yellow 138 ("Paliotol Yellow K0960-HD" manufactured by BASF) were dissolved in 500 parts of 101% sulfuric acid and stirred at 70°C for 8 hours to carry out sulfonation reaction. The end point of the reaction was set to the point where no change in the spectrum was observed when measuring the spectral spectrum of the sulfuric acid solution. Then, the reaction solution was injected into 5000 parts of stirred ice water, and the precipitate was filtered and separated and washed with water. The pigment derivative (B1-1) was obtained by drying at 80°C. Identification was carried out by mass analysis based on LC-MS.

[0194] Pigment derivatives (B1-1)

[0195]

[0196] (Synthesis of Pigment Derivative (B1-2))

[0197] 69.0 parts of an aqueous paste of the pigment derivative (B1-1) (water content: 85.5%) are added to 500 parts of water, stirred and redispersed, and then dissolved by adjusting the pH to 10 using a 25% caustic soda solution. 9.6 parts of an 8% aqueous solution of aluminum chloride hexahydrate are slowly added to the solution. Precipitates continue to appear from the dripped portion, and the pH slowly decreases with the addition. After the addition is completed, no seepage is observed. After filtering and separating the precipitate from the slurry, wash with water, and dry at 80°C to obtain a pigment derivative (B1-2).

[0198] (Synthesis of Pigment Derivative (B1-3))

[0199] Pigment derivative (B1-3) was obtained by the same operation as that of the synthesis of pigment derivative (B1-2) except that 12.3 parts of 8% zinc chloride hydrate aqueous solution was used instead of 9.6 parts of 8% aluminum chloride hexahydrate aqueous solution used in the synthesis of pigment derivative (B1-2).

[0200] (Synthesis of Pigment Derivative (B1-4))

[0201] 47.5 parts of 8-aminoquinaldine, 90.1 parts of tetrachlorophthalic anhydride, and 183.2 parts of benzoic acid were added to 200 parts of methyl benzoate, heated to 120°C, and stirred for 4 hours while distilling off water. Furthermore, 62.4 parts of 2,3-naphthalene dicarboxylic anhydride were added to the reaction mixture, heated to 180°C, and stirred for 4 hours while distilling off water. After cooling to room temperature, the reaction mixture was added to 1200 parts of ethanol and stirred at room temperature for 1 hour. After filtering and separating the precipitated crystals, they were washed with ethanol and dried under reduced pressure to obtain 74.6 parts of compound (Q-1) (yield: 96%). Identification was performed by mass analysis based on TOF-MS.

[0202] Compound (Q-1)

[0203]

[0204] Pigment derivative (B1-4) was obtained by performing the same operation as that of the synthesis of pigment derivative (B1-1), except that 50 parts of the obtained compound (Q-1) were used instead of 50 parts of CI Pigment Yellow 138 ("Paliotol Yellow K0960-HD" manufactured by BASF) used in the synthesis of pigment derivative (B1-1).

[0205] Pigment derivatives (B1-4)

[0206]

[0207] (Synthesis of Pigment Derivative (B1-5))

[0208] 70.0 parts of the aqueous paste of the pigment derivative (B1-4) (water content: 83.0%) are added to 500 parts of water, stirred and redispersed, and then 25% caustic soda solution is used to adjust the pH to 10 to dissolve it. 5.2 parts of an 8% aqueous solution of coconut oil amine acetate (trade name: Acetamin 24, manufactured by Kao Co., Ltd.) are slowly added to the solution. Precipitates continue to appear from the dripped part, and the pH slowly decreases with the addition. After the addition is completed, no exudation is observed. After filtering and separating the precipitate from the slurry, it is washed with water and dried at 80°C to obtain a pigment derivative (B1-5).

[0209] (Synthesis of Pigment Derivative (B1-6))

[0210] 47.5 parts of 8-aminoquinaldine, 120.2 parts of 5,7,8-trichloro-6-sulfo-2,3-naphthalene dicarboxylic anhydride, and 183.2 parts of benzoic acid were added to 200 parts of methyl benzoate, heated to 120°C, and stirred for 6 hours while distilling off water. Furthermore, 51.1 parts of 4-methylphthalic anhydride were further added to the reaction mixture, heated to 180°C, and stirred for 5 hours while distilling off water. After cooling to room temperature, the reaction mixture was put into 1200 parts of ethanol and stirred at room temperature for 1 hour. After filtering and separating the precipitated crystals, they were washed with ethanol and water in sequence, and dried at 80°C to obtain a pigment derivative (B1-6). Identification was performed by mass analysis based on LC-MS.

[0211] Pigment derivatives (B1-6)

[0212]

[0213] (Synthesis of Pigment Derivative (B1-7))

[0214] 47.5 parts of 8-aminoquinaldine, 97.8 parts of phthalic anhydride and 183.2 parts of benzoic acid were added to 200 parts of methyl benzoate, heated to 180°C, and stirred for 5 hours while distilling off water. After cooling to room temperature, the reaction mixture was put into 1200 parts of ethanol and stirred at room temperature for 1 hour. After filtering and separating the precipitated crystals, they were washed with ethanol and dried under reduced pressure to obtain 111.7 parts of compound (Q-2) (yield: 89%). Identification was performed by mass analysis based on TOF-MS.

[0215] Compound (Q-2)

[0216]

[0217] 50 parts of the obtained compound (Q-2) were dissolved in 500 parts of 100% sulfuric acid and stirred at 80°C for 10 hours to perform a sulfonation reaction. The end point of the reaction was set to the point where no change in the spectrum was observed when measuring the spectral spectrum of the sulfuric acid solution. Then, the reaction solution was injected into 5000 parts of stirred ice water, and the precipitate was filtered and separated, washed with water, and then dried under reduced pressure to obtain a pigment derivative (B1-7). Identification was performed by mass analysis based on LC-MS.

[0218] Pigment derivatives (B1-7)

[0219]

[0220] (Synthesis of Pigment Derivative (B2-1))

[0221] 69.0 parts of an aqueous paste of the pigment derivative (B1-1) (water content: 85.5%) are added to 500 parts of water, stirred and redispersed, and then 25% caustic soda solution is added while stirring to adjust the pH to 11.5. During the pH adjustment, the reaction solution changes from a yellow slurry state to a red solution state. The pH is slightly adjusted every 5 minutes and continued for 1 hour. Furthermore, it is heated to 50°C at pH 11.5 and stirred for 3 hours. A 25% aqueous hydrochloric acid solution is added dropwise to the red solution, and the pH is adjusted to 3.5 to obtain a yellow precipitate. The yellow precipitate is separated by filtration, washed with a large amount of water, and dried at 80°C to obtain 40 parts of the pigment derivative (B2-1). Identification is performed by mass analysis based on LC-MS.

[0222] (Pigment derivative (B2-1))

[0223]

[0224] (Synthesis of Pigment Derivative (B2-2))

[0225] 69.0 parts of a water paste of the pigment derivative (B1-1) (water content: 85.5%) are added to 500 parts of water, stirred and redispersed, and then adjusted to pH 11.5 using 25% caustic soda solution. During the pH adjustment, the reaction liquid changes from a yellow slurry state to a red solution state. The pH is finely adjusted every 5 minutes and continued for 1 hour. Furthermore, it is heated to 50°C at pH 11.5 and stirred for 3 hours. 18.2 parts of an 8% aluminum chloride hexahydrate aqueous solution are slowly added to the red solution. Precipitates continue to appear from the dripped portion, and the pH slowly decreases to 3.8 as the addition proceeds. The precipitate is separated by filtration, washed with a large amount of water, and then dried at 80°C to obtain 44 parts of a pigment derivative (B2-2).

[0226] (Synthesis of Pigment Derivative (B2-3))

[0227] 69.0 parts of an aqueous paste of the pigment derivative (B1-1) (water content: 85.5%) are added to 500 parts of water, stirred and redispersed, and then adjusted to pH 11.5 using 25% caustic soda solution. During the pH adjustment, the reaction solution changes from a yellow slurry state to a red solution state. The pH is slightly adjusted every 5 minutes and continued for 1 hour. Furthermore, it is heated to 50°C at pH 11.5 and stirred for 3 hours. 24.0 parts of an 8% aqueous zinc chloride solution are slowly added to the red solution. Precipitates continue to appear from the dripped portion, and the pH slowly decreases to 3.7 as the addition proceeds. The precipitate is separated by filtration, washed with a large amount of water, and then dried at 80°C to obtain 42 parts of a pigment derivative (B2-3).

[0228] (Synthesis of Pigment Derivative (B2-4))

[0229] 70.0 parts of the aqueous paste of compound (Q-1) (water content: 85.0%) are added to 500 parts of water, stirred and redispersed, and then adjusted to pH 11.5 using 25% caustic soda solution. During the pH adjustment, the reaction solution changes from a yellow slurry state to a red solution state. The pH is slightly adjusted every 5 minutes and continued for 1 hour. Furthermore, it is heated to 50°C and stirred for 3 hours at pH 11.5. A 25% aqueous hydrochloric acid solution is added dropwise to the red solution, and the pH is adjusted to 3.5 to obtain a yellow precipitate. The yellow precipitate is separated by filtration, washed with a large amount of water, and dried at 80°C to obtain 41 parts of a pigment derivative (B2-4). Identification is carried out by mass analysis based on LC-MS.

[0230] (Pigment derivative (B2-4))

[0231]

[0232] (Synthesis of Pigment Derivative (B2-5))

[0233] 70.0 parts of the aqueous paste of compound (Q-1) (water content: 85.0%) were added to 500 parts of water, stirred and redispersed, and then adjusted to pH 11.5 using 25% caustic soda solution. During the pH adjustment, the reaction solution changed from a yellow slurry state to a red solution state. The pH was slightly adjusted every 5 minutes and continued for 1 hour. Furthermore, it was heated to 50°C at pH 11.5 and stirred for 3 hours. 10.5 parts of an 8% aqueous solution of coconut oil amine acetate (trade name: Acetamin 24, manufactured by Kao Co., Ltd.) were slowly added to the red solution. Precipitates continued to appear from the dripped part, and the pH slowly decreased to 3.9 as it was added. The yellow precipitate was separated by filtration, washed with a large amount of water, and dried at 80°C to obtain 43 parts of a pigment derivative (B2-5).

[0234] (Synthesis of Pigment Derivative (B2-6))

[0235] 70.0 parts of a water paste of the pigment derivative (B1-6) (water content: 84.5%) are added to 500 parts of water, stirred and redispersed, and then 25% caustic soda solution is added while stirring to adjust the pH to 11.5. During the pH adjustment, the reaction solution changes from a yellow slurry state to a red solution state. The pH is slightly adjusted every 5 minutes and continued for 1 hour. Furthermore, it is heated to 50°C at pH 11.5 and stirred for 3 hours. A 25% aqueous hydrochloric acid solution is added dropwise to the red solution, and the pH is adjusted to 3.5 to obtain a yellow precipitate. The yellow precipitate is separated by filtration, washed with a large amount of water, and dried at 80°C to obtain 40 parts of the pigment derivative (B2-6). Identification is performed by mass analysis based on LC-MS.

[0236] (Pigment derivative (B2-6))

[0237]

[0238] (Synthesis of Pigment Derivative (B2-7))

[0239] 67.0 parts of an aqueous paste of the pigment derivative (B1-7) (water content: 85.2%) are added to 500 parts of water, stirred and redispersed, and then 25% caustic soda solution is added while stirring to adjust the pH to 11.5. During the pH adjustment, the reaction solution changes from a yellow slurry state to a red solution state. The pH is slightly adjusted every 5 minutes and continued for 1 hour. Furthermore, it is heated to 50°C at pH 11.5 and stirred for 3 hours. A 25% aqueous hydrochloric acid solution is added dropwise to the red solution, and the pH is adjusted to 3.5 to obtain a yellow precipitate. The yellow precipitate is separated by filtration, washed with a large amount of water, and dried at 80°C to obtain 40 parts of the pigment derivative (B2-7). Identification is performed by mass analysis based on LC-MS.

[0240] (Pigment derivative (B2-7))

[0241]

[0242] (Synthesis of Dispersant (E-1))

[0243] In a reaction vessel equipped with a stirrer and a thermometer, 41 parts of N,N-dimethylpropylenediamine and 120 parts of chloroform were placed, stirred at room temperature, and 50 parts of methacrylic chloride were added dropwise over 1 hour. After stirring at room temperature for 3 hours, 1 After the reaction was confirmed to be complete by H-nuclear magnetic resonance (NMR), the reaction solution was washed with 300 parts of ion exchange water and 200 parts of saturated saline, and 20 g of magnesium sulfate was added to the organic layer, stirred and filtered. The solvent in the obtained solution was distilled off by a rotary evaporator to obtain 58 parts of the compound [B] represented by the following formula (15) in the form of a light yellow transparent liquid (yield: 85%). The obtained compound was identified by 1 H-NMR was used.

[0244] Formula (15)

[0245]

[0246] In a reaction tank equipped with a gas introduction pipe, a condenser, a stirring blade and a thermometer, 15.7 parts of methyl methacrylate, 47.2 parts of n-butyl methacrylate and 13.2 parts of tetramethylethylenediamine were placed, and stirred at 50°C for 1 hour while nitrogen was flowing, and the system was purged with nitrogen. Next, 2.6 parts of ethyl bromide isobutyrate, 5.6 parts of cuprous chloride and 100 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) were placed, and the temperature was raised to 110°C under a nitrogen flow to start the polymerization of the first block. After 4 hours of polymerization, the polymerization solution was sampled and the solid content was measured. The polymerization conversion rate was confirmed to be 98% or more by conversion based on the non-volatile component.

[0247] Next, 25 parts of PGMAc and 30.3 parts of the compound [B] as the second block monomer were added to the reaction vessel, and the reaction was continued by stirring while maintaining the temperature at 110° C. in a nitrogen atmosphere. Two hours after the addition of the compound [B] represented by the formula (15), the polymerization solution was sampled and the solid content was measured. The conversion of the second block was confirmed to be 98% or more based on the non-volatile content.

[0248] Furthermore, 6.8 parts of benzyl chloride was added to the reaction vessel, and the mixture was stirred for 3 hours while being maintained at 110° C. in a nitrogen atmosphere, and then cooled.

[0249] The block copolymer solution synthesized above was vacuum dried at 40° C. to obtain a white powder dispersant (E-1) having an amine value of 70 mgKOH / g, a quaternary ammonium salt value of 30 mgKOH / g, and a weight average molecular weight (Mw) of 9,800.

[0250] <Production of curable composition>

[0251] [Production Example 1]

[0252] (Pigment dispersion (d-1))

[0253] A mixture of the following composition is uniformly stirred and mixed using a high-speed mixer or the like, and then the obtained mill-base is subjected to a dispersion treatment for about 1 hour using a horizontal sand mill to prepare a pigment dispersion.

[0254]

[0255] [Manufacturing Examples 2 to 33, Comparative Manufacturing Examples 1 to 3]

[0256] (Pigment dispersion (d-2) to pigment dispersion (d-36))

[0257] Pigment dispersions (d-2) to (d-36) were prepared in the same manner as in pigment dispersion (d-1) except that the colorant (A), pigment derivative, dispersant and polymerizable compound (C) were changed to the compositions and amounts shown in Table 1.

[0258]

[0259] The meanings of the abbreviations in Table 1

[0260] <Colorant (A)>

[0261] · "PY139": CI Pigment Yellow 139

[0262] · “PR177”: CI Pigment Red 177

[0263] · "PR254": CI Pigment Red 254

[0264] "PY150": CI Pigment Yellow 150

[0265] · "PY138": CI Pigment Yellow 138

[0266] · "PY231": CI Pigment Yellow 231

[0267] "PG36": CI Pigment Green 36

[0268] · "PG62": CI Pigment Green 62

[0269] · "PG63": CI Pigment Green 63

[0270] "PG58": CI Pigment Green 58

[0271] "PG59": CI Pigment Green 59

[0272] <Dispersant>

[0273] "SP32000": Alkaline pigment dispersion resin "SOLSPERSE 32000" (manufactured by Lubrizol, Japan)

[0274] "PX4701": Alkaline pigment dispersion resin "EFKA PX4701" (manufactured by BASF)

[0275] "BYK111": Acidic pigment dispersion resin "BYK111" (manufactured by BYK)

[0276] <Pigment derivatives>

[0277] <Polymerizable compound (C)>

[0278] DPGDA: Dipropylene glycol diacrylate, "Laromer DPGDA" manufactured by BASF

[0279] PEA: Phenoxyethyl acrylate, "SR339" manufactured by Sartomer

[0280] [Example 1]

[0281] (Curing composition (D-1))

[0282] In a manner to obtain the formula described in Table 2, a mixture of a polymerizable compound, a photopolymerization initiator, and a stabilizer is slowly added to the previously prepared pigment dispersion, and the obtained mixture is stirred. Subsequently, a surface tension adjuster is added to the mixture, and the mixture is shaken for 6 hours using an oscillator to prepare a curable composition (D-1). The obtained curable composition (D-1) is filtered using a polytetrafluoroethylene (PTFE) filter with a pore size of 0.5 microns to remove dust or coarse particles, and is used as an evaluation ink. In addition, the order of adding the raw materials used to obtain the mixture and the order of mixing may be different.

[0283] [Example 2 to Example 44, Comparative Example 1 to Comparative Example 4]

[0284] (Curable composition (D-2) to curable composition (D-48))

[0285] Except having changed the material type and mass as described in Table 2, the same procedure as the curable composition (D-1) was carried out to prepare curable compositions (D-2) to (D-48).

[0286] <Polymerizable compound (C)>

[0287] VEER: 2-(2-vinyloxyethoxy)ethyl acrylate, "VEEA" manufactured by Nippon Catalyst Co., Ltd.

[0288] PEA: Phenoxyethyl acrylate, "SR339" manufactured by Sartomer

[0289] DPGDA: Dipropylene glycol diacrylate, "Laromer DPGDA" manufactured by BASF

[0290] <Stabilizer>

[0291] · BHT: "H-BHT" manufactured by Honshu Chemical Co., Ltd.

[0292] · Phenothiazine: "Phenothiazine" manufactured by Seiko Chemical Co., Ltd.

[0293] <Surface Conditioning Agent>

[0294] BYK-UV3510: manufactured by BYK Chemie, polyether-modified polydimethylsiloxane

[0295] <Polymerization initiator (D)>

[0296] Omnirad 819: manufactured by IGM Resins, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide

[0297] Omnirad TPO: manufactured by IGM Resins, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide

[0298] Omnirad 369: manufactured by IGM Resins, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1

[0299] KAYACURE BMS: 4-Benzoyl-4'-methyl-diphenyl sulfide manufactured by Nippon Kayaku Co., Ltd.

[0300] IRGACURE OXE-04: manufactured by BASF Japan.

[0301] ·D-1: The following compound

[0302]

[0303] ·D-2: The following compounds

[0304]

[0305] <Solvent>

[0306] ·DEDG: Diethylene glycol diethyl ether

[0307] ·Butyl cellosolve acetate: Ethylene glycol monobutyl ether acetate

[0308] <Ink Evaluation Method>

[0309] The evaluation inks prepared in the embodiments and comparative examples were printed using a single-pass inkjet printer ("OnePass Jet" manufactured by TRYTEC Co., Ltd.) having an ink ejection mechanism equipped with a head (KJ4A) manufactured by Kyocera, a mechanism for transporting the substrate on which the ink has landed at a desired speed, and a mechanism for subsequent irradiation with a UV lamp, under printing conditions of an ink droplet volume of 14 pl and 600 dpi×600 dpi, and various characteristics were evaluated.

[0310] The UV lamp used was a GEW UV lamp (240 W) with a cumulative light intensity of 200 mJ / cm 2 The samples of the cured films were prepared under the conditions of . The printing speed or the printing image was changed in each performance evaluation.

[0311] [Storage stability]

[0312] The viscosity of the obtained curable composition was measured and set as the initial viscosity. Furthermore, an accelerated time test was performed at 60°C for two weeks to measure the accelerated time viscosity. The accelerated time viscosity / initial viscosity was calculated as the rate of change due to accelerated time, and evaluated according to the following criteria.

[0313] ◎: Change rate less than 5%

[0314] ○: Change rate is 5% or more and less than 10%

[0315] △: Change rate is 10% or more and less than 20%

[0316] ×: Change rate 20% or more

[0317] [Change rate of 50% diameter]

[0318] For each of the curable compositions prepared above, the curable composition was diluted 200 to 1000 times with methyl ethyl ketone, and the volume-based 50% diameter D1 was measured using a micro track UPA150 (Nikkiso Co., Ltd., wet-type particle size distribution meter). Then, 100 ml of each curable composition was placed in a sample bottle so as not to cause evaporation and sealed, and stored in a thermostatic chamber at 60° C. for one week. The volume-based 50% diameter D2 after storage was measured in the same manner as above, and the change rate of the average particle diameter was calculated according to the following formula, and the storage stability was evaluated according to the following evaluation criteria.

[0319] Change rate of 50% diameter based on volume = {(D2-D1) / D1}×100%

[0320] ◎: The change rate of the average particle size of the curable composition is less than 5%

[0321] ○: The change rate of the average particle size of the curable composition is 5% or more and less than 10%

[0322] △: The change rate of the average particle size of the curable composition is 10% or more and less than 30%

[0323] ×: The change rate of the average particle size of the curable composition is 30% or more

[0324] [Discharge stability]

[0325] A nozzle check pattern was printed on the prepared curable composition using an inkjet printer, and after printing 100,000 times, the nozzle check pattern was printed again, and the ejection property was evaluated based on the number of missing nozzles. The evaluation criteria are as follows.

[0326] The conveyor speed was set at 35 m / min.

[0327] ○: No nozzle loss after 100,000 prints

[0328] △: After printing 100,000 times, 1 to 5 nozzles are missing

[0329] ×: More than 6 nozzles are missing after printing 100,000 times

[0330] [Evaluation of aggregated foreign matter]

[0331] The evaluation ink was printed on a 1.1 mm thick glass substrate using an inkjet printer to obtain a sample of the cured film. The conveyor speed was set to 35 m / min. Afterwards, the surface of the obtained sample was observed. A metal microscope "BX60" manufactured by Olympus system was used for the evaluation. The magnification was set to 500 times, and the number of particles that could be observed in any 5 fields of view was counted and evaluated in a transparent manner. In addition, ◎ is a very good level, ○ is a good level, △ is a practical level, and × is a level that is not suitable for practical use.

[0332] ◎: The number of foreign objects is less than 10

[0333] ○: The number of foreign objects is 10 or more and less than 20

[0334] △: The number of foreign objects is 20 or more and less than 60

[0335] ×: The number of foreign objects is 60 or more

[0336]

[0337]

[0338]

[0339] According to the results of Tables 2-1 to 2-3, Examples 1 to 44 containing a colorant (A), a pigment derivative (B1), and a pigment derivative (B2) have a small change rate in particle size over time, high storage stability, excellent ejectability, and a low foreign matter generation rate.

[0340] [Example 101]

[0341] (Curing composition (DD-1))

[0342] A mixed solution of a polymerizable compound, a photopolymerization initiator, and a polymerization inhibitor was slowly added to the previously prepared pigment dispersion in such a manner as to obtain the formulation described in Table 3, and the obtained mixed solution was stirred. Subsequently, a surface tension adjuster was added to the mixed solution, and the mixture was shaken for 6 hours using an oscillator to prepare a curable composition (DD-1). The obtained curable composition (DD-1) was filtered using a PTFE filter with a pore size of 0.5 μm to remove dust and coarse particles, and was used as an evaluation ink. In addition, the order of adding the raw materials and the order of mixing for obtaining the mixed solution may be different.

[0343] [Example 102 to Example 105, Comparative Example 101]

[0344] (Curing composition (DD-2) to curable composition (DD-6))

[0345] Except having changed the material type and mass as described in Table 3, the same procedure as the curable composition (DD-1) was carried out to prepare curable compositions (DD-2) to (DD-6).

[0346] <Evaluation of Coloring Composition>

[0347] The obtained curable compositions (DD-1) to (DD-6) were evaluated by the same method as that of the curable compositions (D-1) to (D-48).

[0348] [Table 3]

[0349]

[0350] According to the results in Table 3, Examples 101 to 105 containing the colorant (A), the pigment derivative (B1), and the pigment derivative (B2) have a small change rate of particle size over time, high storage stability, excellent ejectability, and a low foreign matter generation rate.

Claims

1. A curable composition comprising a colorant (A), a pigment derivative (B1) represented by the general formula (1), a pigment derivative (B2) represented by the general formula (2), a polymerizable compound (C) and a polymerization initiator (D), wherein the content of the solvent in the curable composition is 5.0% by mass or less; General formula (1) [In the general formula (1), R 101 ~R 113 R each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, -SO3H or a metal salt or alkylammonium salt of -SO3H; 101 ~R 104 and / or R 105 ~R 108 The adjacent groups of may be integrated to form an aromatic ring which may have a substituent; R 101 ~R 113 At least one of them is -SO3H or a metal salt or alkylammonium salt of -SO3H] General formula (2) [In general formula (2), R 114 ~R 126 R each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, -SO3H or a metal salt or alkylammonium salt of -SO3H; 114 ~R 117 and / or R 118 ~R 121 The adjacent groups of may be integrated to form an aromatic ring which may have a substituent; R 114 ~R 126 At least one of them is -SO3H or a metal salt or alkylammonium salt of -SO3H].

2. The curable composition according to claim 1, wherein The polymerizable compound (C) contains a difunctional (meth)acrylate.

3. The curable composition according to claim 1, wherein The colorant (A) contains at least one selected from the group consisting of phthalocyanine pigments, isoindoline pigments, azo metal complex pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, and anthraquinone pigments.

4. The curable composition according to claim 1, wherein The mass ratio of the pigment derivative (B1) represented by the general formula (1) to the pigment derivative (B2) represented by the general formula (2) is 99.9:0.1 to 50.0:50.

0.

5. The curable composition according to claim 1, wherein The pigment derivative (B1) is a pigment derivative having the general formula (1) wherein R 101 ~R 108 In the general formula (2), at least one of the pigment derivatives (B2) is a halogen atom. 114 ~R 121 At least one of them is a halogen atom.

6. The curable composition according to claim 1, wherein The polymerization initiator (D) contains an oxime ester compound.

7. An inkjet ink comprising the curable composition according to claim 1. 8 . A cured film formed from the curable composition according to claim 1 or the inkjet ink according to claim 7 . 9 . A color filter comprising a substrate and the cured film according to claim 8 . 10 . A solid-state imaging element comprising the color filter according to claim 9 .

11. An image display device comprising the color filter according to claim 9.

Images