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

Abstract

To provide: a curable composition that exhibits good long-term storage stability and excellent dischargeability, curability and solvent resistance; an inkjet ink; a cured film using the same; a color filter; and a solid-state imaging element and an image display device, both including the color filter.SOLUTION: A curable composition comprises: a colorant (A); a dispersant (B) represented by the following general formula; a polymerizable compound (C); and a polymerization initiator (D); where the solvent content in the curable composition is 5.0% or less. In the formula: A1 to A4 represent, e.g., a combination selected from a group of conditions including condition A), where two of the moieties A1 to A4 are mutually identical or different monovalent polymer moieties (P) and the other two moieties are mutually identical or different -C(=O)OH or -CH2C(=O)OH; and X1 represents an acid anhydride residue generated by reacting a terminal hydroxyl group of the polymer moieties (P) with an acid anhydride.SELECTED DRAWING: None

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 device, and an image display device.

Background Art

[0002] In recent years, an inkjet recording method has attracted attention in which an ink curable by irradiation with radiation such as ultraviolet rays is applied in an image-like manner to a desired material, and an image is recorded by curing the ink applied in an image-like manner. In an ink (inkjet ink) used in the inkjet recording method, it is important to ensure the storage stability of a colorant. When there is a problem with storage stability, various problems such as aggregation foreign matter depositing on the film and the ejection property of the inkjet ink deteriorating are caused. In order to ensure the storage stability of a colorant, a dispersant is used. In inkjet inks, it is common to use a basic dispersant, and various proposals have been made (Patent Documents 1 and 2). However, there are few acid dispersants that can be used in inkjet inks, and there is a demand for an inkjet ink having good storage stability using a dispersant having a carboxylic acid with high dispersibility. In addition, the solvent resistance to N-methylpyrrolidone and the like has not been satisfactory.

Prior Art Documents

Patent Documents

Patent Document 1

Patent Document 2

[0003] JP 2012-184404

Summary of the Invention

Problems to be Solved by the Invention

[0004] ​The present invention aims to provide a curable composition, an inkjet ink, a cured film using the same, a color filter, a solid-state imaging device including the color filter, and an image display device, which have good long-term storage stability and excellent ejection properties, curability, and solvent resistance.

Means for Solving the Problems

[0005] As a result of intensive studies to solve the above problems, the present inventors have found that, in a curable composition having a solvent content of 5.0% or less, the above problems can be solved by using a dispersant having a specific structure, and thus the present invention has been achieved.

[0006] That is, the present invention relates to a curable composition containing a colorant (A), a dispersant (B) represented by the general formula (1), a polymerizable compound (C), and a polymerization initiator (D), wherein the solvent content in the curable composition is 5.0% or less.

[0007] General formula (1)

Chemical formula

[0008] The present invention also relates to the curable composition, wherein the colorant (A) contains a basic derivative (E).

[0009] In addition, the present invention also relates to the curable composition, wherein X 1 is an acid dianhydride residue of an aromatic tetracarboxylic dianhydride.

[0010] The present invention also relates to the curable composition, wherein the polymerization initiator (D) contains an oxime ester compound.

[0011] The present invention also relates to an inkjet ink containing the curable composition.

[0012] The present invention also relates to a cured film formed by the curable composition or the inkjet ink.

[0013] The present invention also relates to a color filter having the cured film.

[0014] The present invention also relates to a solid-state imaging device including the color filter.

[0015] The present invention also relates to an image display device including the color filter.

Advantages of the Invention

[0016] According to the present invention, it is possible to provide a curable composition, an inkjet ink, a cured film using the same, a color filter, a solid-state imaging device including the color filter, and an image display device, which have good long-term storage stability and are excellent in ejection property, curability, and solvent resistance.

Embodiments for Carrying Out the Invention

[0017] Hereinafter, embodiments for carrying out the curable composition of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments and can be implemented with modifications within a range capable of solving the problems.

[0018] In this specification, “(meth)acryloyl”, “(meth)acrylic”, “(meth)acrylic acid”, “(meth)acrylate”, or “(meth)acrylamide” 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. Also, “C.I.” means Color Index (C.I.; published by The Society of Dyers and Colourists).

[0019] <Colorant (A)> As the colorant (A) contained in the curable composition of the present invention, it can be arbitrarily selected from various conventionally known pigments and dyes. Specific examples of the colorant (A) that can be used in the curable composition are shown by Color Index numbers below.

[0020] As red pigments, 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, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, or 296, pigments described in JP-A-2014-134712, pigments described in Japanese Patent No. 6368844, etc. can be used. Also, red dyes such as xanthene-based, azo-based, disazo-based, and anthraquinone-based dyes can be used. Specifically, salt-forming compounds of xanthene-based acid dyes such as C.I. Acid Red 52, 87, 92, 289, 338, etc. can be mentioned. Among them, from the viewpoints of coloring power and storage stability, C.I. Pigment Red 177, 254, 264, 291 are preferred.

[0021] As orange pigments, orange pigments such as C.I. Pigment Orange 34, 36, 38, 43, 51, 55, 59, 61, 62, 64, 71, or 73 can be used.

[0022] As the yellow pigment, yellow pigments such as C.I. 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, 125, 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 can be used. Also, yellow dyes such as quinoline-based, azo-based, disazo-based, and methine-based dyes can be used. Among them, from the viewpoints of coloring power and storage stability, C.I. Pigment Yellow 139, 150, and 185 are preferred.

[0023] As the green pigment, for example, C.I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, zinc phthalocyanine pigments described in JP-A No. 2008-19383, JP-A No. 2007-320986, JP-A No. 2004-70342, WO 2015 / 118720 pamphlet, etc., aluminum phthalocyanine pigments described in Patent No. 4893859, etc. can also be used. Among them, from the viewpoints of coloring power and storage stability, C.I. Pigment Green 36, 58, 59, and 63 are preferred.

[0024] As the cyan pigment, for example, C.I. 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, etc. can be used.

[0025] As the purple pigment, for example, C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc. can be mentioned, but it is not particularly limited to these.

[0026] In addition, as the inorganic pigments, titanium oxide, barium sulfate, zinc white, lead sulfate, lead yellow, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green, amber, synthetic iron black, etc. can be mentioned. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability, etc. while taking the balance of chroma and lightness.

[0027] (Finely dividing the pigment) When the colorant (A) used in the curable composition of the present invention is a pigment, it is preferably used after being finely divided. The method of fine division is not particularly limited, and for example, any of wet grinding, dry grinding, and solvent precipitation methods can be used, and as exemplified in the present invention, it can be finely divided by performing a salt milling treatment by a kneader method which is one kind of wet grinding. The average primary particle diameter determined by TEM (transmission electron microscope) of the pigment is preferably in the range of 5 to 90 nm. When it becomes smaller than 5 nm, dispersion in the solvent becomes difficult, and when it becomes larger than 90 nm, a sufficient contrast ratio may not be obtained in some cases. For such reasons, a more preferable average primary particle diameter is in the range of 10 to 70 nm.

[0028] Salt milling treatment is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded while heating using a batch-type or continuous kneader such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, a planetary mixer, etc., 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 the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

[0029] As the water-soluble inorganic salt, sodium chloride, potassium chloride, sodium sulfate, etc. can be used, but it is preferable to use sodium chloride (table salt) from the viewpoint of price. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by mass, most preferably 300 to 1000 parts by mass, based on 100 parts by mass of the pigment, from both the viewpoints of treatment efficiency and production efficiency.

[0030] The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent is likely to evaporate, a high-boiling solvent having a boiling point of 120°C or higher is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by mass, most preferably 50 to 500 parts by mass, based on 100 parts by mass of the pigment.

[0031] When performing salt milling treatment on the pigment, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc. can be used. The resin used is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in the above organic solvent. The amount of resin used is preferably in the range of 5 to 200 parts by mass with respect to 100 parts by mass of the pigment.

[0032] <Dispersant (B)> Dispersant (B) is a dispersant represented by the following general formula (1). General formula (1)

Chemical formula

[0033] In general formula (1), A 1 ~A 4 is a combination selected from the group consisting of the following A, B, and C, A) A 1 ~A 4 Among them, two sites are monovalent polymer sites (P) that are the same as or different from each other, and the other two sites are -C(=O)OH or -CH2C(=O)OH that are the same as or different from each other, B) A 1 ~A 4 Among them, one site is a monovalent polymer site (P), and the other three sites are -C(=O)OH or -CH2C(=O)OH that are the same as or different from each other, C) A 1 ~A 4 Among them, one site is a monovalent polymer site (P), the other two sites are -C(=O)OH or -CH2C(=O)OH that are the same as or different from each other, and the other one site is -C(=O)-X a-Ra (wherein Xa is -O- or -N(Ra2)-, Ra is a group selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, and an aryl group having 6 to 18 carbon atoms, and Ra2 is a hydrogen atom or a group selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, and an aryl group having 6 to 18 carbon atoms). The monovalent polymer moiety (P) is a cyclic ester polymer moiety (P1) having a hydroxyl group at one end and a terminal moiety A at the other end, or a vinyl polymer moiety (P2) having a hydroxyl group at the terminal, and the terminal moiety A has a structure derived from a monoalcohol or a monoamine. In addition, X1 in the general formula (1) represents an acid dianhydride residue, and the acid dianhydride residue is formed by reacting the terminal hydroxyl group of the aforementioned polymer moiety (P) with an acid dianhydride.

[0034] Substituent A 1 ~A 4 The combination of two being the monovalent polymer moiety (P) and the other two being -C(=O)OH or -CH2C(=O)OH is preferable, and the combination of two being the monovalent polymer moiety (P) and the other two being -C(=O)OH is more preferable.

[0035] (Polymer moiety (P)) The polymer moiety (P) in the dispersant (B) is a cyclic ester polymer moiety (P1) having a hydroxyl group at one end and a terminal moiety A at the other end, or a vinyl polymer moiety (P2) having a hydroxyl group at the terminal, and the terminal moiety A has a structure derived from a monoalcohol or a monoamine.

[0036] (Cyclic ester polymer moiety (P1)) The cyclic ester polymer moiety (P1) has a hydroxyl group capable of reacting with an acid dianhydride at one terminal moiety. The cyclic ester polymer moiety (P1) can synthesize a cyclic ester polymer having a hydroxyl group at one end by ring-opening polymerization of a cyclic ester using an active hydrogen compound as an initiator. Since the polymerization reaction of the cyclic ester is controlled by the use of the initiator, a cyclic ester polymer with a narrow molecular weight distribution can be obtained.

[0037] The cyclic ester polymer preferably includes a polymer of lactone which is a cyclic ester (polylactone). Lactones include, for example, 3- to 16-membered cyclic esters such as α-acetolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, ζ-enanthrolactone, η-caprylolactone (=8-hydroxyoctanoic acid lactone), 12-hydroxydodecanoic acid lactone, 13-hydroxytetradecanoic acid lactone, 14-hydroxytetradecanoic acid lactone, 15-hydroxypentadecanoic acid lactone and the like. Among these, from the viewpoint of reaction control, δ-valerolactone and ε-caprolactone are preferred, and ε-caprolactone is more preferred.

[0038] For the synthesis of the cyclic ester polymer, cyclic compounds copolymerizable with lactone can be used. Examples of the cyclic compound include lactide, trimethylene carbonate, glycolide, lactam and the like. In the mass of the cyclic ester polymer, polylactone is preferably 50% by mass or more, and preferably 70% by mass or more. The mass is preferably 90% by mass or more, and more preferably 100% by mass.

[0039] The cyclic esters can be used alone or in combination of two or more.

[0040] [Synthesis of cyclic ester polymer moiety (P1)] When a monoalcohol or a monoamine is used in the synthesis of the cyclic ester polymer, a cyclic ester polymer moiety (P1) having a terminal moiety A can be obtained.

[0041] Monoalcohols include, for example, aliphatic monoalcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, tert-butanol, 1-pentanol, isopentanol, 1-hexanol, cyclohexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, isooctanol, 2-ethylhexanol, 1-nonanol, isononanol, 1-decanol, 1-dodecanol, 1-myristyl alcohol, cetyl alcohol, 1-stearyl alcohol, isostearyl alcohol, 2-octyldecanol, 2-octyldodecanol, 2-hexyldecanol, behenyl alcohol, oleyl alcohol; aromatic ring-containing monoalcohols such as benzyl alcohol, phenoxyethyl alcohol, paracumylphenoxyethyl alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, propylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monohexyl ether, dipropylene glycol mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monohexyl ether,Alkylene glycol monoalkyl ethers such as triethylene glycol mono-2-ethylhexyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monohexyl ether, tripropylene glycol mono-2-ethylhexyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol monohexyl ether, tetraethylene glycol mono-2-ethylhexyl ether, tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl ether, tetrapropylene glycol monobutyl ether, tetrapropylene glycol monohexyl ether, tetrapropylene glycol mono-2-ethylhexyl ether, tetra diethylene glycol monomethyl ether, and reactive alcohols such as 3-ethyl-3-oxetanemethanol, 3-ethyl-3-(4-hydroxybutyloxymethyl)oxetane are mentioned. The monoalcohol can be used alone or in combination of two or more.

[0042] Monoamines include, for example, amines having a heterocyclic amino group with aromaticity such as 2-aminomethylpyridine, 3-aminomethylpyridine, 4-aminomethylpyridine, 2-aminoethylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 2-aminomethyl-5-methylpyridine, bis(2-pyridylmethyl)amine, 2-aminomethylpyrazine; amines having a heterocyclic amino group without aromaticity such as N-(3-aminopropyl)piperidine, 1-(3-aminopropyl)-2-methylpiperidine, N-(2-aminoethyl)-4-pipecoline, N-(3-aminopropyl)-4-pipecoline, 4-(aminomethyl)piperidine, 4-aminomethyl-1-butylpiperidine, 1-(2-aminoethyl)pyrrolidine, 2-aminomethylpiperazine; amine compounds having an aliphatic amino group such as 2-(dimethylamino)ethylamine, 3-(dimethylamino)propylamine, 2-diethylaminoethylamine, 3-diethylaminopropylamine, 2-diisopropylaminoethylamine, 3-(dibutylamino)propylamine, N,N-diisopropyl-1,3-propanediamine, 3-(diisobutylamino)propylamine, 3-(2-dimethylaminoethoxy)propylamine, etc. Monoamines can be used alone or in combination of two or more.

[0043] For ring-opening polymerization, it is preferable to use a monoalcohol having a molecular weight of 100 to 300. By setting the molecular weight to 300 or less, a first polymer site with a sharp molecular weight distribution can be obtained, improving the dispersibility of the acidic dispersant. Also, by setting the molecular weight to 100 or more, ring-opening polymerization of the cyclic ester becomes possible at high temperature, improving the yield.

[0044] The usage amount of the initiator is preferably 0.1 to 100 moles, more preferably 0.5 to 100 moles, and even more preferably 1 to 100 moles, per 100 moles of the cyclic ester. Controlling the molar ratio of the cyclic ester to the initiator can adjust the molecular weight of the cyclic ester polymer.

[0045] For ring-opening polymerization, a polymerization catalyst can be used. When using a polymerization catalyst, the reaction temperature can be reduced and the reaction time can be shortened. Examples of the polymerization catalyst include quaternary ammonium salts such as tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide; quaternary phosphonium salts such as tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodide, tetrabutylphosphonium iodide, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide; phosphorus compounds such as triphenylphosphine; organotin compounds such as monomethyltin oxide, monobutyltin oxide, monooctyltin oxide, dibutyltin oxide, dioctyltin dilaurate; organic carboxylates such as potassium acetate, sodium acetate, potassium benzoate, sodium benzoate; alkali metal alcoholates such as sodium alcoholate, potassium alcoholate, and other tertiary amines, organoaluminum compounds, organotitanate compounds, and zinc compounds such as zinc chloride, etc.

[0046] The amount of the polymerization catalyst used is preferably 0.1 ppm to 3000 ppm, more preferably 1 ppm to 1000 ppm, based on 100 parts by mass of the cyclic ester. When used within the above range, it is easy to obtain a cyclic ester polymer with no coloring at a polymerization rate suitable for production.

[0047] The polymerization temperature of the cyclic ester is preferably 100°C to 220°C, more preferably 110°C to 210°C. When carried out within the above range, it is easy to obtain a cyclic ester polymer with few by-products at a polymerization rate suitable for production.

[0048] The weight average molecular weight of the cyclic ester polymer is preferably from 500 to 10,000, more preferably from 1,000 to 8,000, and even more preferably from 1,000 to 5,000. When the molecular weight is 500 or more, the pigment dispersibility can be further improved due to the steric repulsion effect. When the molecular weight is 10,000 or less, appropriate crystallinity and solvent solubility are obtained, resulting in further improved dispersibility.

[0049] (Vinyl polymer moiety (P2)) The vinyl polymer moiety (P2) has a hydroxyl group at its terminal that can react with an acid dianhydride. For example, a vinyl polymer having a hydroxyl group at its terminal can be synthesized by polymerizing a vinyl monomer in the presence of a thiol group-containing alcohol compound.

[0050] Examples of the vinyl monomer include linear or branched alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cetyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, or isostearyl (meth)acrylate; methoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolytetramethylene glycol (meth)acrylate, or methoxypolyethylene glycol polypropylene glycol (meth)acrylate; Cyclic alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, or isobornyl (meth)acrylate; Fluoroalkyl (meth)acrylates such as trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, or tetrafluoropropyl (meth)acrylate; (Meth)acryloxy-modified polydimethylsiloxane (silicone macromer); (Meth)acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth)acrylate, or glycidyl (meth)acrylate, 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane; (Meth)acrylates having an aromatic ring such as benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, parachlorophenylphenoxyethyl (meth)acrylate, parachlorophenylphenoxypolyethylene glycol (meth)acrylate, or nonylphenoxypolyethylene glycol (meth)acrylate; (Meth)acrylic acid, acrylic acid dimer, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth)acrylate, β-carboxyethyl (meth)acrylate, or ω-carboxypolycaprolactone (meth)acrylate, etc. (meth)acrylate having a carboxyl group; Vinyl such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth)acrylate, or allyl (meth)acrylate; (Meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or N-substituted type (meth)acrylamide such as acryloylmorpholine; Amino group-containing (meth)acrylate such as N,N-dimethylaminoethyl (meth)acrylate or N,N-diethylaminoethyl (meth)acrylate; Nitrile such as (meth)acrylonitrile; (Meth)acrylate having a blocked isocyanate group such as 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate, 2-[0-(1'-methylpropylideneamino)carboxyamino]ethyl (meth)acrylate, etc.; can be mentioned.

[0051] The vinyl polymer preferably contains a thermally crosslinkable group such as a vinyl monomer having a t-butyl group, a vinyl monomer having an oxetane group, or a vinyl monomer having a blocked isocyanate group. Specifically, vinyl monomers having a t-butyl group such as t-butyl methacrylate and t-butyl acrylate, vinyl monomers having an oxetane group such as 3-ethyl-3-methacryloyloxymethyloxetane and 3-ethyl-3-acryloyloxymethyloxetane, and vinyl monomers having a blocked isocyanate group such as 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate and 2-[0-(1'-methylpropylideneamino)carboxylamino]ethyl (meth)acrylate are preferred. By having these thermally crosslinkable groups, the heat resistance of the acidic dispersant is improved.

[0052] The amount of the vinyl monomer having a thermally crosslinkable group used is preferably 5 to 90% by weight, more preferably 20 to 60% by weight, based on the monomers used for the synthesis of the vinyl polymer. When used in an appropriate amount, a crosslinking effect can be obtained without impairing the polymerization stability.

[0053] [Thiol group-containing alcohol compound] The thiol group-containing alcohol compound is preferably a compound having one or more hydroxyl groups and a thiol group in the molecule, and more preferably a compound having two hydroxyl groups and one thiol group in the molecule. Thereby, the vinyl polymer can form a second polymer site by reaction with an acid dianhydride.

[0054] Examples of the compound having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerol), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, or 2-mercaptoethyl-2-ethyl-1,3-propanediol. Compounds having one hydroxyl group and one thiol group in the molecule include mercaptomethanol, 2-mercaptoethanol, 3-mercapto-1-propanol, 1-mercapto-2-butanol, 2-mercapto-3-butanol, and the like. Among these, compounds having two hydroxyl groups and one thiol group in the molecule are preferred, and 3-mercapto-1,2-propanediol is more preferred from the viewpoints of polymerization control and odor.

[0055] The amount of the compound having two hydroxyl groups and one thiol group used is preferably 1 to 10 parts by mass, more preferably 2 to 9% by mass, and even more preferably 3 to 8% by mass with respect to 100 parts by mass of all vinyl monomers. When used in an appropriate amount, a vinyl polymer with an appropriate molecular weight that functions as a steric repulsion site of the dispersant is easily obtained, and the viscosity stability is improved.

[0056] The polymerization temperature is preferably 40 to 150 °C, more preferably 50 to 110 °C. Polymerization at an appropriate temperature facilitates the control of the polymerization reaction and the adjustment of the molecular weight.

[0057] A polymerization initiator is used for the polymerization of vinyl monomers. The amount of the polymerization initiator used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the monomer. Examples of the polymerization initiator include azo compounds and organic peroxides.

[0058] Examples of the azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), or 2,2'-azobis[2-(2-imidazolin-2-yl)propane], etc.

[0059] Organic peroxides include, for example, benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate, t-butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, or diacetyl peroxide, etc.

[0060] The polymerization initiator can be used alone or in combination of two or more.

[0061] The weight average molecular weight of the vinyl polymer is preferably 1,000 to 20,000. Being in this range can lower the heat-melt viscosity of the acidic dispersant and improve productivity without impairing heat resistance.

[0062] (Acid dianhydride residue) The dispersant (B) of the present invention is represented by the general formula (1), and X 1 represents an acid dianhydride residue. The acid dianhydride residue is formed by reacting the terminal hydroxyl group of the aforementioned polymer moiety (P) with an acid dianhydride.

[0063] [Acid dianhydride] Examples of the acid dianhydride include aliphatic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, or polycyclic tetracarboxylic dianhydrides.

[0064] Aliphatic tetracarboxylic dianhydrides include, for example, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 2,3,5,6-tetracarboxycyclohexane dianhydride, 2,3,5,6-tetracarboxynorbornane dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, and the like.

[0065] Aromatic tetracarboxylic dianhydrides include, for example, pyromellitic dianhydride, ethylene glycol dianhydride trimellitate, propylene glycol dianhydride trimellitate, butylene glycol dianhydride trimellitate, 3,3’,4,4’-benzophenonetetracarboxylic dianhydride, 2,2’,3,3’-benzophenonetetra Carboxylic dianhydrides, 3,3’,4,4’-biphenylsulfone tetracarboxylic dianhydride, 2,2’,3,3’-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3’,4,4’-biphenyl ether tetracarboxylic dianhydride, 3,3’,4,4’-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3’,4,4’-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4’-bis(3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4’-bis(3,4-dicarboxyphenoxy) diphenyl sulfone dianhydride, 4,4’-bis(3,4-dicarboxyphenoxy) diphenyl propane dianhydride, 3,3’,4,4’-perfluoroisopropylidene diphthalic dianhydride, 3,3’,4,4’-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, M-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4’-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4’-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl) fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, and the like can be mentioned.

[0066] Examples of the polycyclic tetracarboxylic dianhydrides include 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalenesuccinic dianhydride, and the like.

[0067] Among these, from the viewpoints of reactivity and adsorptivity to pigments, aliphatic tetracarboxylic dianhydrides and aromatic tetracarboxylic dianhydrides are more preferable, and aromatic tetracarboxylic dianhydrides are even more preferable. That is, the acid anhydride residue preferably has an aromatic ring.

[0068] (Method for Producing Dispersant (B)) In this specification, the dispersant (B) may have a polymer moiety (P) and an acid dianhydride residue, and its synthesis method is not limited. The polymer moiety (P) may be either the aforementioned cyclic ester polymer moiety (P1) or the vinyl polymer moiety (P2), or both may be used in combination. By using both the cyclic ester polymer moiety (P1) and the vinyl polymer moiety (P2) in the polymer moiety (P), the storage stability is improved.

[0069] In the production of the dispersant (P) in this specification, in the presence of a polymer containing a cyclic ester polymer moiety (P1), a thiol group-containing alcohol and a vinyl monomer are reacted to synthesize a polymer containing a vinyl polymer moiety (P2) in step (1). Next, it preferably has step (2) of reacting an acid dianhydride with these polymers to synthesize the dispersant of the present invention.

[0070] In step (1), in the presence of the cyclic ester polymer synthesized as described above, a thiol group-containing alcohol and a vinyl monomer are reacted to synthesize a vinyl polymer having a hydroxyl group at one end. Since the cyclic ester polymer functions as a reaction solvent during the polymerization of the vinyl monomer, polymerization can be carried out without using an organic solvent. Note that the above description does not exclude the use of an organic solvent during the polymerization. The synthesis of the vinyl polymer is as described above.

[0071] The acid dianhydride used in step (2) is as described above.

[0072] When the total amount of hydroxyl groups in the cyclic ester polymer and the vinyl polymer is 1 mol, the amount of the acid dianhydride used is preferably 0.5 to 1.5 mol, more preferably 0.6 to 1.2 mol, and even more preferably 0.7 to 1.0 mol. By reacting an appropriate amount, an acidic dispersant in which the acid dianhydride residue of the pigment adsorption site and the polymer moiety (P) are appropriately bonded can be obtained.

[0073] In the step (2), an esterification reaction catalyst can be used. The esterification reaction catalyst is preferably a tertiary amine. Examples of the tertiary amine include triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo-[5.4.0]-7-undecene, or 1,5-diazabicyclo-[4.3.0]-5-nonene.

[0074] The reaction temperature in the step (2) is preferably 40 to 150°C, more preferably 50 to 120°C. When the reaction is carried out at an appropriate temperature, the reaction is easy to control.

[0075] During the reaction in the step (2), a terminal capping agent (for example, monoalcohol, monoamine) can be reacted with the acid anhydride group to form a capping site. Thereby, the storage stability of the acidic dispersant is improved.

[0076] It is preferable that the cyclic ester polymer part (P1) is contained in the dispersant (B) in an amount of 20 to 90% by mass, more preferably 30 to 70% by mass, and still more preferably 40 to 65% by mass. By containing the cyclic ester polymer part (P1) in an amount of 20% by mass or more, the balance between thermal meltability and crystallinity is excellent, and the reaction control during polymerization and the handling property of the acidic dispersant at room temperature are improved. By setting the cyclic ester polymer part (P1) to 90% by mass or less, a dispersant excellent in viscosity stability and heat resistance can be obtained.

[0077] It is preferable that the vinyl polymer part (P2) is contained in the dispersant (B) in an amount of 5 to 70% by mass, more preferably 10 to 65% by mass, and still more preferably 20 to 60% by mass. By containing the vinyl polymer part (P2) in an amount of 5% by mass or more, an acidic dispersant excellent in viscosity stability can be obtained. By setting the vinyl polymer part (P2) to 70% by mass or less, the viscosity of the acidic dispersant during heat melting decreases, and the productivity of the acidic dispersant is improved.

[0078] [Molecular weight] The weight average molecular weight of the dispersant (B) in the present invention is preferably from 2,000 to 35,000, more preferably from 2,000 to 30,000, and even more preferably from 3,000 to 20,000. When the molecular weight is 2,000 or more, in addition to the improvement of the dispersion stability of the pigment due to the steric repulsion effect of the polymer moiety (P), the heat resistance is further improved. When the molecular weight is 35,000 or less, the dispersibility is further improved.

[0079] [Acid value] The acid value of the dispersant (B) in the present invention is preferably from 10 to 200 mgKOH / g, more preferably from 20 to 150 mgKOH / g, even more preferably from 30 to 120 mgKOH / g, and most preferably from 30 to 110 mgKOH / g. When the acid value is 10 mgKOH / g or more, the pigment adsorption ability is improved and the pigment dispersibility is further improved. On the other hand, when it is 200 mgKOH / g or less, there is no excessive interaction between the resins, and for example, the viscosity of the pigment dispersion can be kept low.

[0080] The curable composition of the present invention may contain a dispersant other than the dispersant (B). Regarding the dispersant, the descriptions in known documents such as JP-A-2011-225848 can be appropriately referred to. Specifically, for example, the SOLSPERSE series of Lubrizol Corporation (e.g., SOLSPERSE16000, 21000, 32000, 33000, 41000, J180, J200, etc.), the DISPERBYK series of BYK-Chemie GmbH (e.g., DISPERBYK102, 110, 111, 118, 165, 168, 190, etc.), and the TEGO Dispers series of Evonik Industries AG (e.g., TEGO Dispers 610, 630, 651, 655, 750W, 755W, etc.) can be mentioned.

[0081] [Polymerizable compound (C)] The curable composition of the present invention contains a polymerizable compound (C). The polymerizable compound (C) is not particularly limited, and conventionally known monofunctional, bifunctional, and polyfunctional monomers and oligomers having three or more functional groups can be used. The polymerizable compound (C) may be used alone or in combination of two or more.

[0082] Examples of monofunctional monomers include monofunctional acrylic monomers and monofunctional vinyl monomers, etc. Specific examples of compounds include benzyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, (ethoxy(or propoxy)ated)2-phenoxyethyl (meth)acrylate, 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 EO-modified acrylate, nonylphenol PO-modified acrylate, o-phenylphenol EO-modified acrylate, 2-ethylhexyl EO-modified acrylate, β-carboxyethyl (meth)acrylate, trimethylolpropane formal (meth)acrylate, isoamyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentanyl (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 monofunctional acrylic monomers such as N-acryloyloxyethylhexahydrophthalimide, and monofunctional vinyl monomers such as N-vinylcaprolactam, N-vinylpyrrolidone, and N-vinylformamide, etc. These compounds may be used alone or in combination of two or more. It is okay.

[0083] The polyfunctional monomer includes a compound having two or more polymerizable functional groups in the molecule. For example, polyfunctional acrylic monomers other than 2-(2-vinyloxyethoxy)ethyl acrylate, vinyl monomers, etc. can be mentioned. Examples of specific compounds include dimethyloltricyclodecane 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, (ethoxy(or propoxy)ated) 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol acrylate, 1,10-decanediol diacrylate, (ethoxy(or propoxy)ated) neopentyl glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, 2-(2-vinyloxyethoxy)ethyl acrylate, (neopentyl glycol-modified) trimethylolpropane di(meth)acrylate, tripropylene glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, pentaerythritol tri(or tetra)(meth)acrylate, trimethylolpropane tri(or tetra)(meth)acrylate, tetramethylolmethane tri(or tetra)(meth)acrylate, and dipentaerythritol hexa(meth)acrylate, etc. As another example of the polyfunctional monomer, a polyfunctional vinyl monomer containing a plurality of vinyl groups in the molecule can be mentioned. Examples of specific compounds include 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 Examples include rue ether, pentaerythritol tri(or tetra)allyl ether, etc. These compounds may be used alone or in combination of two or more. Note that "EO modification" represents ethylene oxide modification, and "PO modification" represents propylene oxide modification. It represents modification.

[0084] Particularly preferred is a polymerizable compound that dissolves a polymer dispersant and / or a basic derivative. Specifically, examples include 2-phenoxyethyl acrylate, acryloylmorpholine, 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, vinylcaprolactam, vinylpyrrolidone, N-vinylformamide, 2-hydroxy-3-phenoxypropyl acrylate.

[0085] From the viewpoint of storage stability, when mixing a pigment, a basic derivative, etc. and performing a dispersion treatment, it is preferable to add a bifunctional (meth)acrylate and attach it to the surface of the pigment, basic derivative, etc. Particularly preferably, dipropylene glycol diacrylate is attached. During the dispersion treatment, it is preferably substantially free of monofunctional (meth)acrylate.

[0086] Further, the curable composition of the present invention preferably contains 2-(2-vinyloxyethoxy)ethyl acrylate as the polymerizable compound (C) after the dispersion treatment. 2-(2-Vinyloxyethoxy)ethyl acrylate is commercially available, for example, as "VEEA" and "VEEA-AI" manufactured by Nippon Shokubai Co., Ltd. 2-(2-Vinyloxyethoxy)ethyl acrylate has a low viscosity and high reactivity. Therefore, it is excellent as a material for producing a curable composition with a low viscosity and high sensitivity. The content of 2-(2-vinyloxyethoxy)ethyl acrylate is preferably 5 to 50% by mass, more preferably 5 to 35% by mass, based on the total weight of the curable composition.

[0087] <Polymerization initiator (D)> 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 preferable to use a polymerization initiator that generates radicals by a molecular cleavage type or a hydrogen abstraction type. In the present invention, the polymerization initiator (D) may be used alone or in combination of two or more. Further, a polymerization initiator that generates radicals and a polymerization initiator that generates cations may be used in combination.

[0088] Specific examples of the polymerization initiator (D) include α-hydroxyalkylphenone compounds such as 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one, phenylglyoxylic acid methyl ester; α-aminoalkylphenone compounds such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butanone-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholyl)phenyl]-1-butanone; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime), ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetoxyoxime); benzophenone compounds such as benzophenone, 4-phenylbenzophenone, isophthalophenone, 4-benzoyl-4'-methyl-diphenyl sulfide;Triazine compounds such as 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-(naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine, etc. can be mentioned.;

[0089] In commercially available products, as α-hydroxyalkylphenone-based compounds, Omnirad 127, 184, 1173, 2959 manufactured by IGM Resins; as aminoalkylphenone-based compounds, Omnirad 907, 369E, 379EG manufactured by IGM Resins; as acylphosphine oxide-based compounds, Omnirad 819, TPO manufactured by IGM Resins; as oxime ester compounds, IRGACURE OXE-01, 02, 03, 04, 05 manufactured by BASF Japan, Adeka Arcles N-1919, NCI-730, 831E, 930 manufactured by ADEKA, 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 Daito Chemicals, etc. can be mentioned. Among these, oxime ester compounds are preferred.

[0090] (Oxime ester compound) The oxime ester compound absorbs ultraviolet rays, causing cleavage of the N-O bond of the oxime and generating iminyl radicals and alkoxy radicals. Since these radicals further decompose to generate highly active radicals, the ink can be cured with a small exposure amount. Because the oxime ester compound has a high quantum efficiency, a coating film with high curability and a coating film with few foreign substances can be obtained.

[0091] Examples of the oxime ester compound also include the 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, International Publication No. 2021 / 175855, etc.

[0092] 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 blended in an appropriate amount, the photocurability is further improved.

[0093] <Basic derivative (E)> The curable composition of the present invention preferably contains a basic derivative (E). The basic derivative (E) is a compound in which a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal is introduced into a skeleton having an affinity for a pigment such as a pigment skeleton. For example, pyrrolopyrrole-based compounds, anthraquinone-based compounds, quinacridone-based compounds, dioxazine-based compounds, perinone-based compounds, perylene-based compounds, thiazine indigo-based compounds, triazine-based compounds, benzimidazolone-based compounds, indole-based compounds such as benzisoindole, isoindoline-based compounds, isoindolinone-based compounds, quinophthalone-based compounds, naphthol-based compounds, quinacridone-based compounds, fluorene-based compounds, metal complex-based compounds, azo-based compounds such as azo, disazo, and polyazo, and squarylium-based compounds, etc. A compound having a structure in which a part of the structure is substituted with a basic group.

[0094] The basic derivative (E) can be used alone or in combination of two or more.

[0095] The basic derivative (E) is preferably added in an amount of 1 to 100 parts by mass, more preferably 3 to 50 parts by mass, and even more preferably 5 to 30 parts by mass based on 100 parts by mass of the colorant (A).

[0096] Specific examples of the basic derivative (E) of the present invention are shown below with compound numbers, but the present invention is not limited thereto.

[0097] Compound 1

Chemical formula

[0098] Compound 2

Chemical formula

[0099] Compound 3

Chemical formula

[0100] Compound 4

Chemical formula

[0101] Compound 5

Chemical formula

[0102] Compound 6

Chemical formula

[0103] Compound 7

Chemical formula

[0104] Compound 8 [Chem.]

[0105] In addition to the basic derivative (E), the curable composition of the present invention may contain an acidic derivative which is a compound having an acidic substituent such as a sulfo group or a carboxy group introduced into a skeleton having an affinity for a pigment such as a dye skeleton.

[0106] [Solvent] In order to reduce the viscosity of the curable composition and improve the wetting and spreading properties on the substrate, a small amount of a solvent may be contained in the curable composition. The solvent is selected in consideration of the solubility of each component of the curable composition and further the safety. The content of the solvent is 5.0% or less in the curable composition from the viewpoint of curability. The content of the solvent is preferably 0.1 to 5.0% in the curable composition, and more preferably 0.2 to 4.0% from the viewpoint of discharge stability.

[0107] The boiling point of the solvent to be used is preferably 120°C to 300°C, and more preferably 140 to 270°C. Preferred solvents include monoacetates, diacetates, diols, monoalkyl ethers, and dialkyl ethers of glycol compounds, and lactate esters. Among them, monoacetates, monoalkyl ethers, and dialkyl ethers of glycol compounds are preferred. More specifically, tetraethylene glycol dialkyl ether, ethylene glycol monobutyl ether acetate, and diethylene glycol diethyl ether are preferred.

[0108] [Sensitizer] Furthermore, a sensitizer can be contained in the curable composition of the present invention. Examples of the sensitizer include chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, polymethine dyes such as cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyllin 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, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like.

[0109] Among the above-mentioned sensitizers, particularly preferred sensitizers that can sensitize suitably include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. 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. are used.

[0110] More specifically, the sensitizers described in Noboru Okawara et al. (eds.), "Dye Handbook" (1986, Kodansha), Noboru Okawara et al. (eds.), "Chemistry of Functional Dyes" (1981, CMC), Chuuzou Ikemori et al. (eds.), and "Special Functional Materials" (1986, CMC) are included, but not limited to these. In addition, other sensitizers that exhibit absorption for light from ultraviolet to near-infrared regions can also be included. The sensitizer can be used alone or in combination of two or more.

[0111] <Polymerization inhibitor> In order to enhance the storage stability over time, the discharge stability after aging, and the storage stability in an inkjet recording apparatus, the curable composition of the present invention can use a polymerization inhibitor. As the polymerization inhibitor, hindered phenol-based compounds, phenothiazine-based compounds, hindered amine-based compounds, and phosphorus-based compounds are particularly preferably used. Specifically, 4-methoxyphenol, hydroquinone, methylhydroquinone, t-butylhydroquinone, 2,6-di-t-butyl-4-methylphenol, phenothiazine, aluminum salt of N-nitrosophenylhydroxylamine, etc. are included. From the viewpoint of enhancing the stability over time while maintaining the curability, it is preferably blended at a ratio of 0.01 to 2% by mass based on the whole curable composition.

[0112] <Antioxidant> The curable composition of the present invention can contain an antioxidant. The antioxidant can prevent the polymerization initiator (D) contained in the curable composition from oxidizing and yellowing, thereby improving the transmittance of the coating film.

[0113] 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.

[0114] 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.

[0115] The antioxidant can be used alone or in combination of two or more.

[0116] Also, when the content of the antioxidant is 0.5 to 5.0% by mass in 100% by mass of the solid content of the curable composition, the transmittance and spectral characteristics are better, which is more preferable.

[0117] <Surface conditioner> The surface conditioner described in this specification means a substance that reduces the surface tension of the ink by addition. Examples of the surface conditioner include silicone-based surface conditioners, fluorine-based surface conditioners, acrylic-based surface conditioners, acetylene glycol-based surface conditioners, etc. From the viewpoints of the ability to reduce the surface tension and the compatibility with the polymerizable compound (C), it is preferable to use a silicone-based surface conditioner.

[0118] Specific silicone-based surface modifiers include modified products of dimethylsiloxane skeletons. Among them, polyether-modified silicone-based surface modifiers are preferred. Polyethers may be, for example, polyethylene oxide and polypropylene oxide. In one embodiment of the present invention, a commercially available polyether-modified silicone surfactant can be used. Examples of typical products that can be preferably used include polyether-modified silicones such as BYK (registered trademark)-378, 348, and 349 of BYK Chemie; and polyether-modified polydimethylsiloxanes such as BYK-UV3500 and UV3510. Also, polyether-modified silicone copolymers such as TEGO (registered trademark) GLIDE450, 440, 435, 432, 410, 406, 130, 110, and 100 of Evonik Degussa are included. Among these, from the viewpoint of forming good image quality, polyether-modified silicone-based surface modifiers such as BYK-331, 378, 348, UV3510, TEGO GLIDE 450, 440, 432, and 410 are preferred.

[0119] The content of the silicone-based surface modifier is preferably in the range of 0.1% by mass or more and less than 5.0% by mass with respect to the total amount of the curable composition. By setting the above 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 above content to less than 5.0% by mass, it becomes easy to ensure the storage stability of the curable composition.

[0120] <Storage stabilizer> The curable composition of the present invention can contain a storage stabilizer to stabilize the viscosity of the composition over time. Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl 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 storage stabilizer can be used in an amount of 0.1 to 10% by mass based on the total amount of the colorant (100% by mass).

[0121] <Other components> The curable composition of the present invention can contain other components other than the above. Examples of the other components include a binder resin, a thermal crosslinking agent, a curing agent, a curing accelerator, an acid generator, a curing catalyst, a chain transfer agent, a silane coupling agent, and a near-infrared absorber. The content of the other components can be appropriately set within a range capable of solving the problems of the present invention.

[0122] <Method for producing the curable composition> The curable composition of the present invention is prepared by finely dispersing a colorant (A) together with a colorant carrier such as a dispersant (B) and a polymerizable compound (C) using various dispersion means 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, and then adding and diluting a polymerizable compound (C), a polymerization initiator (D), etc. to the resulting colorant dispersion. When preparing the colorant dispersion, two or more colorants may be dispersed in the colorant carrier simultaneously, or those separately dispersed in the colorant carrier may be mixed. When the solubility of the colorant such as a dye is high, specifically, when the solubility in the polymerizable compound (C) to be used is high and there is no foreign matter confirmed after dissolution by stirring, it is not necessary to produce it by finely dispersing as described above.

[0123] <Water content> From the viewpoint of stability, the curable composition of the present invention preferably has a water content of 2.0% by mass or less contained in the curable composition.

[0124] The water content contained in the curable composition is more preferably 1.5% by mass or less, and particularly preferably 1.0% by mass or less. Also, the lower limit of the water content is preferably as low as possible, and there is no particular limitation.

[0125] The method for controlling the water content is not particularly limited, and known methods can be used. For example, each of the above-described components is sufficiently dried, etc., and those with a reduced water content contained in the components are used. Further, methods for producing a curable composition while blowing dry air, an inert gas, or a mixed gas thereof can be mentioned.

[0126] <Specific metal atom> In addition to the constituent components of the colorant (A), dispersant (B), polymerizable compound (C), and polymerization initiator (D), the curable composition of the present invention may contain a metal component containing a small amount of Li, Na, Mg, K, Cs, Co, Ca, Fe, Si, and Zr (hereinafter also referred to as specific metal atoms). When a large amount of the metal component containing these specific metal atoms is present, the storage stability may be inhibited, the heat resistance may be lowered, or the dischargeability may be deteriorated. In addition, a color filter prepared using a curable composition in which a large amount of the metal component containing such specific metal atoms is present may generate foreign matters, and as a result, it is likely to cause 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 to 1000 mass ppm with respect to the entire curable composition.

[0127] <Average dispersed particle diameter> The average dispersed particle diameter (secondary particle diameter) of the particles in the curable composition is preferably 30 to 300 nm, more preferably 40 to 250 nm. When the particles have an appropriate particle diameter, a curable composition with high storage stability can be easily obtained.

[0128] As a method for measuring the average dispersed particle diameter (secondary particle diameter), for example, using Microtrac UPA-EX150 manufactured by Nikkiso Co., Ltd. that employs the dynamic light scattering method (FFT power-spectrum method), the particle permeability is set to the absorption mode, the particle shape is set to non-spherical, and the D50 particle diameter is set as the average diameter. As the dilution solvent for measurement, the solvents used for dispersion are each used, and when measuring the sample treated with ultrasonic waves immediately after sample preparation, results with less variation are easily obtained and are preferable.

[0129] <Removal of coarse particles> The curable composition 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 such as centrifugation, filtration using a sintered filter or a membrane filter. The curable composition of the present invention preferably contains substantially no particles of 0.5 μm or more, and more preferably contains no particles of 0.3 μm or less.

[0130] <Inkjet ink> The curable composition of the present invention can be made into an inkjet ink by appropriately adjusting its composition. There is no particular limitation on the use as an inkjet ink, but it is preferably used as an inkjet ink for color filters.

[0131] The viscosity of the inkjet ink of the present invention is preferably adjusted to 5 to 50 mPa·s at 25°C. If the viscosity is within this range, the followability and stability of ejection are excellent.

[0132] (Printing method) Printing methods by the inkjet printing method include a one-pass printing method and a multi-pass printing method. The one-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 by one head scan. On the other hand, the multi-pass printing method (also referred to as a serial printing method) is a method in which a predetermined printing area is printed by a plurality of head scans The inkjet ink of the present invention has excellent curability and can be used in the one-pass printing method.

[0133] As the optimum ink film thickness, 2 μm or more and 30 μm or less is preferable, more preferably 3 μm or more and 25 μm or less, and still more preferably 4 μm or more and 20 μm or less. If it is within the above range, good color development and excellent curability are obtained.

[0134] (Inkjet head) As the inkjet head used in the inkjet printing method, on-demand Either a discontinuous or a continuous mode may be used. As the ejection method, electro-mechanical conversion methods (e.g., single cavity type, double cavity type, vender type, piston type, share mode type, shared wall type, etc.), electro-thermal conversion methods (e.g., thermal inkjet type, bubble jet (registered trademark) type, etc.), electrostatic attraction methods (e.g., electric field control type, slit jet type, etc.), discharge methods (e.g., spark jet type, etc.) can be cited as specific examples, but any ejection method may be used.

[0135] (Ink droplet size) The volume of the ink droplets ejected from the inkjet head is preferably in the range of 0.5 to 100 pL. From the viewpoint of less coating unevenness and higher printing speed, it is more preferably in the range of 2 to 20 pL.

[0136] In the one-pass printing method, it is preferable to use a wide-width head in which nozzles are arranged side by side over a width equal to or greater than the width of the desired coating pattern. When forming a plurality of independent coating patterns that are not continuous with each other on the same substrate, a wide-width head with a width of at least the width of each coating pattern may be used.

[0137] The active energy ray for curing the inkjet ink may be any energy ray that can affect the electron orbits of the irradiated object and induce polymerization reactions such as radicals, cations, and anions. Although not particularly limited, specific examples include electron beams, ultraviolet rays, and infrared rays. In the present invention, ultraviolet rays are preferably used.

[0138] Specific examples that can be used as a light source for ultraviolet rays include a high-pressure mercury lamp, a metal halide lamp, a low-pressure mercury lamp, an extra-high pressure mercury lamp, an ultraviolet laser, an LED, and sunlight. From the viewpoints of convenience and price, it is preferable to use a high-pressure mercury lamp, a metal halide lamp, an LED, or the like. The peak emission wavelength is preferably from 200 to 600 nm, more preferably from 300 to 450 nm, still more preferably from 320 to 420 nm, and particularly preferably ultraviolet rays in the range of 340 to 400 nm.

[0139] <Hardened film> The hardened film of the present invention is formed from the curable composition of the present invention or the inkjet ink of the present invention.

[0140] <Color filter> The color filter of the present invention has a substrate and the hardened film of the present invention. The color filter of the present invention includes at least one red filter segment, at least one green filter segment, and at least one blue filter segment. Further, in addition to the three-color filter segments, a yellow filter segment can also be included.

[0141] <Method for manufacturing a color filter> The color filter of the present invention can be manufactured by a printing method.

[0142] Since the formation of the filter segment by the printing method can be patterned by printing the curable composition prepared as an inkjet ink, as a method for manufacturing a color filter, it is low-cost and excellent in mass productivity. Further, due to the development of printing technology, it is possible to print a fine pattern having high dimensional accuracy and smoothness. In order to perform printing, it is preferable to have a composition such that the ink does not dry or solidify on the printing plate or on the blanket. Also, control of the fluidity of the ink on the printing machine is important, and it is also possible to adjust the ink viscosity with a dispersant or an extender pigment.

[0143] <Solid-state imaging device> The solid-state imaging device of the present invention has the color filter. The form used in the solid-state imaging device is not particularly limited. For example, on a substrate, it has a plurality of photodiodes constituting the light-receiving area of the solid-state imaging device (such as a CCD image sensor, a CMOS image sensor, etc.) and transfer electrodes made of polysilicon or the like, and has a light-shielding film with only the light-receiving portion of the photodiode opened on the photodiode and the transfer electrodes, and has a device protection film made of silicon nitride or the like formed so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode on the light-shielding film, and has a configuration having a filter on the device protection film. Further, a configuration having a condensing means (such as a microlens, etc. The same applies hereinafter) on the device protection film and below the filter (closer to the substrate side), or a configuration having a condensing means on the filter may be used. Also, the filter may have a structure in which a cured film forming each colored pixel is embedded in a space partitioned, for example, in a lattice shape by partition walls. In this case, the partition walls preferably have a low refractive index with respect to each colored pixel. The imaging device provided with the solid-state imaging device of the present invention can be used in various applications such as, for example, a digital camera, an electronic device having an imaging function (such as a smartphone, a tablet terminal, etc.), an in-vehicle camera, a surveillance camera, and an optical sensor.

[0144] <Image display device> 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 EL display, and the like. The form used in the image display device is not particularly limited, but it can be used as a color filter, a black matrix, a light-shielding filter, an infrared cut filter, or an infrared transmission filter. The form used in the image display device only needs to function as an image display device and is not particularly limited. For example, the configurations described in "Next-generation liquid crystal display technology" (written by Tatsuo Uchida, published by Kogyo Chosa Kai, Inc. in 1994) and the like can be mentioned. For the definition of the image display device and the details of each image display device, refer to, for example, "Electronic Display Devices (written by Akio Sasaki, published by Kogyo Chosa Kai Co., Ltd. in 1990)", "Display Devices (written by Junsho Ibuki, published by Sangyo Tosho Co., Ltd. in 1989)", etc.

Example

[0145] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited thereto. Note that "parts" means "parts by mass" and "%" means "% by mass".

[0146] (Weight-average molecular weight (Mw) of the resin) It was measured by gel permeation chromatography (GPC) equipped with an RI detector. As the apparatus, HLC-8220GPC (manufactured by Tosoh Corporation) was used. Two separation columns were connected in series, and for both packing materials, "TSK-GEL SUPER HZM-N" was connected in a pair and used. 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 composed of 1 wt% of the above eluent and 20 microliters were injected. All molecular weights are in terms of polystyrene conversion.

[0147] (Acid value of the resin) About 1 g of the object for measuring the acid value was weighed, 30 g of pyridine and 1 g of water were added, and after stirring for 10 minutes, a 0.1 N potassium hydroxide ethanol solution was used as the titrant, and titration was performed using a potentiometric titrator (manufactured by Kyoto Electronics Industry Co., Ltd., apparatus name "Automatic Potentiometric Titrator AT-710M") to measure the acid value of the resin and calculate the acid value per non-volatile content.

[0148] (Reaction rate of acid dianhydride groups) To 0.5 - 1.0 g of the sample, add 30 ml of a mixed solution of 1,4 - dioxane and water (10:1), and stir to dissolve uniformly. Then, add 10 ml of the following hexylamine adjustment solution, stir for 5 minutes to obtain a measurement sample solution. Next, using a 0.02 mol / L perchloric acid (1,4 - dioxane) solution as the titrant, titrate using an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd., model "COM - 555") to obtain the titration volume (B ml). Similarly, titrate only 10 ml of the hexylamine adjustment solution to obtain the blank titration volume (C ml). Then, calculate the reaction rate of the acid dianhydride groups of the resin using the following formula. Hexylamine adjustment solution: A mixed solution of 0.79 g of hexylamine and 400 g of 1,4 - dioxane S: Sampling amount of the sample (g) A: Amount of amine compound contained in the sample (mmol / g) = Amount of amine in the resin solid content (%) / Molecular weight of amine Measured acid dianhydride value of the resin (mmol / g) = { (Blank titration volume C × 0.02) - (Sample titration volume B × 0.02 - S × Non - volatile content concentration × A)} / (S × Non - volatile content concentration) Charged acid dianhydride value (mmol / g) = Charged amount of acid dianhydride in the acidic dispersant (wt%) / Molecular weight of acid dianhydride × Acid dianhydride group number of acid dianhydride Reaction rate of acid dianhydride groups (mol%) = { 1 - (Measured acid dianhydride value / Charged acid dianhydride value)} × 100

[0149] [Production Example 1] Synthesis of Dispersant (B1) Into a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, charge 35.6 parts of 1 - dodecanol, 164.4 parts of ε - caprolactone, and 0.1 part of monobutyltin(IV) oxide as a catalyst. After purging with nitrogen gas, heat and stir at 120 °C for 4 hours. Confirm by non - volatile content measurement that 98% has reacted, and terminate the first step (referred to as "Production Step 1" described in the following tables).

[0150] To the above reaction product, 20.8 parts of pyromellitic dianhydride and 0.1 part of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) were added, and the mixture was reacted at 100 °C for 5 hours. By measuring the acid value, it was confirmed that 97% or more of the acid anhydride was half-esterified, and the second step (Manufacturing Step 2 described in each of the following tables) was completed. The obtained dispersant had a weight average molecular weight of 3620 and an acid value of 51 mgKOH / g.

[0151] [Production Examples 2 to 7] Synthesis of Dispersants (B2) to (B7) Synthesis was carried out in the same manner as in the production example of dispersant (B1) except that the raw materials and charged amounts described in Table 1-1 were used, and dispersants (B2) to (B7) were obtained.

[0152] [Production Example 8] Synthesis of Dispersant (B8) Into a reaction vessel equipped with a gas introduction tube, thermometer, condenser, and stirrer, 11.2 parts of benzyl alcohol, 88.8 parts of ε-caprolactone, and 0.1 part of monobutyltin oxide as a catalyst were charged. After purging with nitrogen gas, the mixture was heated and stirred at 120 °C for 4 hours. By measuring the non-volatile content, it was confirmed that 98% or more had reacted, and a cyclic ester polymer was obtained.

[0153] Next, the above reaction product was cooled to 40 °C, 50.0 parts of tert-butyl acrylate, 45.0 parts of methyl methacrylate, 5.0 parts of methacrylic acid, and 7.1 parts of 3-mercapto-1,2-propanediol (1-thioglycerol) were charged, and the mixture was stirred well. Further, 0.12 g of dimethyl 2,2'-azobis(2-methylpropionate) was charged as an initiator, the temperature was raised to 85 °C, and the mixture was reacted for 7 hours. It was confirmed that the non-volatile content reached 95% or more, and a vinyl polymer was obtained (however, it is a mixture with the cyclic ester polymer).

[0154] Next, while maintaining the internal temperature at 85°C, 19.2 parts of pyromellitic dianhydride were added to the above reaction product, and the temperature was raised to 100°C with stirring. Then, 0.13 part of N,N-dimethylbenzylamine was added, and the reaction was carried out at 120°C for 3 hours and further at 100°C for 2 hours. It was confirmed by measuring the reaction rate of the dianhydride group that 95% or more of the acid anhydride was half-esterified, and a dispersant (B8) was obtained. The obtained dispersant had a weight average molecular weight of 4,900 and an acid value of 68 mgKOH / g.

[0155] [Production Examples 9 to 12] Synthesis of Dispersants (B9) to (B12) Synthesis was carried out in the same manner as in the production example of the dispersant (B8) except that the raw materials and charged amounts described in Table 1-2 were used, and dispersants (B9) to (B12) were obtained.

[0156]

Table 1-1

[0157]

Table 1-2

[0158] Abbreviations in Tables 1-1 and 1-2: PMA ··· Pyromellitic dianhydride BTA ··· 1,2,3,4-Butanetetracarboxylic dianhydride BPDA ··· 3,3′,4,4′-Biphenyltetracarboxylic dianhydride t-BA ··· t-Butyl acrylate MMA ··· Methyl methacrylate MAA ··· Methacrylic acid

[0159] <Production of the curable composition> [Production Example 13] (Pigment dispersion (d-1)) After uniformly stirring and mixing a mixture with the following composition using a high-speed mixer or the like, the obtained mill base was dispersed using a horizontal sand mill for about 1 hour to prepare a pigment dispersion. 13.5 parts of C.I. Pigment Red PR254 1.5 parts of basic derivative (E1) 7.5 parts of dispersant (B1) 47.5 parts of dipropylene glycol diacrylate

[0160] [Production Examples 14 to 50, Comparative Production Examples 1 to 3] (Pigment dispersions (d-2) to (d-41)) Hereinafter, pigment dispersions (d-2) to (d-41) were prepared in the same manner as the pigment dispersion (d-1), except that the colorant (A), basic derivative (E), dispersant (B), and polymerizable compound (C) were changed to the compositions and amounts shown in Table 2.

[0161]

Chemical formula

[0162]

Table 2

[0163] Meanings of the abbreviations in Table 2 〈Colorant (A)〉 · "PR254"; C.I. Pigment Red 254 · "PR264"; C.I. Pigment Red 264 · "PR269"; C.I. Pigment Red 269 · "PR291"; C.I. Pigment Red 291 · "PR177"; C.I. Pigment Red 177 · "PY150"; C.I. Pigment Yellow 150 · "PY139"; C.I. Pigment Yellow 139 · "PY138"; C.I. Pigment Yellow 138 · "PG36"; C.I. Pigment Green 36 · "PG58"; C.I. Pigment Green 58 · "PG59"; C.I. Pigment Green 59 · "PG62"; C.I. Pigment Green 62 · "PG63"; C.I. Pigment Green 63 · "PG15:6"; C.I. Pigment Green 15:6 · "PG15:3"; C.I. Pigment Green 15:3 · "PV23"; C.I. Pigment Violet 23 〈Dispersant〉 · "SP32000"; Basic Pigment Dispersing Resin "Solsperse 32000" (manufactured by Nippon Lubrizol Corporation) · "BYK111"; Acidic Pigment Dispersing Resin "BYK111" (manufactured by BYK) 〈Polymerizable Compound (C)〉 · DPGDA: Dipropylene Glycol Diacrylate, "Laromer DPGDA" manufactured by BASF mer DPGDA · PEA: Phenoxyethyl Acrylate, "SR339" manufactured by Sartomer

[0164] [Example 1] (Curable Composition (D-1)) To the previously prepared pigment dispersion, a mixed solution of a polymerizable compound, a photoinitiator, and a stabilizer was slowly added so as to achieve the formulation described in Table 3, and the resulting mixed solution was stirred. Next, a surface tension adjuster was added to the above mixed solution, and then the mixture was shaken on a shaker for 6 hours. Thereafter, the composition was filtered through a PTFE filter with a pore diameter of 0.5 microns to remove dust and coarse particles, thereby obtaining a curable composition (D-1). Note that the addition and mixing of the raw materials for obtaining the above mixed solution may be in any order.

[0165] [Examples 2 to 43, Comparative Examples 1 to 4] (Curable Compositions (D-2) to (D-47)) The curable compositions (D-2) to (D-47) were prepared in the same manner as the curable composition (D-1), except that the material types and masses were changed as described in Tables 3-1 to 3-3.

[0166] <Evaluation Method of Curable Composition> The curable compositions prepared in each example and each comparative example were printed using a single-pass inkjet printer (One Pass Jet manufactured by Trytec Co., Ltd.) having an inkjet ejection mechanism equipped with a head (KJ4A) manufactured by Kyocera, a mechanism for transporting the substrate on which the ink landed at a desired speed, and a mechanism for subsequent irradiation with a UV lamp. Printing was performed under the conditions of a droplet volume of 14 pl and 600×600 dpi, and various properties were evaluated. As the UV lamp, a UV lamp (240W) manufactured by GEW was used, and a sample of the cured film was prepared under the condition of an integrated light amount of 200 mJ / cm 2 . The printing speed and the printed image were changed in each performance evaluation.

[0167] [Storage Stability] The viscosity of the obtained curable composition was measured and used as the initial viscosity. Further, an accelerated aging test was performed at 60°C for 2 weeks, and the accelerated aging viscosity was measured. As the change rate due to accelerated aging, the accelerated aging viscosity / initial viscosity was calculated and evaluated according to the following criteria. ◎ : Change rate less than 5% ○ : Change rate 5% or more and less than 10% △ : Change rate 10% or more and less than 20% × : Change rate 20% or more

[0168] [Curability] The curable composition 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 changed to 20 to 75 m / min, and the degree of curability was judged from the printing speed at which the printed cured film was cured in one pass. The state in which the uncured curable composition no longer adhered to the cotton swab was judged as cured. The evaluation criteria are as follows, and ○ or more is regarded as good curability. ◎ : Cures at 50 m / min or more ○ : Cures at 35 m / min or more and less than 50 m / min △: Cures at speeds above 20 m / min and below 35 m / min ×: Does not cure at speeds below 20 m / min

[0169] [Discharge stability] The prepared curable composition was printed with a nozzle check pattern using an inkjet printer. After printing 100,000 drops, the nozzle check pattern was printed again, and the dischargeability was evaluated based on the number of clogged nozzles. The evaluation criteria are as follows. The conveyor speed was set at 35 m / min. ◎: No clogged nozzles after printing 100,000 drops ○: 1 - 2 clogged nozzles after printing 100,000 drops △: 3 - 5 clogged nozzles after printing 100,000 drops ×: 6 or more clogged nozzles after printing 100,000 drops

[0170] [Solvent resistance evaluation] A curable composition 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 at 35 m / min. The obtained cured film was immersed in an N-methylpyrrolidone solution for 30 minutes, then washed with ion-exchanged water and air-dried, and evaluated using an optical microscope. The evaluation criteria are as follows. ○: No particular change in appearance (good) △: Slight change in appearance (practicable) ×: Discoloration occurred (not practicable)

[0171]

Table 3-1

[0172]

Table 3-2

[0173]

Table 3-3

[0174] Meanings of the abbreviations in Tables 3-1 to 3-3 〈Polymerizable compound (C)〉 · C-1: 2-(2-Vinyloxyethoxy)ethyl acrylate, “VEEA” manufactured by Nippon Shokubai Co., Ltd. · C-2: Ethoxylated (3) trimethylolpropane triacrylate, “SR454” manufactured by Sartomer Company · C-3: Dipropylene glycol diacrylate, “Laromer DPGDA” manufactured by BASF mer DPGDA Above, C-1, C-2, and C-3 were mixed at a mass ratio of 3:3:1 to obtain the polymerizable compound (C1). 〈Stabilizer〉 · BHT: “H-BHT” manufactured by Honshu Chemical Industry Co., Ltd. · Phenothiazine: “Phenothiazine” manufactured by Seiko Chemical Co., Ltd. 〈Surface conditioner〉 · BYK-UV3510: Polyether-modified polydimethylsiloxane manufactured by BYK Chemie 〈Polymerization initiator (D)〉 · Omnirad819: Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide manufactured by IGM Resins · OmniradTPO-L: 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide manufactured by IGM Resins · Omnirad369: 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 manufactured by IGM Resins · KAYACURE BMS: 4-Benzoyl-4'-methyl-diphenyl sulfide manufactured by Nippon Kayaku Co., Ltd. · Irgacure OXE-04: Manufactured by BASF Japan · D-1: The following compound

Chemical formula

Chemical formula

[0175] From the results in Table 3, Examples 1 to 43 had high storage stability, excellent ejection properties, curability, and solvent resistance.

[0176] [Example 101] (Curable composition (DD-1)) To the previously prepared pigment dispersion, a mixed solution of a polymerizable compound, a photoinitiator, and a polymerization inhibitor was slowly added so as to have the formulation described in Table 4, and the resulting mixed solution was stirred. Next, a surface tension modifier was added to the above mixed solution, and then the mixture was shaken for 6 hours with a shaker to prepare a curable composition (DD-1). The obtained curable composition (DD-1) was filtered through a PTFE filter with a pore diameter of 0.5 μm to remove dust and coarse particles, and used as a curable composition. Note that the addition and mixing of the raw materials for obtaining the above mixed solution may be in any order.

[0177] [Examples 102 to 105] (Curable compositions (DD-2) to (DD-5)) Curable compositions (DD-2) to (DD-5) were prepared in the same manner as the curable composition (DD-1), except that the types and masses of the materials were changed as described in Table 4.

[0178] [Evaluation of the coloring composition] The obtained curable compositions (DD-1) to (DD-5) were evaluated in the same manner as the curable compositions (D-1) to (D-47). The test results are shown in Table 4.

[0179]

Table 4

[0180] From the results of Table 4, Examples 101 to 105 had high storage stability, excellent discharge properties, curability, and solvent resistance.

[0181] A color filter was created by printing the curable composition of the present invention. Due to its excellent properties, the obtained color filter is expected to be suitably used when used in a solid-state imaging device, an image display device, or the like.

Claims

1. A curable composition comprising a colorant (A), a dispersant (B) represented by the general formula (1), a polymerizable compound (C), and a polymerization initiator (D), wherein the content of the solvent in the curable composition is 5.0% or less. General formula (1) 【Chemical 1】 In the general formula (1), A １ to A ４ is a combination selected from the group consisting of the following A, B, and C, A) A １ ~A ４ Of which two sites are each a monovalent polymer moiety (P) that is identical to or different from each other, and the other two sites are each -C(=O)OH or -CH ２ C(=O)OH, and B) A １ ~A ４ One of the sites is a monovalent polymer site (P), and the other three sites are the same or different from each other -C(=O)OH or -CH ２ C(=O)OH, and C) A １ ~A ４ One of the three sites is a monovalent polymer site (P), and the other two sites are the same or different from each other -C(=O)OH or -CH ２ C(=O)OH, and the other remaining site is -C(=O)-Xa-Ra (where Xa is -O-, or -N(Ra ２ )-, and Ra is a group selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, and an aryl group having 6 to 18 carbon atoms, and Ra ２ is a hydrogen atom or a group selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, and an aryl group having 6 to 18 carbon atoms). The monovalent polymer moiety (P) is a cyclic ester polymer moiety (P1) having a hydroxyl group at one end and a terminal moiety A at the other end, or a vinyl polymer moiety (P2) having a hydroxyl group at the terminal, and the terminal moiety A is a structure derived from a monoalcohol or a monoamine. In addition, X in the general formula (1) １ represents an acid dianhydride residue, and the acid dianhydride residue is formed by reacting the terminal hydroxyl group of the aforementioned polymer moiety (P) with an acid dianhydride.

2. The curable composition according to claim 1, further comprising a basic derivative (E).

3. X １ The curable composition according to claim 1, wherein X is an acid dianhydride residue of an aromatic tetracarboxylic dianhydride.

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

5. An inkjet ink comprising the curable composition according to claim 1.

6. A cured film formed from the curable composition according to any one of claims 1 to 4, or the inkjet ink according to claim 5.

7. A color filter having a substrate and the cured film according to claim 6.

8. A solid-state imaging device comprising the color filter according to claim 7.

9. An image display device comprising the color filter according to claim 7.

Images