Colored composition, colored cured film, color filter, display element, light-receiving element, light-emitting element, and colorant dispersion liquid

Abstract

The present application provides a kind of coloring composition, coloring hard film, color filter, display element, light receiving element, light emitting element and colorant dispersion liquid capable of forming the coloring hard film of inhibited light leakage under black display and excellent contrast ratio. A kind of coloring composition contains (A) colorant comprising halogenated metal phthalocyanine pigment, (B) binder resin and (C) polymerizable compound, and in the coloring composition, (A) colorant also comprises quinophthalone compound represented by the following formula (1), (A 1 ) halogenated metal phthalocyanine pigment and (A 2 ) the mass ratio [(A 1 ) / (A 2 )] of quinophthalone compound represented by the following formula (1) is 99 / 1-85 / 15.

Description

Technical Field

[0001] This invention relates to a coloring composition, a coloring curing film, and color filters, display elements, light-receiving elements, light-emitting elements, and colorant dispersions. More specifically, it relates to a coloring composition for forming color curing films used in transmissive or reflective color liquid crystal display elements, solid-state imaging elements, organic electroluminescence (EL) display elements, electronic paper, etc., a color curing film as a cured form of the coloring composition, and color filters, display elements, light-receiving elements, and light-emitting elements including the color curing film. Background Technology

[0002] Color filters in liquid crystal display devices and the like have red pixels (R), green pixels (G), and blue pixels (B), each of which has a structure in which a hardened film of a coloring composition in which organic pigments are dispersed is disposed on a substrate. As organic pigments, red, green, and blue organic pigments can be used; for example, in the case of forming green pixels, color index (CI) pigment green 7, CI pigment green 36, and other green pigments are used. However, since it is difficult to sufficiently obtain the desired color reproducibility or contrast ratio using only green pigments, it has been proposed to adjust the emission spectrum by combining at least one green pigment selected from CI pigment green 7 and CI pigment green 36 with at least one yellow pigment selected from CI pigment yellow 139, CI pigment yellow 150, and CI pigment yellow 185 (Patent Document 1).

[0003] [Existing technical documents]

[0004] [Patent Literature]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2010-26268 Summary of the Invention

[0006] [The problem the invention aims to solve]

[0007] The inventors have discovered that the pixels of a color filter typically appear as black (dark state) when a low voltage is applied or even when no voltage is applied. However, in a color filter containing green pixels with metal halide phthalocyanine pigments as colorants, even when black is to be displayed, the following phenomenon (hereinafter referred to as "light leakage") is particularly prone to occur: some light leaks out from the green pixels and appears green.

[0008] The problem of the present invention is to provide a coloring composition capable of forming a color-curing film that suppresses light leakage under black display and has an excellent contrast ratio. Furthermore, the problem of the present invention is to provide a color-curing film formed using the coloring composition, and a color filter, display element, light-receiving element, and light-emitting element including the color-curing film.

[0009] [Technical means to solve the problem]

[0010] In view of the aforementioned facts, the inventors conducted detailed research and discovered that a coloring composition capable of forming a color-curing film with suppressed light leakage and excellent contrast ratio under black display can be obtained by: containing a metal halide phthalocyanine pigment as a colorant together with an adhesive resin and a polymerizable compound, and containing a quinoline ketone compound having a specific structure in a specific amount ratio relative to the metal halide phthalocyanine pigment.

[0011] That is, the present invention provides a coloring composition comprising (A) a colorant including a metal halide phthalocyanine pigment, (B) a binder resin and (C) a polymerizable compound, wherein in the coloring composition,

[0012] (A) The colorant also contains a quinoline compound represented by formula (1) below.

[0013] (A 1 ) metal halide phthalocyanine pigments and (A 2 The mass ratio of quinoline compounds represented by the following formula (1) [(A 1 ) / (A 2 The value is 99 / 1 to 85 / 15.

[0014] [Chemistry 1]

[0015]

[0016] In formula (1),

[0017] R 1 ~R 13 Each of the following can be independently represented: a hydrogen atom; a halogen atom; an alkyl group that may have substituents; an alkoxy group that may have substituents; an aryl group that may have substituents; a monovalent to trivalent metal salt or alkylammonium salt of -SO3H, -COOH, or these acidic groups; a phthalimide methyl group that may have substituents; or an aminosulfonyl group that may have substituents; wherein, R 1 ~R 4 At least one adjacent set of bases and / or R 10 ~R 13 At least one adjacent group of groups in the mixture becomes integral to form an aromatic ring that may have substituents.

[0018] Furthermore, the present invention provides a color-cured film as a cured form of the coloring composition, and a color filter, display element, light-receiving element, and light-emitting element including the color-cured film. Examples of color-cured films include: pixels of various colors used in display elements or solid-state imaging elements, banks (isolation walls) defining the area for forming the light-emitting layer, black matrices, etc. Among these, green pixels of the color filter used in display elements or solid-state imaging elements are preferred for easily enjoying the effects of the present invention.

[0019] [The effects of the invention]

[0020] According to the present invention, a coloring composition is provided that can form a color-curing film that suppresses light leakage under black display and has an excellent contrast ratio. Therefore, the coloring composition of the present invention is extremely suitable for manufacturing display elements such as color liquid crystal display elements, organic EL display elements, electronic paper, and solid-state imaging elements such as complementary metal oxide semiconductor (CMOS) image sensors. Detailed Implementation

[0021] The present invention will now be described in detail.

[0022] Coloring Composition

[0023] -(A) Coloring agent-

[0024] The colorant (A) of the present invention contains (A) 1 Metal halide phthalocyanine pigments.

[0025] As a component (A) 1 Metal halide phthalocyanine pigments may contain metals such as zinc, copper, aluminum, magnesium, titanium, vanadium, manganese, iron, cobalt, nickel, tin, germanium, and indium. (A) 1 Metal halide phthalocyanine pigments, such as zinc halide phthalocyanine pigments, copper halide phthalocyanine pigments, magnesium halide phthalocyanine pigments, aluminum halide phthalocyanine pigments, titanium halide phthalocyanine pigments, vanadium halide phthalocyanine pigments, manganese halide phthalocyanine pigments, iron halide phthalocyanine pigments, cobalt halide phthalocyanine pigments, nickel halide phthalocyanine pigments, tin halide phthalocyanine pigments, germanium halide phthalocyanine pigments, indium halide phthalocyanine pigments, etc.

[0026] In addition, as a component (A) 1 The halogens in metal halide phthalocyanine pigments can include fluorine, chlorine, bromine, and iodine, and may contain one or more of these. Chlorine and bromine are preferred.

[0027] Among them, as (A) 1From the viewpoint of suppressing light leakage and improving contrast ratio, the metal halide phthalocyanine pigment is preferably selected from one or more of copper halide phthalocyanine pigment, zinc halide phthalocyanine pigment and aluminum halide phthalocyanine pigment, more preferably zinc halide phthalocyanine pigment and aluminum halide phthalocyanine pigment, and even more preferably selected from at least one of zinc bromide phthalocyanine pigment, zinc bromide chloride phthalocyanine pigment and aluminum bromide chloride phthalocyanine pigment, especially preferably zinc bromide chloride phthalocyanine pigment and aluminum bromide chloride phthalocyanine pigment.

[0028] As zinc chloride bromide phthalocyanine pigment or aluminum chloride bromide phthalocyanine pigment, zinc chloride bromide phthalocyanine pigment represented by the following formula (2) is preferred. For example, it can be obtained in the form of pigments classified as CI pigment green 58, CI pigment green 59, or CI pigment green 62 in the color index (CI) name.

[0029] [Chemistry 2]

[0030]

[0031] In formula (2),

[0032] M indicates zinc or aluminum;

[0033] X represents a hydrogen atom, a chlorine atom, or a bromine atom, respectively; wherein, of all X atoms, at least one is a chlorine atom, 10 to 15 are bromine atoms, and the remainder are hydrogen atoms.

[0034] In formula (2), among all X, chlorine atoms are preferably 1 to 6. In this case, bromine atoms can be appropriately selected in the range of 10 to 15 such that the total number of X is 16, and all X can be composed of bromine atoms and chlorine atoms.

[0035] In this invention, (A) 1 Metal halide phthalocyanine pigments may contain one or more of the following:

[0036] The colorant (A) of the present invention further contains (A) 2 The quinoline compound represented by the following formula (1) (hereinafter also referred to as "(A)") 2 (quinoline compounds).

[0037] [Chemistry 3]

[0038]

[0039] In formula (1),

[0040] R 1 ~R 13Each of the following can be independently represented: a hydrogen atom; a halogen atom; an alkyl group that may have substituents; an alkoxy group that may have substituents; an aryl group that may have substituents; a monovalent to trivalent metal salt or alkylammonium salt of -SO3H, -COOH, or these acidic groups; a phthalimide methyl group that may have substituents; or an aminosulfonyl group that may have substituents; wherein, R 1 ~R 4 At least one adjacent set of bases and / or R 10 ~R 13 At least one adjacent group of groups in the mixture becomes integral to form an aromatic ring that may have substituents.

[0041] As R 1 ~R 13 Halogen atoms in the atom can be listed as: fluorine atom, chlorine atom, bromine atom, and iodine atom. Among them, chlorine atom and bromine atom are preferred.

[0042] R 1 ~R 13 The alkyl group can be in any form, either straight-chain or branched-chain, and the number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 12, and especially preferably 1 to 6. Specific examples of alkyl groups include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, 1-methyldecyl, dodecyl, 1-methylundecyl, 1-ethyldecyl, tridecyl, tetradecyl, tert-dodecyl, pentadecyl, 1-heptyloctyl, hexadecyl, octadecyl, etc. Substituents for alkyl groups include: halogen atoms, alkoxy groups that may have substituents, nitro groups, aryl groups that may have substituents, etc. Furthermore, the position and number of substituents are arbitrary, and when there are two or more substituents, the substituents may be the same or different. Specific examples of alkyl groups with substituents include: trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-dibromoethyl, 2,2,3,3-tetrafluoropropyl, 2-ethoxyethyl, 2-butoxyethyl, 2-nitropropyl, benzyl, 4-methylbenzyl, 4-tert-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl, 2,4-dichlorobenzyl, etc.

[0043] R 1 ~R 13The alkoxy group can be in any form, either linear or branched, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 6. Specific examples of alkoxy groups include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, neopentoxy, hexoxy, octyloxy, octadecoxy, 2,3-dimethyl-3-pentoxy, 2-ethylhexoxy, etc. Substituents for alkoxy groups include: halogen atoms, alkoxy groups that may have substituents, nitro groups, aryl groups that may have substituents, etc. Furthermore, the position and number of substituents are arbitrary, and when there are two or more substituents, the substituents may be the same or different. Specific examples of alkoxy groups with substituents include: trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropoxy, 2,2-ditrifluoromethylpropoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-nitropropoxy, benzyloxy, etc.

[0044] R 1 ~R 13 The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 14, and even more preferably 6 to 10. Specific examples of aryl groups include: phenyl, naphthyl, anthraceneyl, phenanthryl, biphenyl, azulel, 9-fluorenyl, etc. Substituents for the aryl group include: halogen atoms, nitro groups, alkoxy groups that may have substituents, amino groups that may have substituents, hydroxyl groups, alkyl groups that may have substituents, etc. Furthermore, the position and number of substituents are arbitrary; when two or more substituents are present, the substituents may be the same or different. Specific examples of aryl groups with substituents include: p-bromophenyl, p-nitrophenyl, p-methoxyphenyl, 2,4-dichlorophenyl, pentafluorophenyl, 2-aminophenyl, 2-methyl-4-chlorophenyl, 4-hydroxy-1-naphthyl, 6-methyl-2-naphthyl, 4,5,8-trichloro-2-naphthyl, anthraquinone, 2-aminoanthraquinone, etc.

[0045] R 1 ~R 13 The acidic group in the form is -SO3H or -COOH, and these acidic groups can be monovalent to trivalent metal salts or alkylammonium salts. Examples of metal salts include sodium, potassium, magnesium, calcium, iron, and aluminum salts. Examples of alkylammonium salts include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine, and stearylamine; and quaternary alkylammonium salts such as palmityltrimethylammonium salt, dilauryl dimethylammonium salt, and distearyl dimethylammonium salt.

[0046] As R 1 ~R 13Substituents in phthalimide methyl (C6H4(CO)2N-CH2-) and aminosulfonyl (H2NSO2-) can include: halogen atoms, alkyl groups that may have substituents, alkoxy groups that may have substituents, aryl groups that may have substituents, etc. Specific examples of these groups can be listed as groups that are the same as those described above.

[0047] Additionally, R 1 ~R 4 At least one adjacent set of bases and / or R 10 ~R 13 At least one adjacent group of groups in the aromatic ring is integrated to form an aromatic ring that may have substituents. Examples of aromatic rings include hydrocarbon aromatic rings and heteroaromatic rings. Examples of hydrocarbon aromatic rings include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, etc. Examples of heteroaromatic rings include pyridine rings, pyrazine rings, pyrrole rings, quinoline rings, quinoxaline rings, furan rings, benzofuran rings, thiophene rings, benzothiophene rings, oxazole rings, thiazole rings, imidazole rings, pyrazole rings, indole rings, carbazole rings, etc. Hydrocarbon aromatic rings are preferred, and benzene rings are even more preferred. Examples of substituents in the aromatic ring include halogen atoms, nitro groups, alkoxy groups that may have substituents, amino groups that may have substituents, hydroxyl groups, alkyl groups that may have substituents, etc. Halogen atoms are preferred.

[0048] As (A) 2 The preferred quinoline compounds are those represented by formulas (1A) to (1C).

[0049] [Chemistry 4]

[0050]

[0051] In equations (1A) to (1C),

[0052] R 1 ~R 13 The meaning of R in equation (1) 1 ~R 13 same,

[0053] R 21 ~R 24 R 31 ~R 34 Each of the following can be independently represented: a hydrogen atom; a halogen atom; an alkyl group that may have substituents; an alkoxy group that may have substituents; an aryl group that may have substituents; a monovalent to trivalent metal salt or alkylammonium salt of -SO3H, -COOH, or these acidic groups; a phthalimide methyl group that may have substituents; or an aminosulfonyl group that may have substituents.

[0054] R 21 ~R 24 R31 ~R 34 The specific structures of the halogen atom, alkyl group (which may have substituents), alkoxy group (which may have substituents), aryl group (which may have substituents), monovalent to trivalent metal salts or alkylammonium salts of acidic groups, phthalimide methyl group (which may have substituents), and aminosulfonyl group (which may have substituents) are shown in R. 1 ~R 13 As explained in the text.

[0055] Among them, R 1 ~R 4 R 10 ~R 13 R 21 ~R 24 R 31 ~R 34 Each is preferably a hydrogen atom or a halogen atom, R. 5 ~R 9 Each of the following is preferred independently: a hydrogen atom, an alkoxy group that may have a substituent, or an aryl group that may have a substituent.

[0056] As (A) 2 Specific examples of quinoline compounds include, for example, the quinoline compounds (a) to (r) shown below, but the present invention is not limited to these.

[0057] [Chemistry 5]

[0058]

[0059] [Chemistry 6]

[0060]

[0061] [Chemistry 7]

[0062]

[0063] In this invention, (A) 2 Quinoline compounds may contain one or more of the following:

[0064] Regarding the coloring composition of the present invention, (A) 1 ) metal halide phthalocyanine pigments and (A 2 ) The mass ratio of quinoline compounds [(A 1 ) / (A 2 The ratio is 99 / 1 to 85 / 15. From the viewpoint of suppressing light leakage and improving contrast ratio, it is preferably 98.9 / 1.1 to 86.3 / 13.7, more preferably 98.9 / 1.1 to 86.5 / 13.5, and even more preferably 98.7 / 1.3 to 86.7 / 13.3.

[0065] In addition, relative to all colorants, (A) 1 The preferred content of the metal halide phthalocyanine pigment is 61% to 79% by mass, more preferably 63% to 77% by mass, and even more preferably 65% ​​to 75% by mass.

[0066] Furthermore, relative to all colorants, (A) 2 The content of the quinoline compound is preferably 0.5% to 11% by mass, more preferably 0.8% to 10.5% by mass, and even more preferably 1% to 10% by mass.

[0067] The coloring composition of the present invention may contain (A) 1 ) metal halide phthalocyanine pigments and (A 2 Other colorants besides quinoline compounds may be used as colorant (A). There are no particular limitations on other colorants; the color or material can be appropriately selected according to the application. If (A) is used as colorant... 1 ) metal halide phthalocyanine pigments and (A 2 Colorants other than quinoline compounds may also be pigments, dyes, and natural pigments. From the viewpoint of improving brightness and contrast, organic pigments are preferred as pigments, and organic dyes are preferred as dyes. Furthermore, other colorants may contain one or more of these compounds.

[0068] As organic pigments, for example, compounds classified as pigments in the Dyestuff Index (CI; published by The Society of Dyers and Colourists) can be listed, namely compounds with Dyestuff Index (CI) numbers as described below.

[0069] CI Pigment Yellow 150, CI Pigment Yellow 180, and other azo pigments; CI Pigment Yellow 138, and other quinoline ketone pigments (of which, (A 2 (Except for quinoline compounds);

[0070] CI Pigment Yellow 139, CI Pigment Yellow 185 and other isoindoline pigments;

[0071] Anthraquinone pigments such as Pigment Red 177;

[0072] CI pigments, including Red 123 and other perylene pigments;

[0073] CI Pigment Orange 43 and other violet ketone pigments;

[0074] CI Pigment Red 122 and other quinacridone pigments;

[0075] CI pigments such as Pigment Violet 23 and other dioxazine pigments;

[0076] CI Pigment Yellow 109 and other isoindolinetone pigments;

[0077] CI pigments such as Orange 66 and Red 88 are indigo pigments.

[0078] In addition, examples of inorganic pigments include carbon black and titanium black. Furthermore, examples of lake pigments include those described in Japanese Patent Application Publication Nos. 2001-081348, 2010-026334, 2010-237384, 2010-237569, 2011-006602, and 2011-145346.

[0079] Among these, in terms of effectively suppressing light leakage and further improving the contrast ratio, pigments selected from azo pigments and quinoline ketone pigments are preferred (wherein, (A 2 (excluding quinoline compounds), and more preferably at least one selected from CI Pigment Yellow 138, CI Pigment Yellow 150 and CI Pigment Yellow 180.

[0080] In this invention, recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or combinations thereof can also be used (A). 1 ) metal halide phthalocyanine pigments, (A 2 The pigments can be used by refining quinoline compounds and other pigments mixed in any way. Alternatively, the surface of these pigment particles can be modified with resin as desired. Examples of resins for modifying the surface of pigment particles include the vehicle resin described in Japanese Patent Application Publication No. 2001-108817 or various commercially available pigment dispersion resins. Furthermore, organic pigments can be used by refining the primary particles through a process called salt milling. For example, the method disclosed in Japanese Patent Application Publication No. Hei 8-179111 can be used for salt milling.

[0081] There are no particular limitations on the type of dye used; for example, compounds classified as dyes in the Color Index (CI; published by The Society of Dyers and Colourists) and existing dyes can be used. Examples of such dyes include: xanthracene dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes, azo dyes, dipyrrole methylene dyes, quinoline dyes, coumarin dyes, pyrazolone dyes, quinoline dyes, nitro dyes, quinone imine dyes, phthalocyanine dyes, squaric acid lactone dyes, acridine dyes, indigo dyes, etc. Furthermore, any type of acid dye, basic dye, or nonionic dye can be used.

[0082] Furthermore, in this invention, in the presence of (A) 1 ) metal halide phthalocyanine pigments, (A 2 In addition to quinoline compounds and any other colorants mixed together, it may also contain existing dispersants and dispersing aids.

[0083] Existing dispersants include, for example, urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene alkylphenyl ether-based dispersants, polyethylene glycol diester-based dispersants, sorbitan fatty acid ester-based dispersants, polyester-based dispersants, and acrylic dispersants.

[0084] Such dispersants are commercially available. Examples include, for instance, acrylic dispersants such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, and BYK-LPN22102 (all manufactured by BYK Chemical Company), and carbamate dispersants such as Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, and Disperbyk-182 (and so on). The above are examples of dispersants manufactured by BYK Corporation, such as Solsperse 76500 (manufactured by Lubrizol Corporation). Other examples of polyethyleneimine-based dispersants include Solsperse 24000 (manufactured by Lubrizol Corporation). Examples of polyester-based dispersants include Ajisper PB821, Ajisper PB822, Ajisper PB880, and Ajisper PB881 (all manufactured by Ajinomoto Fine-Techno Corporation), as well as BYK-LPN21324 (manufactured by BYK Corporation).

[0085] In addition, examples of pigment derivatives include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinoline ketone.

[0086] Regarding the suppression of light leakage and the formation of pixels with excellent brightness and contrast ratio, (A) the content of the colorant in the solid components of the coloring composition is typically 5% to 70% by mass, preferably 10% to 60% by mass. Here, the solid components refer to components other than the solvent described later. Furthermore, when other colorants are contained, the content of the other colorants can be appropriately selected within a range that does not impair the purpose of the present invention, preferably 50% by mass or less, and more preferably 40% by mass or less, relative to all colorants. The lower limit is not particularly limited, and 0.01% by mass or more is acceptable.

[0087] -(B) Adhesive Resin-

[0088] The coloring composition of the present invention contains an adhesive resin as component (B).

[0089] The adhesive resin (B) is not particularly limited, but is preferably a resin having acidic functional groups such as carboxyl groups or phenolic hydroxyl groups. Among these, polymers having carboxyl groups (hereinafter also referred to as "carboxyl-containing polymers") are preferred, for example, copolymers of vinyl unsaturated monomers (hereinafter also referred to as "unsaturated monomers (b1)") having one or more carboxyl groups with other copolymerizable vinyl unsaturated monomers (hereinafter also referred to as "unsaturated monomers (b2)"). Furthermore, the adhesive resin (B) may contain one or more of these functional groups.

[0090] Examples of unsaturated monomers (b1) include: (meth)acrylic acid, maleic acid, maleic anhydride, mono[2-(meth)acryloyloxyethyl] succinate, ω-carboxylated polycaprolactone mono(meth)acrylate, p-vinylbenzoic acid, etc. Furthermore, one or more unsaturated monomers (b1) may be used.

[0091] Furthermore, examples of unsaturated monomasks (b2) include:

[0092] N-substituted maleimides such as N-phenylcis-butenyl diimide and N-cyclohexylcis-butenyl diimide;

[0093] Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthene;

[0094] Methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, allyl methacrylate, benzyl methacrylate, polyethylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polypropylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polyethylene glycol (degree of polymerization 2-10) mono(meth)acrylate, polypropylene glycol (degree of polymerization 2-10) mono(meth)acrylate, cyclohexyl methacrylate, isobornyl methacrylate, tricyclo[5.2.1.0] 2,6 Decane-8-yl(meth)acrylate, dicyclopentenyl(meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyphenyl(meth)acrylate, ethylene oxide-modified (meth)acrylate of p-cumylphenol, glycidyl(meth)acrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]-3-ethyloxetane, etc. (meth)acrylates;

[0095] Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0] 2,6Vinyl ethers such as decane-8-yl vinyl ether, pentacyclic pentadecyl vinyl ether, and 3-(vinyloxymethyl)-3-ethyloxetane;

[0096] Polystyrene, poly(methyl methacrylate), poly(n-butyl methacrylate), polysiloxane, and other macromonomers with mono(meth)acryloyl groups at the ends of their polymer chains are examples. Furthermore, one or more unsaturated monomers (b2) may be used.

[0097] In the copolymer of unsaturated monomer (b1) and unsaturated monomer (b2), the copolymerization ratio of unsaturated monomer (b1) in the copolymer is preferably 5% to 50% by mass, and more preferably 10% to 40% by mass. By copolymerizing the unsaturated monomer (b1) within this range, a coloring composition with excellent alkali developability and storage stability can be obtained.

[0098] Specific examples of copolymers of unsaturated monomer (b1) and unsaturated monomer (b2) include those disclosed in Japanese Patent Application Publication Nos. 7-140654, 8-259876, 10-31308, 10-300922, 11-174224, 11-258415, 2000-56118, and 2004-101728.

[0099] Furthermore, in this invention, as disclosed in, for example, Japanese Patent Application Publication Nos. 5-19467, 6-230212, 7-207211, 9-325494, 11-140144, and 2008-181095, a carboxyl-containing polymer having polymerizable unsaturated bonds such as (meth)acryloyl groups in the side chain can also be used as an adhesive resin.

[0100] The (B) binder resin of this invention has a polystyrene-converted weight-average molecular weight (Mw) determined by gel permeation chromatography (GPC) (dissolution solvent: tetrahydrofuran), typically ranging from 1,000 to 100,000, preferably from 3,000 to 50,000. Furthermore, the ratio of Mw to number-average molecular weight (Mn) of the (B) binder resin (Mw / Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. Mn is the polystyrene-converted number-average molecular weight determined by GPC (dissolution solvent: tetrahydrofuran). By adopting this configuration, a coloring composition that not only suppresses light leakage and improves contrast ratio but also exhibits excellent alkali developability or storage stability can be prepared.

[0101] (B) The adhesive resin can be manufactured by existing methods, and its structure or Mw, Mw / Mn can be controlled by methods disclosed in Japanese Patent Application Publication No. 2003-222717, Japanese Patent Application Publication No. 2006-259680, International Publication No. 2007 / 029871, etc.

[0102] The content of (B) binder resin is typically 10 to 1,000 parts by weight relative to 100 parts by weight of (A) colorant, preferably 20 to 500 parts by weight, more preferably 50 to 200 parts by weight, and even more preferably 80 to 150 parts by weight. This configuration not only suppresses light leakage and improves contrast ratio, but also further enhances alkaline developability, the storage stability of the coloring composition, pattern shape, and colorimetric characteristics. Additionally, it suppresses the formation of precipitates or coating foreign matter.

[0103] -(C) Polymerizing compounds-

[0104] In this specification, the term "polymerizable compound" refers to a compound having two or more polymerizable groups. Examples of polymerizable groups include: vinyl unsaturated groups, oxetyl, oxetyl, N-alkoxymethylamino, etc. Examples of vinyl unsaturated groups include: vinyl, allyl, (meth)acryloyl, etc. From the viewpoint of suppressing migration and improving heat resistance, compounds having two or more (meth)acryloyl groups or compounds having two or more N-alkoxymethylamino groups are preferred as polymerizable compounds, and even more preferably compounds having two or more (meth)acryloyl groups. (C) Polymerizable compounds may contain one or more of these groups.

[0105] Specific examples of compounds having two or more (meth)acryloyl groups include: polyfunctional (meth)acrylates as products of aliphatic polyhydroxy compounds and (meth)acrylic acid; polyfunctional (meth)acrylates modified with caprolactone; polyfunctional (meth)acrylates modified with epoxide; polyfunctional (meth)acrylate carbamates as products of hydroxyl-containing (meth)acrylates and polyfunctional isocyanates; and polyfunctional (meth)acrylates with carboxyl groups as products of hydroxyl-containing (meth)acrylates and acid anhydrides.

[0106] Examples of aliphatic polyhydroxy compounds include: divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and trivalent or higher aliphatic polyhydroxy compounds such as glycerol, trimethylolpropane, pentaerythritol, and dipentaerythritol. Examples of (meth)acrylates containing hydroxyl groups include: 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and glycerol dimethacrylate. Examples of polyfunctional isocyanates include: toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include: anhydrous dicarboxylic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride; tetracarboxylic anhydride such as pyromellitic dianhydride, biphenyl tetracarboxylic dianhydride, and benzophenone tetracarboxylic dianhydride.

[0107] In addition, as a caprolactone-modified polyfunctional (meth)acrylate, the compounds described in paragraphs

[0015] to

[0018] of Japanese Patent Application Publication No. 11-44955 can be cited as examples. Examples of polyfunctional (meth)acrylates modified with alkyl oxides include: bisphenol A dimethacrylate modified with at least one selected from ethylene oxide and propylene oxide; isocyanuric acid trimethacrylate modified with at least one selected from ethylene oxide and propylene oxide; trimethylolpropane trimethacrylate modified with at least one selected from ethylene oxide and propylene oxide; pentaerythritol trimethacrylate modified with at least one selected from ethylene oxide and propylene oxide; pentaerythritol tetramethacrylate modified with at least one selected from ethylene oxide and propylene oxide; dipentaerythritol pentamethacrylate modified with at least one selected from ethylene oxide and propylene oxide; and dipentaerythritol hexamethacrylate modified with at least one selected from ethylene oxide and propylene oxide.

[0108] As compounds having two or more oxecyclopropyl groups, in addition to epoxy resins and (co)polymers of vinyl unsaturated monomers having oxecyclopropyl groups, multifunctional epoxy resins such as EHPE3150 (manufactured by Daicel Inc.) can also be used.

[0109] In addition, as compounds having two or more oxetane groups, besides (co)polymers of vinyl unsaturated monomers having oxetane groups, examples include Aron Oxetane OXT-121 and Aron Oxetane OXT-221 (both manufactured by Toa Synthetic Co., Ltd.).

[0110] In addition, aliphatic conjugated diene compounds such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene, and 2,3-dimethyl-1,3-butadiene, as well as non-conjugated diene compounds such as divinylbenzene, diisopropenylbenzene, and trivinylbenzene, can also be used.

[0111] Among these polymerizable compounds, polyfunctional (meth)acrylates, which are products of trivalent or higher aliphatic polyhydroxy compounds and (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylates, polyfunctional (meth)acrylate carbamates, polyfunctional (meth)acrylates with carboxyl groups, and (co)polymers of vinyl unsaturated monomers with oxetyl groups are preferred. From the viewpoint of suppressing light leakage and improving contrast ratio, among polyfunctional (meth)acrylates that are products of trivalent or higher aliphatic polyhydroxy compounds and (meth)acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are preferred. Among polyfunctional (meth)acrylates with carboxyl groups, products of pentaerythritol triacrylate and succinic anhydride, and products of dipentaerythritol pentaacrylate and succinic anhydride are preferred.

[0112] The content of the polymeric compound (C) is preferably 10 to 1,000 parts by mass relative to 100 parts by mass of colorant (A), more preferably 20 to 800 parts by mass, and even more preferably 100 to 500 parts by mass. By setting it in this manner, light leakage can be suppressed to a higher level and the contrast ratio can be improved.

[0113] Furthermore, regarding the coloring composition of the present invention, from the viewpoint of suppressing light leakage and improving contrast ratio, the mass ratio of (B) binder resin to (C) polymeric compound [(B) / (C)] is preferably 95 / 5 to 61 / 39, more preferably 93 / 7 to 63 / 37, and even more preferably 90 / 10 to 65 / 35.

[0114] -(D) Photopolymerization initiator-

[0115] The coloring composition of the present invention may contain a photopolymerization initiator. This imparts a radiosensitive linearity to the coloring composition. The photopolymerization initiator used in the present invention is a compound of an active species that can initiate the polymerization of (C) polymerizable compounds upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. (D) The photopolymerization initiator may contain one or more of these.

[0116] Examples of photopolymerization initiators include: thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, and onium salt compounds. Among these, at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds is preferred as the (D) photopolymerization initiator.

[0117] Among the preferred photopolymerization initiators of this invention, specific examples of thioxanthone compounds include: thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc.

[0118] In addition, specific examples of acetophenone compounds include: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butane-1-one, etc.

[0119] In addition, specific examples of bimidazole compounds include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bimidazole, etc.

[0120] Furthermore, when using biimidazole compounds as photopolymerization initiators, it is preferable to use hydrogen donors in conjunction with them to improve sensitivity. The term "hydrogen donor" as used herein refers to a compound that can provide hydrogen atoms to free radicals generated from the biimidazole compound through exposure. Examples of hydrogen donors include thiol-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; and amine-based hydrogen donors such as 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone. In this invention, two or more hydrogen donors can be used alone or in combination. For further improvement in sensitivity, it is preferable to use one or more thiol-based hydrogen donors and one or more amine-based hydrogen donors in combination.

[0121] In addition, specific examples of triazine compounds include: 2,4,6-tris(trichloromethyl)-triazine, 2-methyl-4,6-bis(trichloromethyl)-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-triazine, and 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-triazine. Triazine compounds containing halogenated methyl groups, such as 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-triazine, and 2-(4-butoxyphenyl)-4,6-bis(trichloromethyl)-triazine.

[0122] In addition, specific examples of O-acyl oxime compounds include: 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyl oxime), acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime), acetone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime), acetone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxacyclopentyl)methoxybenzoyl}-9H-carbazole-3-yl]-,1-(O-acetyl oxime), etc. Commercially available O-acyloxime compounds include NCI-831 and NCI-930 (both manufactured by ADEKA Corporation).

[0123] In this invention, when using photopolymerization initiators other than biimidazole compounds such as acetophenone compounds, a sensitizer may also be used in conjunction. Examples of such sensitizers include: 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminophenylacetone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzyl)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone, etc.

[0124] The content of photopolymerization initiator (D) is preferably 0.01 to 120 parts by mass, and more preferably 1 to 100 parts by mass, relative to 100 parts by mass of polymerizable compound (C). This allows for a higher level of suppression of light leakage and improvement of contrast ratio.

[0125] -(E)solvent-

[0126] As the solvent for (E), any solvent may be appropriately selected that disperses or dissolves (A) the colorant, (B) the binder resin, and (C) the polymeric compound, and other components constituting the coloring composition, without reacting with these components, and has moderate volatility. Organic solvents are typically used as the solvent for (E). The solvent for (E) may contain one or more of these components.

[0127] As an organic solvent, examples include:

[0128] Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. (poly)alkyl glycol monoalkyl ethers;

[0129] alkyl lactate esters such as methyl lactate and ethyl lactate;

[0130] Methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tert-butanol, octanol, 2-ethylhexanol, cyclohexanol and other (cyclo)alkyl alcohols;

[0131] Ketone alcohols such as diacetone alcohol;

[0132] Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, etc. (poly)alkyl glycol monoalkyl ether acetates;

[0133] Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers;

[0134] Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;

[0135] Diacetates such as propylene glycol diacetate, 1,3-butanediol diacetate, and 1,6-hexanediol diacetate;

[0136] Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxypropionate, 3-methyl-3-methoxybutyl propionate, and other alkoxycarboxylic acid esters;

[0137] Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate, and other esters;

[0138] Aromatic hydrocarbons such as toluene and xylene;

[0139] Amides or lactams such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0140] Among these, the preferred solvents for (E) are propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, and ethyl pyruvate, etc., from the viewpoints of solubility, storage stability, and coatability.

[0141] (E) The content of the solvent is not particularly limited, but it is preferable that the total concentration of all components of the coloring composition other than the solvent is 5% to 50% by mass, and more preferably 10% to 40% by mass. By setting it in this manner, a colorant dispersion with good dispersibility and stability and a coloring composition with good coatability can be prepared.

[0142] -additive-

[0143] The coloring composition of the present invention may also contain various additives as needed.

[0144] Examples of additives include: fillers for glass and alumina; polymers such as polyvinyl alcohol and poly(fluoroalkyl acrylates); surfactants such as fluorinated surfactants and silicone surfactants; adhesion promoters such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane; 2,2-thiobis(hydroxyethyl)silane. Antioxidants such as 4-methyl-6-tert-butylphenol and 2,6-di-tert-butylphenol; UV absorbers such as 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and alkoxybenzophenones; anti-coagulation agents such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, medoconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1, Residue improvers such as 2-propanediol, 2-amino-1,3-propanediol, and 4-amino-1,2-butanediol; developer improvers such as mono[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acryloyloxyethyl] phthalate, and ω-carboxylated polycaprolactone mono(meth)acrylate; and siloxane oligomers with reactive functional groups disclosed in Japanese Patent Application Publication No. 2008-242078.

[0145] The coloring composition of the present invention can be prepared by suitable methods. For example, it can be prepared by mixing / dispersing (A) colorant, (B) binder resin and (C) polymeric compound with solvent or other optional ingredients using a bead mill, roller mill or the like.

[0146] Colored hardened film and its formation method

[0147] The coloring and curing film of the present invention is a cured product formed using the coloring composition of the present invention.

[0148] The following describes the color-curing film used in color filters constituting display elements or solid-state imaging elements and the method for forming it.

[0149] As a method for manufacturing a color filter, the following method can be listed first. First, a light-shielding layer (black matrix) is formed on the surface of a substrate as needed to divide the areas where pixels will form. Then, a liquid composition of, for example, a green radiosensitive linear coloring composition of the present invention is coated onto the substrate. Next, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Then, the coating film is exposed using a photomask, and then developed using an alkaline developer to dissolve and remove the unexposed portions of the coating film. Finally, a pixel array with a green pixel pattern (color-cured film) arranged in a predetermined pattern is formed by post-baking.

[0150] Subsequently, using either red or blue radiosensitive linear coloring compositions, the coating, pre-baking, exposure, development, and post-baking of the respective radiosensitive linear coloring compositions are performed in the same manner as described above, thereby sequentially forming a red pixel array and a blue pixel array on the same substrate. Thus, a color filter with pixel arrays of the three primary colors—red, blue, and green—arranged on a substrate can be obtained. However, in this invention, the order in which the pixels of each color are formed is not limited to that described above.

[0151] The black matrix can be formed by using photolithography to set a desired pattern on a thin film of metal such as chromium, which is formed by sputtering or evaporation. Alternatively, it can be formed in the same way as the pixel formation using a radiosensitive linear coloring composition in which a black colorant is dispersed.

[0152] Examples of substrates include: glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamide-imide, polyimide, etc.

[0153] In addition, as needed, these substrates can be pretreated with appropriate methods such as chemical treatment using silane coupling agents, plasma treatment, ion plating, sputtering, vapor phase reaction, and vacuum evaporation.

[0154] When applying the coloring composition to the substrate, appropriate coating methods can be used, such as spraying, roller coating, spin coating, slot coating, and bar coating. Spin coating and slot coating are preferred, in particular.

[0155] Pre-baking is usually carried out at 70℃~110℃ for about 1 minute to 10 minutes.

[0156] The coating thickness is typically 0.6 μm to 8 μm, and preferably 1.2 μm to 5 μm, which is the film thickness after drying.

[0157] Examples of light sources that can be used to form radiation selected from at least one of pixels and a black matrix include: xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, etc., or laser sources such as argon ion lasers, yttrium aluminum garnet (YAG) lasers, XeCl excimer lasers, nitrogen lasers, etc. Ultraviolet light-emitting diodes (LEDs) can also be used as exposure light sources. Radiation with wavelengths in the range of 190 nm to 450 nm is preferred.

[0158] Generally speaking, the preferred exposure dose for radiation is 10 J / m². 2 ~10,000J / m 2 .

[0159] In addition, as an alkaline developer, aqueous solutions of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene, etc., are preferred.

[0160] In alkaline developing solutions, appropriate amounts of water-soluble organic solvents such as methanol and ethanol, or surfactants, can be added. Furthermore, a water wash is typically performed after alkaline development.

[0161] As a developing method, spray developing, dipping developing, and puddle developing can be used. The preferred developing conditions are 5 to 300 seconds at room temperature.

[0162] The post-baking conditions are usually carried out at 180℃~280℃ for about 10 to 60 minutes.

[0163] The thickness of the pixel formed in the manner described is typically 0.5 μm to 5 μm, preferably 1.0 μm to 3 μm.

[0164] Alternatively, as a second method for manufacturing color filters, the inkjet printing method disclosed in Japanese Patent Application Publication No. 7-318723 and Japanese Patent Application Publication No. 2000-310706 can be used to obtain pixels of various colors. In this method, firstly, a light-shielding barrier is formed on the surface of a substrate. Then, a liquid composition, such as a thermosetting green coloring composition, is sprayed into the formed barrier using an inkjet printer. Next, a pre-baking process is performed to evaporate the solvent. Then, the coating is exposed as needed, and then post-baked to harden it and form a green pixel pattern.

[0165] Subsequently, using either red or blue thermosetting coloring compositions, red pixel patterns and blue pixel patterns are sequentially formed on the same substrate, similarly to the above. Thus, a color filter with pixel patterns of the three primary colors—red, blue, and green—arranged on a substrate can be obtained. However, in this invention, the order in which the pixels of each color are formed is not limited to that described above.

[0166] Furthermore, the isolation wall not only serves a light-shielding function but also prevents the various thermosetting coloring compositions sprayed into the defined area from mixing, thus resulting in a thicker film compared to the black matrix used in the first method. Therefore, the isolation wall is typically formed using a black radiosensitive linear composition.

[0167] The substrate or radiation source used in forming the color filter, as well as the pre-baking or post-baking method or conditions, are the same as in the first method. Thus, the film thickness of the pixel formed by inkjet printing is the same as the height of the isolation wall.

[0168] On the pixel pattern obtained in the manner described, a protective film is formed as needed, and then a transparent conductive film is formed by sputtering. Alternatively, after forming the transparent conductive film, spacers can be formed to create a color filter. The spacers are typically formed using a radiosensitive linear composition, but can also be configured as light-shielding spacers (black spacers). In this case, a radiosensitive linear coloring composition in which a black colorant is dispersed can be used, but the curing composition of the present invention can also be suitably used to form the black spacers.

[0169] The coloring composition of the present invention can also be suitably used to form a color-cured film of any of the color pixels, black matrices, black spacers, etc. used in the color filter.

[0170] The color filter with the color-curing film of the present invention formed in the manner described above has light leakage suppressed and a high contrast ratio, and is therefore extremely useful for color liquid crystal display elements, color camera tube elements, color sensors, organic EL display elements, electronic paper, etc.

[0171] Color filters

[0172] The color filter of the present invention includes the color-curing film of the present invention. Specifically, it is sufficient to include the color-curing film of the present invention as a component such as the color pixels, black matrix, and black spacers used in the color filter.

[0173] Display elements

[0174] The display element of the present invention includes the color-curing film of the present invention. Examples of display elements include: color liquid crystal display elements, organic EL display elements, electronic paper, etc.

[0175] The color liquid crystal display element including the color-curing film of the present invention can be either transmissive or reflective, and can employ a suitable structure. For example, a structure can be adopted in which the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is disposed, such that the driving substrate and the substrate on which the color filter is formed face each other separated by a liquid crystal layer. Alternatively, a structure can be adopted in which the substrate on which the color filter is formed on the surface of the driving substrate on which the thin film transistor (TFT) is disposed faces the substrate on which the indium tin oxide (ITO) electrode or the indium zinc oxide (IZO) electrode is formed, separated by a liquid crystal layer. The latter structure has the advantage of significantly improving the aperture ratio and obtaining a clear and highly detailed liquid crystal display element. Furthermore, in the case of the latter structure, the black matrix or black spacers can be formed on either the side of the substrate on which the color filter is formed or the side of the substrate on which the ITO electrode or the IZO electrode is formed.

[0176] A color liquid crystal display element including the color-curing film of the present invention may include a cold cathode fluorescent lamp (CCFL) and a backlight unit that uses a white LED as the light source. Examples of white LEDs include: a white LED that obtains white light by combining and mixing red, green, and blue LEDs; a white LED that obtains white light by combining and mixing blue, red, and green phosphors; a white LED that obtains white light by combining and mixing blue, red, and green phosphors; a white LED that obtains white light by mixing blue LEDs with YAG phosphors; a white LED that obtains white light by combining and mixing blue, orange, and green phosphors; and a white LED that obtains white light by combining and mixing ultraviolet LEDs, red phosphors, green phosphors, and blue phosphors.

[0177] In color liquid crystal display elements including the color hardening film of the present invention, appropriate liquid crystal modes such as twisted nematic (TN), super twisted nematic (STN), in-planar switching (IPS), vertical alignment (VA), and optically compensated birefringence (OCB) can be applied.

[0178] Furthermore, the organic EL display element including the color-curing film of the present invention can adopt a suitable structure, for example, the structure disclosed in Japanese Patent Application Publication No. 11-307242.

[0179] Furthermore, the electronic paper including the coloring and curing film of the present invention can adopt a suitable structure, for example, the structure disclosed in Japanese Patent Application Publication No. 2007-41169 can be cited.

[0180] Optical receiving element

[0181] The light-receiving element of the present invention includes the colored hardening film of the present invention.

[0182] The light-receiving element of the present invention can adopt a suitable structure. For example, the color-curing film of the present invention can be used as a color filter constituting a solid-state imaging element, and combined with a photodiode, thereby constituting an imaging element such as a solid-state imaging element. Alternatively, the color-curing film of the present invention can be used as an infrared light-transmitting film, and combined with a photodiode to form a pixel for infrared light detection.

[0183] Light-emitting element

[0184] The light-emitting element of the present invention includes the color-curing film of the present invention.

[0185] The light-emitting element of the present invention can adopt a suitable structure. For example, in an organic EL light-emitting element having a structure in which a transparent conductive layer containing an anode with a transparent electrode, a light-emitting layer, and a cathode layer containing a metal electrode are stacked, the color-curing film of the present invention is used as a protective film, an insulating film, and a wavelength-selective component for emission. The light-emitting layer can be formed using the coloring composition of the present invention and in accordance with the method for forming the color-curing film of the present invention.

[0186] Colorant dispersion

[0187] The colorant dispersion of the present invention contains (A) a colorant comprising a metal halide phthalocyanine pigment, and (A) the colorant further comprises a quinoline ketone compound represented by formula (1), (A) 1) metal halide phthalocyanine pigments and (A 2 The mass ratio of the quinoline compound represented by formula (1) [(A 1 ) / (A 2 The value is 99 / 1 to 85 / 15.

[0188] (A) The colorant may be the same as that used in the coloring composition of the present invention, preferably within the same range. Furthermore, it may also include any components such as dispersants, binder resins, and solvents.

[0189] [Example]

[0190] The following examples illustrate the implementation of the present invention in more detail. However, the present invention is not limited to the following examples.

[0191] <(B) Synthesis of Adhesive Resins>

[0192] Synthesis example B1

[0193] A flask containing 100 parts by weight of propylene glycol monomethyl ether acetate was purged with nitrogen. The contents of the flask were heated to 80°C, and a mixed solution comprising 100 parts by weight of propylene glycol monomethyl ether acetate, 20 parts by weight of methacrylic acid, 10 parts by weight of styrene, 5 parts by weight of benzyl methacrylate, 15 parts by weight of 2-hydroxyethyl methacrylate, 23 parts by weight of 2-ethylhexyl methacrylate, 12 parts by weight of N-phenylcis-butenediamide, 15 parts by weight of mono(2-acryloyloxyethyl) succinate, and 6 parts by weight of 2,2'-azobis(2,4-dimethylpentanonitrile) was added dropwise over 1 hour. The temperature was maintained, and polymerization was carried out for 2 hours. Then, the temperature of the reaction solution was raised to 100°C and maintained, and polymerization was carried out for another 1 hour, thereby obtaining an adhesive resin solution (solids concentration = 33.3% by weight). The obtained adhesive resin solution had a Mw of 12,200 and a Mn of 6,500. The adhesive resin solution is designated as "resin solution (B-1)".

[0194] <Preparation of Colorant Dispersion>

[0195] Preparation Example 1

[0196] Colorant dispersion (A-1)

[0197] A green colorant dispersion (A-1) was prepared by mixing and dispersing 7.2 parts by mass of CI pigment green 58, 0.1 parts by mass of the quinoline ketone compound (a) as described below, and 5.7 parts by mass of CI pigment yellow 138 as colorants; 10.8 parts by mass of BYK-LPN22102 (manufactured by BYK Corporation) (solid content concentration = 40% by mass) as dispersants and 13.0 parts by mass of resin solution (B-1); and 63.2 parts by mass of propylene glycol monomethyl ether acetate as solvent using a bead mill. Furthermore, the quinoline ketone compound (a) was synthesized by the method described in the examples of Japanese Patent Application Publication No. 2012-226110.

[0198] [Chemistry 8]

[0199]

[0200] Preparation Examples 2 to 57

[0201] Colorant dispersions (A-2) to (A-57)

[0202] As described in Table 1, the type and amount of colorant were changed. Otherwise, colorant dispersions (A-2) to (A-57) were prepared in the same manner as colorant dispersion (A-1). Furthermore, the quinoline compounds (b) to (g) described in Table 1 are the following compounds, and were synthesized by the method described in the examples of Japanese Patent Application Publication No. 2012-226110.

[0203] [Chemistry 9]

[0204]

[0205] [Table 1]

[0206]

[0207]

[0208] <Preparation of the coloring composition>

[0209] Example 1

[0210] Preparation of coloring composition

[0211] The following components were selected: 42.0 parts by weight of colorant dispersion (A-1) as (A) colorant; 10.4 parts by weight of resin solution (B-1) as (B) binder resin; 4.2 parts by weight of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as (C) polymerizable compound; and 0.7 parts by weight of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one (Ciba Distillery Co., Ltd.) as (D) photopolymerization initiator. The coloring composition (S-1) was prepared by mixing 1.0 parts by weight of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) (manufactured by BASF, trade name IRGACURE OXE02), 0.05 parts by weight of Megafac F-554 (manufactured by DIC Corporation) as a fluorinated surfactant, and 41.7 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) as an (E) solvent.

[0212] Examples 2 to 46, Comparative Examples 1 to 11

[0213] Coloring compositions (S-2) to (S-57)

[0214] As described in Table 2, the type of colorant dispersion and the amounts of (B) binder resin, (C) polymerizable compound and (E) solvent are changed. Otherwise, coloring compositions (S-2) to (S-57) are prepared in the same manner as coloring composition (S-1).

[0215] [Table 2]

[0216]

[0217]

[0218] <Production of the Light Leakage Evaluation Unit>

[0219] Coloring compositions (S-1) to (S-57) were applied to an ITO film-forming substrate using a spinner, and then pre-baked at 100°C on a hot plate for 100 seconds to form a 2.4 μm thick film. An exposure machine (TOPCON TME-400R) was used, with a cumulative irradiation dose of 40 J / m². 2The obtained coating was exposed to light, and the substrate was heated at 230°C for 20 minutes in a clean oven to form a colored hardening film on the ITO film-forming substrate. Subsequently, an alignment film facing the IPS mode was coated onto the colored hardening film using a spinner, and then pre-baked at 100°C on a hot plate for 100 seconds to form a film thickness of [insert thickness here]. The substrate was coated. Substrate A was fabricated by heating the substrate at 230°C for 20 minutes in a clean oven. Substrate B was fabricated using the same substrate as the ITO film-forming substrate and under the same conditions as the alignment film formation. For substrates A and B with the alignment film, rubbing was performed using a rubbing device (ING, EL03) at a rubbing depth of 0.4 mm / 400 rpm.

[0220] Substrate A and substrate B, after rubbing to the alignment film, are supplied to the next cell fabrication process. First, a 5.5 μm high sealant is applied to substrate A, followed by pre-baking at 100°C on a hot plate for 60 seconds to evaporate the solvent. For substrate B, 3.5 μm bead spacers are distributed inside a glove box to maintain the cell gap. Substrate A is stacked on top of substrate B and pressed together, then heated at 230°C for 60 minutes in a clean oven to heat-cure the sealant. Next, liquid crystal facing the IPS is injected into the cell using a vacuum liquid crystal injection apparatus (SEIMITSU CS320). Then, the liquid crystal injection section is sealed using an ultraviolet (UV) curable sealant. Finally, a metal halide lamp exposure machine (USHIO PLA-501F) is used with a cumulative irradiation dose of 1 J / m². 2 The light leakage evaluation unit is created by exposing the light on a hot plate at 80°C for 10 minutes and annealing it.

[0221] <Light Leakage Evaluation Method>

[0222] The polarizing plates of the cell fabricated using the described method were arranged in an alternating configuration, and the display was set to be black when no voltage was applied. Regarding the applied voltage, an Agilent 4294A was used, and a voltage of 3V was applied. Light leakage in the direction and perpendicular to the electric field generated during rubbing was observed according to the following criteria. The evaluation results are shown in Table 3.

[0223] [Evaluation Criteria]

[0224] ○: No light leakage

[0225] △: Weak light leakage (light leakage length less than 0.3mm)

[0226] ×: Light leakage intensity (light leakage length is 0.3mm or more)

[0227] <Contrast Ratio Evaluation>

[0228] Evaluation of chromaticity characteristics

[0229] The obtained coloring compositions (S-1) to (S-57) were respectively coated onto glass substrates using a spin coater. Then, they were pre-baked on a hot plate at 100°C for 2 minutes to form three coatings of different thicknesses. Subsequently, these substrates were cooled to room temperature. Then, the coatings on the substrates were subjected to radiation at 1000 J / m² using a high-pressure mercury lamp with wavelengths including 365 nm, 405 nm, and 436 nm, without the need for a light-blocking mask. 2 Each coating was exposed to the specified exposure level. Then, it was baked at 220°C for 20 minutes to form a hardened film on the substrate. For the three hardened films obtained, the chromaticity coordinates (x, y) in the CIE colorimetric system were measured using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) with a C light source and a 2-degree field of view. Based on the measurement results, the chromaticity coordinate value x and the stimulus value (Y) when the chromaticity coordinate value y = 0.59 were calculated.

[0230] For the three hardened films obtained in the "Evaluation of Chromaticity Characteristics" section, the contrast ratio was measured using a contrast meter (CT-1 contrast measuring instrument manufactured by Tsubosaka Electric). The contrast ratio at a chromaticity coordinate value of y = 0.59 was calculated based on the measurement results. A contrast ratio value of 9000 or higher was marked as "○", a contrast ratio value of 8000 or higher but less than 9000 was marked as "△", and a contrast ratio less than 8000 was marked as "×". The evaluation results are shown in Table 3.

[0231] [Table 3]

[0232]

[0233]

Claims

1. A colored composition comprising (A) a colorant comprising a halogenated metal phthalocyanine pigment, (B) a binder resin, and (C) a polymerizable compound, wherein, The (A) colorant further comprises (A 1 ) a halogenated metal phthalocyanine pigment, with (A 2 ) a quinophthalone compound represented by the following formula (1), (A 1 ) halogenated metal phthalocyanine pigments and (A 2 ) quinophthalone compounds represented by the following formula (1) : (A 1 ) / (A 2 ) is 99 / 1 to 85 / 15. in the formula (1), R 1 ~R 13 each independently represents a hydrogen atom; a halogen atom; an alkyl group which can have a substituent (s) ; an alkoxy group which can have a substituent (s) ; an aryl group which can have a substituent (s) ; -SO3H, -COOH or a monovalent to trivalent metal salt or an alkylammonium salt of these acidic groups; a sulfonamide group which can have a substituent (s) ; or a phthalimido group which can have a substituent (s) ; wherein, at least one adjacent group of R 1 ~R 4 and / or at least one adjacent group of R 10 ~R 13 is integrated to form an aromatic ring which can have a substituent (s).

2. The colored composition according to claim 1, wherein, The content ratio of the (A 1 ) halogenated metal phthalocyanine pigment is 61 to 79 mass %.

3. The colored composition of claim 1, wherein, The content ratio of the quinophthalone compound is 0.5 to 11 mass% relative to the total colorant. 2 ) quinophthalone compound is 0.5 to 11 mass% relative to the total colorant.

4. The colored composition of claim 1, wherein, (A 1 ) The halogenated metal phthalocyanine pigment is one or two or more selected from a halogenated copper phthalocyanine pigment, a halogenated zinc phthalocyanine pigment, and a halogenated aluminum phthalocyanine pigment.

5. The colored composition of claim 1, wherein, the mass ratio of the (B) binder resin to the (C) polymerizable compound, i.e., (B) / (C), is 95 / 5 to 61 / 39.

6. The colored composition of claim 1, wherein, (A) the colorant further comprises at least one selected from the group consisting of azo pigments and (A 2 ) quinophthalone pigments other than quinophthalone compounds as (A 1 ) halogenated metal phthalocyanine pigments and (A 2 ) colorants other than quinophthalone compounds.

7. The colored composition according to claim 6, wherein, (A 1 ) halogenated metal phthalocyanine pigments and (A 2 ) colorants other than quinophthalone compounds are at least one selected from the group consisting of C.I. Pigment Yellow 138, C.I. Pigment Yellow 150 and C.I. Pigment Yellow 180.

8. A colored cured film which is a cured product of the colored composition according to claim 1.

9. A color filter comprising the colored cured film according to claim 8.

10. A display element comprising the colored cured film according to claim 8.

11. A light-receiving element comprising the colored cured film according to claim 8.

12. A light-emitting element comprising the colored cured film according to claim 8.

13. A colorant dispersion liquid comprising the (A) colorant comprising a halogenated metal phthalocyanine pigment in the colored composition according to claim 1.

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