Hardening coloring composition

Abstract

To provide a curable coloring composition which is useful for manufacture of a color filter whose roughness on a surface is reduced.SOLUTION: A curable coloring composition contains a coloring agent (A), a resin (B), a silicone compound (C), a polymerizable compound (D), and a polymerization initiator (E), in which the silicone compound (C) satisfies condition (1). <Condition (1)> A contact angle of a coated film formed by spin coating a mixture (H) containing a resin (B-1) having a structural unit of Formula (1), the silicone compound (C), a leveling agent (F) and a solvent (G) and whose content of the silicone compound (C) is 21 mass% in 100 mass% of the total amount of a solid content onto a glass substrate, and baking the mixture at 230°C for 20 minutes, and ion exchange water is 70° or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable colored composition. [Background technology]

[0002] Color filters used in displays such as liquid crystal displays, electroluminescent displays, and plasma displays, and solid-state imaging devices such as CCD and CMOS sensors, are produced from curable coloring compositions. Known examples of such curable coloring compositions include liquid coloring compositions containing a surface conditioner such as dimethylpolysiloxane having polyalkylene oxide and an organic solvent (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-186683 Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention addresses the problem of providing a curable coloring composition that is useful for producing a cured film (for example, a color filter) having a surface roughness reduced compared to conventional compositions. [Means for solving the problem]

[0005] The present invention includes the following inventions. [1] A curable coloring composition comprising a colorant (A), a resin (B), a silicone compound (C), a polymerizable compound (D), and a polymerization initiator (E), A curable colored composition characterized in that the silicone compound (C) satisfies condition (1). <Condition (1)> A mixture (H) containing a resin (B-1) having a structural unit of formula (1), the silicone compound (C), a leveling agent (F), and a solvent (G), in which the content of the silicone compound (C) is 21% by mass relative to 100% by mass of the total solid content, is spin-coated onto a glass substrate and baked at 230°C for 20 minutes, to form a coating film, which has a contact angle of 70° or more with ion-exchanged water. [ka] [2] The curable colored composition according to [1], wherein the colorant (A) contains a dye. [3] The curable colored composition according to [2], wherein the dye is a salt-forming compound and / or a xanthene dye. [4] The curable colored composition according to [3], wherein the salt-forming compound is a triarylmethane salt-forming compound. [5] The curable colored composition according to any one of [1] to [4], wherein the content of the silicone compound (C) relative to the total amount of the curable colored composition is 2.0 mass % or less. [6] The curable colored composition according to any one of [1] to [5], which is capable of forming a cured film having an arithmetic mean roughness Ra of the surface of 6.0 or less. [7] A color filter formed from the curable coloring composition according to any one of [1] to [6]. [8] A display device comprising the color filter according to [7]. [Effects of the Invention]

[0006] The cured film formed from the curable colored composition of the present invention has reduced surface roughness. DETAILED DESCRIPTION OF THE INVENTION

[0007] The curable coloring composition of the present invention contains a colorant (hereinafter sometimes referred to as "colorant (A)"), a resin (hereinafter sometimes referred to as "resin (B)"), a silicone compound (hereinafter sometimes referred to as "silicone compound (C)"), a polymerizable compound (hereinafter sometimes referred to as "polymerizable compound (D)"), and a polymerization initiator (hereinafter sometimes referred to as "polymerization initiator (E)"). Furthermore, the silicone compound (C) satisfies condition (1). <Condition (1)> A mixture (H) containing a resin (B-1) having a structural unit of formula (1), a silicone compound (C), a leveling agent (F), and a solvent (G), in which the content of the silicone compound (C) is 21% by mass relative to 100% by mass of the total solid content, is spin-coated onto a glass substrate and baked at 230°C for 20 minutes, and the contact angle of the formed coating film with ion-exchanged water is 70° or more.

[0008] [ka]

[0009] By incorporating the silicone compound (C) that satisfies the above condition (1) into the curable coloring composition, it is possible to reduce the surface roughness of the cured film formed from the curable coloring composition.

[0010] The curable coloring composition of the present invention preferably further contains a leveling agent (hereinafter, may be referred to as leveling agent (F)). Furthermore, the curable coloring composition of the present invention preferably contains a solvent (hereinafter, may be referred to as solvent (G)).

[0011] Each component will be described in detail below. In this specification, the compounds exemplified as each component can be used alone or in combination, unless otherwise specified.

[0012] <Colorant (A)> The colorant (A) preferably contains a dye. Since the silicone compound (C) reacts easily with the dye, the effect of reducing surface roughness by the silicone compound (C), which will be described later, is easily exhibited. Furthermore, the dye is preferably a salt-forming compound. The salt-forming compound has an ionic bond.

[0013] Preferred examples of the dye include triarylmethane dyes, coumarin dyes, cyanine dyes, squarylium dyes, and xanthene dyes, with triarylmethane dyes and xanthene dyes being more preferred. From the viewpoint of improving contrast, triarylmethane dyes are more preferred, and from the viewpoint of reducing surface roughness, xanthene dyes are more preferred. These dyes may be used alone or in combination of two or more.

[0014] Preferred examples of salt-forming compounds include triarylmethane salt-forming compounds, coumarin salt-forming compounds, cyanine salt-forming compounds, squarylium salt-forming compounds, and xanthene salt-forming compounds. Xanthene salt-forming compounds and triarylmethane salt-forming compounds are more preferred, and triarylmethane salt-forming compounds are even more preferred. These salt-forming compounds may be used alone or in combination of two or more. Preferred examples of coumarin salt-forming compounds, cyanine salt-forming compounds, and squarylium salt-forming compounds include the coumarin salt-forming compounds, cyanine salt-forming compounds, and squarylium salt-forming compounds described in JP 2018-194747 A. Preferred examples of xanthene dyes include the xanthene dyes described in JP 2013-234319 A. Preferred examples of xanthene salt-forming compounds include xanthene dyes having an ionic bond. Triarylmethane salt-forming compounds and xanthene dyes are described in detail below.

[0015] <Triarylmethane salt-forming compounds> The triarylmethane salt-forming compound may be a compound consisting of a cation having a triarylmethane skeleton and an anion not having a triarylmethane skeleton, or may be a compound consisting of an anion having a triarylmethane skeleton and a cation not having a triarylmethane skeleton. The triarylmethane skeleton is a skeleton in which three aromatic rings are bonded to one carbon, and preferably two of the three aromatic rings are aromatic hydrocarbon rings and one is an aromatic heterocyclic ring.

[0016] The triarylmethane salt-forming compound is preferably at least one selected from the group consisting of a compound represented by formula (A1) (hereinafter, sometimes referred to as compound (A1)) and a compound represented by formula (A2) (hereinafter, sometimes referred to as compound (A2)), and more preferably compound (A1).

[0017] <<Compound (A1)>>

[0018] [ka] [In formula (A1), R 41b ~R 44b each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, and the substituent which the aromatic hydrocarbon group and the aralkyl group may have is -SO3 - or -SO2-N - -SO2-R f The hydrogen atoms contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or a halogen atom, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent -CH2- are not simultaneously replaced with -O-. R 41b and R 42band may combine to form a ring together with the nitrogen atom to which they are attached, and R 43b and R 44b may combine to form a ring together with the nitrogen atom to which they are attached. R 47b ~R 54b are each independently a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, -SO3 - , -SO2-N - -SO2-R f or an alkyl group having 1 to 8 carbon atoms, wherein -CH2- constituting the alkyl group may be replaced by -O- or -CO-, and R 48b and R 52b and may be bonded to each other to form -NH-, -S-, or -SO2-, provided that adjacent -CH2- groups in the alkyl group are not simultaneously substituted with -O-. Ring T 2b represents an aromatic heterocyclic ring having 3 to 10 carbon atoms or an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and the aromatic heterocyclic ring and the aromatic hydrocarbon ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amino group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. The substituent which the aromatic hydrocarbon group may have is, for example, -SO3 - or -SO2-N - -SO2-R f may be. M r+ represents a metal ion with a valence of r. k is R 41b ~R 44b , R 47b ~R 54b and Ring T 2b has -SO3 - The number of -SO2-N - -SO2-R f represents the sum of the number of r represents an integer of 1 or greater. R f represents a fluoroalkyl group having 1 to 12 carbon atoms. However, R 41b ~R 44b , R 47b ~R 54b and Ring T2b is -SO3 - or -SO2-N - -SO2-R f has at least one When a single molecule contains a plurality of structures represented by the following formula, they may be the same structure or different structures. [ka] [In the formula, ring T 2b , R 41b ~R 44b and R 47b ~R 54b have the same meanings as above.

[0019] Ring T 2b The aromatic heterocycle represented by the formula (I) may be a single ring or a condensed ring. 2b The number of carbon atoms in the aromatic heterocycle represented by the formula (I) is preferably 3 to 10, and more preferably 3 to 8. The aromatic heterocycle is preferably a 5- to 10-membered ring, and more preferably a 5- to 9-membered ring. Examples of monocyclic aromatic heterocycles include 5-membered rings containing a nitrogen atom, such as a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, and a thiazole ring; 5-membered rings containing no nitrogen atom, such as a furan ring and a thiophene ring; and 6-membered rings containing a nitrogen atom, such as a pyridine ring, a pyrimidine ring, a pyridazine ring, and a pyrazine ring. Examples of fused aromatic heterocycles include fused rings containing a nitrogen atom, such as an indole ring, a benzimidazole ring, a benzothiazole ring, and a quinoline ring; and fused rings containing no nitrogen atom, such as a benzofuran ring. Among them, Tamaki T 2b The aromatic heterocycle is preferably an aromatic heterocycle containing a nitrogen atom, and more preferably a five-membered aromatic heterocycle containing a nitrogen atom.

[0020] Ring T 2bExamples of the substituent that the aromatic heterocycle may have include a halogen atom, a cyano group, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a substituted or unsubstituted amino group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and preferred are a saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amino group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. 2b preferably has an amino group which may have a substituent, and the substituent which the amino group may have is preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent.

[0021] Ring T 2b is preferably a ring represented by formula (A1-t1).

[0022] [ka]

[0023] [In formula (A1-t1), R 56b represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. X2b is an oxygen atom, -N(R 57b )- or a sulfur atom. R 57b represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R 45b and R 46bR each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent -CH2- are not simultaneously replaced with -O-. 45b and R 46b may combine to form a ring together with the nitrogen atom to which they are attached. * represents a bond to the carbocation.

[0024] Also, Ring T 2b is also preferably a ring represented by formula (A1-t2).

[0025] [ka]

[0026] [In formula (A1-t2), R 59b represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent. R 60b represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. R 61b is a hydrogen atom, -SO3 - , or -SO2-N - -SO2-R f Represents. * represents a bond to the carbocation.

[0027] Ring T 2b Examples of the aromatic hydrocarbon ring represented by the formula (I) include a benzene ring and a naphthalene ring. 2bExamples of the substituent that the aromatic hydrocarbon ring represented by the following formula may have include the substituents that the aromatic heterocycle mentioned above may have.

[0028] R 41b ~R 46b , R 56b and R 59b ~R 60b and saturated hydrocarbon groups having 1 to 20 carbon atoms represented by the formula 2b The saturated hydrocarbon group having 1 to 20 carbon atoms that may be carried by the amino group that may be carried by the amino group may be linear, branched, or cyclic. Examples of the linear or branched saturated hydrocarbon group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and icosyl; and branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl. The saturated hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 6 carbon atoms.

[0029] R 41b ~R 46b , R 56b and R 59b ~R 60b and ring T 2b The cyclic saturated hydrocarbon group that the amino group that may be present in may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include alicyclic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group. The number of carbon atoms in the cyclic saturated hydrocarbon group is preferably 3 to 10, and more preferably 6 to 10.

[0030] R 41b ~R 46b , R 56b and R 59b ~R 60b saturated hydrocarbon groups represented by the formula 2bThe saturated hydrocarbon group that the amino group that may be present in may have a substituted or unsubstituted amino group or a halogen atom as a substituent. Examples of the substituted amino group include alkylamino groups such as methylamino, dimethylamino, and diethylamino. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. When the halogen atom is a fluorine atom, the saturated hydrocarbon group having a fluorine atom as a substituent is preferably a perfluoroalkyl group such as a trifluoromethyl group, a perfluoroethyl group, or a perfluoropropyl group.

[0031] R 47b ~R 54b Examples of the alkyl group having 1 to 8 carbon atoms represented by the formula: 41b Among the linear or branched saturated hydrocarbon groups exemplified as the saturated hydrocarbon group represented by the formula (I), groups having 1 to 8 carbon atoms can be mentioned. Also, R 57b As the alkyl group having 1 to 10 carbon atoms represented by the formula 41b Among the linear or branched saturated hydrocarbon groups exemplified as the saturated hydrocarbon group represented by the formula: groups having 1 to 10 carbon atoms can be mentioned.

[0032] R 41b ~R 46bWhen the saturated hydrocarbon group represented by the formula (I) has 2 to 20 carbon atoms, -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent -CH2- are not simultaneously replaced with -O-. In this case, the saturated hydrocarbon group is preferably a linear or branched saturated hydrocarbon group (i.e., a linear or branched alkyl group), and more preferably a linear saturated hydrocarbon group (i.e., a linear alkyl group). The saturated hydrocarbon group in which -CH2- may be replaced with -O- or -CO- preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms. Furthermore, when -CH2- is replaced with -O- or -CO-, the number of carbon atoms between the terminal and -O- or -CO-, or between -O- or -CO- and -O- or -CO-, is preferably 1 to 5, more preferably 2 to 3, and even more preferably 2.

[0033] Also, R 41b ~R 46b , R 56b and R 59b ~R 60b and an aromatic hydrocarbon group having a substituent represented by the formula: 2b The aromatic hydrocarbon group which the amino group may have (which may have a substituent) preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 12 carbon atoms. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group. Preferred examples include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group, and particularly preferred examples are a phenyl group, a tolyl group, and a xylyl group. The aromatic hydrocarbon group may have one or more substituents. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom, or a bromine atom; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group; a hydroxy group; a sulfamoyl group; an alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group; an alkoxycarbonyl group having 1 to 6 carbon atoms such as a methoxycarbonyl group or an ethoxycarbonyl group; -SO3 -;-SO2-N - -SO2-R f ; etc., halogen atoms such as fluorine atom, chlorine atom, iodine atom, bromine atom, etc.; -SO3 - ;-SO2-N - -SO2-R f is preferably a fluorine atom or -SO3 - However, -SO3 - and -SO2-N - -SO2-R f is preferably directly bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group, that is, it is preferably substituted for a hydrogen atom bonded to the aromatic hydrocarbon ring. Specific examples of the aromatic hydrocarbon group which may have a substituent include groups represented by the following formula: In the following formula, * represents a bond.

[0034] [ka]

[0035] [ka]

[0036] R 41b ~R 46b , R 59b and an aralkyl group having a substituent represented by the formula: 2b Examples of the aralkyl group that the amino group that may be carried by the aromatic hydrocarbon group (which may have a substituent) include groups in which an alkanediyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), such as a methylene group, ethylene group, or propylene group, is bonded to a group explained above as the aromatic hydrocarbon group. The number of carbon atoms in the aralkyl group is preferably 7 to 30, more preferably 7 to 20, and even more preferably 7 to 17.

[0037] R 41b and R 42b are bonded to form a ring together with the nitrogen atom to which they are attached, R43b and R 44b are bonded to form a ring together with the nitrogen atom to which they are attached, and R 45b and R 46b Examples of the ring formed by bonding together with the nitrogen atom to which they are bonded include nitrogen-containing non-aromatic 4- to 7-membered rings such as a pyrrolidine ring, a morpholine ring, a piperidine ring, and a piperazine ring, and preferably include 4- to 7-membered rings having only one nitrogen atom as a hetero atom such as a pyrrolidine ring and a piperidine ring.

[0038] Among them, R 41b ~R 44b , R 56b , R 59b ~R 60b are each independently preferably a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent, and are each independently preferably a saturated hydrocarbon group having 1 to 8 carbon atoms or a group represented by the following formula: 41b and R 43b are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms, and R 42b and R 44b are each more preferably an aromatic hydrocarbon group which may have a substituent, and R 56b is more preferably an aromatic hydrocarbon group which may have a substituent. R 56b , R 59b ~R 60b is even more preferably a group represented by the following formula: In the following formula, * represents a bond.

[0039] [ka]

[0040] [ka]

[0041] R 45b ~R 46bare each independently a saturated hydrocarbon group having 1 to 20 carbon atoms, a group in which one -CH2- in an alkyl group having 2 to 20 carbon atoms is replaced with -O- or -CO-, or an aromatic hydrocarbon group which may have a substituent, or R 45b and R 46b and preferably combine to form a ring together with the nitrogen atom to which they are attached. 45b ~R 46b are each independently a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, a group represented by the following formula, or an aromatic hydrocarbon group which may have a substituent, or R 45b and R 46b and R are more preferably bonded to form a 4- to 7-membered ring having only one nitrogen atom as a heteroatom, and are each independently a saturated hydrocarbon group having 1 to 8 carbon atoms, an aromatic hydrocarbon group having a substituent, an alkoxyalkyl group, or a group represented by the following formula: 45b is a saturated hydrocarbon group having 1 to 4 carbon atoms, and R 46b is even more preferably a tolyl group. In the following formula, * represents a bond to the nitrogen atom.

[0042] [ka]

[0043] [ka]

[0044] Also R 47b ~R 54b As the group in which -CH2- constituting the alkyl group having 2 to 8 carbon atoms represented by the formula (1) is replaced by -O- or -CO- (provided that adjacent -CH2- in the alkyl group are not simultaneously replaced by -O-), the above-mentioned R 41b ~R 46b Examples of the alkyl group include groups having 8 or less carbon atoms, which are represented by the following formula: wherein —CH2— in the alkyl group having 2 to 20 carbon atoms is replaced with —O— or —CO—.

[0045] R 47b ~R 54b are preferably each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, more preferably each independently a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom, and further preferably each independently a hydrogen atom. Also, R 57b is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 61b is preferably a hydrogen atom.

[0046] X2b is preferably -S-.

[0047] M r+ Examples of r-valent metal ions represented by the formula (1) include alkali metal ions such as lithium ion, sodium ion, and potassium ion; alkaline earth metal ions such as beryllium ion, magnesium ion, calcium ion, strontium ion, and barium ion; transition metal ions such as titanium ion, zirconium ion, chromium ion, manganese ion, iron ion, cobalt ion, nickel ion, and copper ion; and typical metal ions such as zinc ion, cadmium ion, aluminum ion, indium ion, tin ion, lead ion, and bismuth ion. r is 1 or more, preferably 2 or more, and is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less. M r+ As the cation, alkaline earth metal ions and typical metal ions are more preferred, alkaline earth metal ions and zinc ions are even more preferred, and alkaline earth metal ions are even more preferred.

[0048] In formula (A1), M r+ The number of 41b ~R 44b , R 47b ~R 54b and Ring T 2b has -SO3 - The number of -SO2-N - -SO2-R fThis is one less than the sum (k) of the numbers of atoms in the compound (A1). Therefore, the compound (A1) has a valence of 0, i.e., it is an electrically neutral compound.

[0049] R f Examples of the fluoroalkyl group having 1 to 12 carbon atoms represented by the formula (I) include a monofluoromethyl group, a difluoromethyl group, a perfluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, a perfluoroethyl group, a monofluoropropyl group, a difluoropropyl group, a trifluoropropyl group, a tetrafluoropropyl group, a pentafluoropropyl group, a hexafluoropropyl group, a perfluoropropyl group, a monofluorobutyl group, a difluorobutyl group, a trifluorobutyl group, a tetrafluorobutyl group, a pentafluorobutyl group, a hexafluorobutyl group, a heptafluorobutyl group, an octafluorobutyl group, and a perfluorobutyl group. f The fluoroalkyl group represented by R is preferably a perfluoroalkyl group. f The fluoroalkyl group represented by the formula (I) preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms.

[0050] In formula (A1), R 41b ~R 44b , R 47b ~R 54b and Ring T 2b is -SO3 - or -SO2-N - -SO2-R f At least one of the following is preferably -SO3 - R 41b ~R 44b , R 47b ~R 54b and Ring T 2b has -SO3 - and -SO2-N - -SO2-R f The sum (k) of the numbers of these is preferably 1 to 7, more preferably 2 to 7, even more preferably 2 to 4, still more preferably 2 or 3, and particularly preferably 2.

[0051] -SO3 - or -SO2-N - -SO2-R f It is preferable that at least one of the following conditions (Ia) to (Id) be satisfied, and it is more preferable that at least one of the following conditions (Ia) and (Ib) be satisfied. (Ia) R above 47b ~R 54b Included as either (Ib)R 41b ~R 44b and the like, which is bonded to any one of the aromatic hydrocarbon groups having 6 to 20 carbon atoms and which may have a substituent represented by the following formula: (Ic)R 41b ~R 44b and the like, which is bonded to an aralkyl group having 7 to 30 carbon atoms and which may have a substituent represented by (Id)T 2b is bonded to any of the aromatic hydrocarbon groups having 6 to 20 carbon atoms that substitute a hydrogen atom of an aromatic heterocycle represented by

[0052] However, aromatic hydrocarbon groups or aralkyl groups have -SO3 - or -SO2-N - -SO2-R f When bonded, -SO3 - or -SO2-N - -SO2-R f is preferably directly bonded to the aromatic hydrocarbon group or the aromatic hydrocarbon ring of the aralkyl group. - or -SO2-N - -SO2-R f is preferably substituted for a hydrogen atom bonded to an aromatic hydrocarbon ring. -SO3 - or -SO2-N - -SO2-R f is R 41b ~R 44b or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent represented by 41b ~R 44bIn the aromatic hydrocarbon ring (for example, a benzene ring) of the aralkyl group having 7 to 30 carbon atoms which may have a substituent represented by the following formula, it is preferably bonded at the para position relative to the bonding position to the nitrogen atom. Compound (A1) contains multiple -SO3 - or -SO2-N - -SO2-R f If it contains multiple -SO3 - or -SO2-N - -SO2-R f may be bonded to the same aromatic hydrocarbon ring, but are preferably bonded to different aromatic hydrocarbon rings.

[0053] The compound (A1) preferably does not have an ethylenically unsaturated bond.

[0054] The compound (A1) is preferably a compound represented by the following formula (II-1) (hereinafter, sometimes referred to as compound (II-1)).

[0055] [ka]

[0056] [In formula (II-1), R 81b ~R 90b are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, -SO3 - or -SO2-N - -SO2-R f Represents. k1 is R 41b , R 43b , R 47b ~R 54b , R 81b ~R 90b and Ring T 2b has -SO3 - The number of -SO2-N - -SO2-R f represents the sum of the number of R 41b , R 43b , R 47b ~R54b , T 2b , M r+ , r, R f has the same meaning as above. However, R 41b , R 43b , R 47b ~R 54b , R 81b ~R 90b and Ring T 2b is -SO3 - or -SO2-N - -SO2-R f ]

[0057] R 81b ~R 90b As the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 41b Examples of the saturated hydrocarbon group represented by R include the same groups as those exemplified above. 81b ~R 90b Examples include hydrogen atoms, saturated hydrocarbon groups with 1 to 8 carbon atoms, and -SO3 - or -SO2-N - -SO2-R f is preferred, and a hydrogen atom, a saturated hydrocarbon group having 1 to 4 carbon atoms, -SO3 - or -SO2-N - -SO2-R f is more preferred, and is a hydrogen atom, a saturated hydrocarbon group having 1 to 4 carbon atoms, or -SO3 - is more preferable.

[0058] -SO3 - or -SO2-N - -SO2-R f It is preferable that at least one of the conditions selected from (Ie) to (Ig) is satisfied, it is more preferable that at least one of the conditions selected from (If) and (Ig) is satisfied, and it is even more preferable that the condition (If) is satisfied. (Ie)R 47b ~R 54b Included as either (If)R 81b ~R 90b Included as either (Ig)T 2bis bonded to an aromatic hydrocarbon group having 6 to 20 carbon atoms that substitutes a hydrogen atom of an aromatic heterocycle represented by

[0059] -SO3 - or -SO2-N - -SO2-R f It is even more preferable that condition (If') is satisfied. (If')R 86b and R 89b Included in either or both of

[0060] In formula (II-1), R 41b , R 43b , R 47b ~R 54b , R 81b ~R 90b and Ring T 2b has -SO3 - and -SO2-N - -SO2-R f The sum of the numbers (k1) is preferably 1 to 7, more preferably 1 to 4, and even more preferably 1 or 2.

[0061] Examples of the compound (A1) include the compounds shown below (compounds represented by formulae (A1-1) to (A1-13)).

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] [ka]

[0073] [ka]

[0074] [ka]

[0075] Among the compounds represented by formulae (A1-1) to (A1-13), compounds represented by formula (A1-7), (A1-11), or (A1-13) are preferred, with compounds represented by formula (A1-7) being particularly preferred.

[0076] <<Compound (A2)>>

[0077] [ka] [In formula (A2), R 11b ~R 14b each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, and in the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or a halogen atom, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, -CH2- contained in the saturated hydrocarbon group may be substituted with -O- or -CO-, provided that in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent -CH2- are not simultaneously substituted with -O-. 11b and R 12b and may combine to form a ring together with the nitrogen atom to which they are attached, and R 13b and R 14b may combine to form a ring together with the nitrogen atom to which they are attached.

[0078] R 17b ~R 24b R each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms, and one or more —CH2— groups constituting the alkyl group may be substituted with —O— or —CO—. 18b and R 22b may be bonded to each other to form -NH-, -O-, -S- or -SO2-. Ring T 1b represents an aromatic heterocyclic ring having 3 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring having 6 to 10 carbon atoms which may have a substituent. [Y] m- represents any m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and oxygen. m represents any natural number. When a single molecule contains a plurality of structures represented by the following formula, they may be the same structure or different structures.

[0079] [ka] [In the formula, ring T 1b , R 11b ~R 14b , and R 17b ~R 24b have the same meanings as above.

[0080] Ring T 1b The aromatic heterocycle may be a single ring or a condensed ring. Ring T 1b Examples of the substituent that the aromatic heterocycle may have include a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms that may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms that may have a substituent, and an amino group that may have a substituent. 1b It is preferable that the amino group has an amino group which may have a substituent such as an alkyl group having 1 to 10 carbon atoms. Among them, Tamaki T 1b The aromatic heterocycle is preferably an aromatic heterocycle containing a nitrogen atom, and more preferably a five-membered aromatic heterocycle containing a nitrogen atom.

[0081] Furthermore, Ring T 1b is particularly preferably a ring represented by formula (A2-t1).

[0082] [ka] [In formula (A2-t1), R 26b represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group which may have a substituent. X1b is an oxygen atom, -NR 27b - or a sulfur atom. R 27brepresents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R 15b and R 16b R each independently represent a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an alkyl group having 2 to 20 carbon atoms in which -CH2- in the alkyl group may be replaced with -O-, an aromatic hydrocarbon group which may have a substituent, an aralkyl group which may have a substituent, or a hydrogen atom. 15b and R 16b may combine to form a ring together with the nitrogen atom to which they are attached. However, adjacent -CH2- are not simultaneously substituted with -O-, and -CH2- bonded to a nitrogen atom are not simultaneously substituted with -O-. * represents a bond to the carbocation.

[0083] Ring T 1b Examples of the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring. Ring T 1b Examples of the substituent that the aromatic hydrocarbon ring may have include a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and an amino group which may have a substituent.

[0084] R 11b ~R 16b , and R 26b The saturated hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) may be linear, branched, or cyclic. Examples of linear or branched saturated hydrocarbon groups include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and icosyl; and branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl. The saturated hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 6 carbon atoms.

[0085] R11b ~R 16b , and R 26b The cyclic saturated hydrocarbon group represented by the formula (I) may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group. The cyclic saturated hydrocarbon group preferably has 3 to 10 carbon atoms, and more preferably has 6 to 10 carbon atoms.

[0086] R 11b ~R 16b , and R 26b The saturated hydrocarbon group may be substituted with a halogen atom or an optionally substituted amino group. Examples of the optionally substituted amino group include an amino group; and alkylamino groups such as a methylamino group, a dimethylamino group, and a diethylamino group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. When the halogen atom is a fluorine atom, it is preferable that the halogen atom be substituted so as to form a perfluoroalkyl unit such as a trifluoromethyl unit, a pentafluoroethyl unit, or a heptafluoropropyl unit.

[0087] R 17b ~R 24b Examples of the alkyl group having 1 to 8 carbon atoms represented by the formula: 11b Examples of the saturated hydrocarbon group represented by the formula include groups having 1 to 8 carbon atoms among the linear or branched saturated hydrocarbon groups exemplified above. Also, R 27b Examples of the alkyl group having 1 to 10 carbon atoms represented by the formula: 11b Examples of the saturated hydrocarbon group represented by the formula include groups having 1 to 10 carbon atoms among the linear or branched saturated hydrocarbon groups exemplified above.

[0088] R 11b ~R 16bWhen the saturated hydrocarbon group (preferably an alkyl group) represented by the formula (I) has 2 or more carbon atoms, -CH2- contained in the saturated hydrocarbon group (preferably an alkyl group) may be substituted with -O- or -CO-, preferably with -O-. The saturated hydrocarbon group (preferably an alkyl group) preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms. When -CH2- is substituted with -O- or -CO-, the number of carbon atoms between the terminal and -O- or -CO-, or between -O- or -CO- and -O- or -CO-, is, for example, 1 to 5, preferably 2 to 3, more preferably 2. However, adjacent -CH2- are not simultaneously substituted with -O-.

[0089] Also, R 11b ~R 16b , and R 26b The aromatic hydrocarbon group, which may have a substituent, preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 12 carbon atoms. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl, tolyl, xylyl, naphthyl, anthryl, phenanthryl, biphenyl, and terphenyl. Preferred are phenyl, naphthyl, tolyl, and xylyl groups, and particularly preferred are phenyl and tolyl groups. The aromatic hydrocarbon group may have one or more substituents, and examples of the substituents include halogen atoms such as fluorine, chlorine, iodine, and bromine; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; hydroxy groups; sulfamoyl groups; alkylsulfonyl groups having 1 to 6 carbon atoms such as methylsulfonyl; and alkoxycarbonyl groups having 1 to 6 carbon atoms such as methoxycarbonyl and ethoxycarbonyl.

[0090] R 11b ~R 16b Examples of the optionally substituted aralkyl group represented by the following formula (I) include a group in which an alkanediyl group having 1 to 5 carbon atoms, such as a methylene group, an ethylene group, or a propylene group, is bonded to the group explained above as the aromatic hydrocarbon group.

[0091] R 11b and R 12b are bonded to form a ring together with the nitrogen atom to which they are attached, R 13b and R 14b and R bonded together to form a ring together with the nitrogen atom to which they are attached, and 15b and R 16b Examples of the ring formed by bonding together with the nitrogen atom to which they are bonded include nitrogen-containing non-aromatic 4- to 7-membered rings such as a pyrrolidine ring, a morpholine ring, a piperidine ring, and a piperazine ring, and preferably include 4- to 7-membered rings having only one nitrogen atom as a hetero atom such as a pyrrolidine ring and a piperidine ring.

[0092] Among them, R 11b ~R 14b , and R 26b is preferably a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent, and more preferably each independently is a saturated hydrocarbon group having 1 to 8 carbon atoms or a group represented by the following formula: In the following formula, * represents a bond, and Me represents a methyl group.

[0093] [ka]

[0094] R 11b and R 13b are preferably each independently a saturated hydrocarbon group having 1 to 10 carbon atoms, and R 12b and R 14b are preferably each independently an aromatic hydrocarbon group which may have a substituent, and R 26b is preferably an aromatic hydrocarbon group which may have a halogen atom. R 11b and R 13b are each independently a saturated hydrocarbon group having 1 to 6 carbon atoms, and R 12b and R 14b are each independently an aromatic hydrocarbon group, and R 26bis more preferably an aromatic hydrocarbon group which may have a fluorine atom. R 11b and R 13b are each independently a methyl group or an ethyl group, and R 12b and R 14b are each more preferably independently a phenyl group, and R 26b is more preferably a phenyl group having a fluorine atom.

[0095] R 15b and R 16b are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms, a group in which -O- is inserted between carbon atoms of an alkyl group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group which may have a substituent, or R 15b and R 16b and R are preferably bonded to form a ring together with the nitrogen atom to which they are attached. 15b and R 16b are each independently a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or a group represented by the following formula, or R 15b and R 16b are bonded to form a 4- to 7-membered ring having only one nitrogen atom as a hetero atom. In the following formula, * represents a bond to the nitrogen atom, and Me represents a methyl group.

[0096] [ka]

[0097] Also, R 17b ~R 24b and a group in which -CH2- in an alkyl group having 2 to 8 carbon atoms is substituted with -O- or -CO-, are 11b ~R 16b Examples of the groups include those having 8 or less carbon atoms selected from the corresponding groups of the above.

[0098] R 17b ~R 24bFrom the viewpoint of ease of synthesis, it is preferable that each of the is independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, more preferably each of the is independently a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom, and further preferably each of the is independently a hydrogen atom.

[0099] X1b is preferably a sulfur atom.

[0100] Examples of the cation moiety of formula (A2) include cations 1 to 14 represented by formula (I-1), as shown in Table 1 below.

[0101] [ka]

[0102] [Table 1]

[0103] In Table 1, Ph1 to Ph9 represent groups represented by the following formulae: In the formulae, * represents a bond.

[0104] [ka]

[0105] Of these, as the cation moiety of formula (A2), cations 1 to 6 and cations 11 to 14 are preferred, cation 1, cation 2, or cations 12 to 14 are more preferred, and cation 12 is even more preferred.

[0106] [Y] m- is an m-valent anion containing oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus. Compounds containing such an anion tend to have good heat resistance and solvent resistance.

[0107] m is preferably 1 to 20, more preferably 1 to 14, even more preferably 2 to 8, and even more preferably 2 to 6.

[0108] [Y] m- The anion represented by the formula (I) is preferably an anion of a tungsten-containing heteropolyacid or an anion of a tungsten-containing isopolyacid.

[0109] Examples of the anion of a tungsten-containing heteropolyacid or isopolyacid include Keggin-type phosphotungstate ion α-[PW 12 O 40 ] 3- , Dawson-type phosphotungstate ion α-[P2W 18 O 62 ] 6- , β-[P2W 18 O 62 ] 6- , Keggin-type tungstosilicic acid ion α-[SiW 12 O 40 ] 4- , β-[SiW 12 O 40 ] 4- , γ-[SiW 12 O 40 ] 4- , [P2W 17 O 61 ] 10- , [P2W 15 O 56 ] 12- , [H2P2W 12 O 48 ] 12- , [NaP5W 30 O 110 ] 14- , α-[SiWO 34 ] 10- , γ-[SiW 10 O 36 ] 8- , α-[SiW 11 O 39 ] 8- , β-[SiW 11 O 39 ] 8- , [W6O 19 ] 2- , [W10 O 32 ] 4- , WO4 2- and mixtures thereof.

[0110] [Y] m- The anion represented by the formula (I) is also preferably an anion composed of oxygen and at least one element selected from the group consisting of silicon and phosphorus. The anion consisting of at least one element selected from the group consisting of silicon and phosphorus and oxygen is SiO3 2- , PO4 3- Examples include:

[0111] Due to the ease of synthesis and post-treatment, phosphotungstate anions such as Keggin-type phosphotungstate ion and Dawson-type phosphotungstate ion; silicotungstate anions such as Keggin-type silicotungstate ion; [W 10 O 32 ] 4- Among these, Keggin-type phosphotungstate anions and tungsten-based isopolyacid anions are particularly preferred.

[0112] Examples of the compound (A2) include compounds represented by formulae (A2-1) to (A2-52) in Tables 2 and 3 below.

[0113] [Table 2]

[0114] [Table 3]

[0115] As the compound (A2), the compounds represented by formulae (A2-41) to (A2-44) are preferred, and the compound represented by formula (A2-41) is more preferred.

[0116] Compound (A2) can be produced in accordance with the method described in JP-A-2015-28121.

[0117] The content of compound (A1) and / or compound (A2) is preferably 50 to 100 mass%, more preferably 70 to 100 mass%, even more preferably 90 to 100 mass%, even more preferably 95 to 100 mass%, and most preferably 100 mass%, based on 100 mass% of the total solid content of colorant (A). When compound (A1) and compound (A2) are used in combination, this content refers to the total content of these.

[0118] <Xanthene dyes> Xanthene dyes are dyes having a xanthene skeleton in the molecule. The xanthene dye is preferably a dye containing a compound represented by formula (1a) (hereinafter sometimes referred to as "compound (1a)"). Compound (1a) may be a tautomer thereof. When compound (1a) is used, the content of compound (1a) in the xanthene dye is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. It is particularly preferred to use only compound (1a) as the xanthene dye.

[0119] [ka]

[0120] [In formula (1a), R 1 ~R 4 each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and -CH2- contained in the saturated hydrocarbon group is -O-, -CO- or -NR 11 - may be replaced by R 1 and R 2 may be bonded to form a ring together with the adjacent nitrogen atom, and R 3 and R 4 may be bonded to form a ring together with the adjacent nitrogen atom. R5 -OH, -SO3 - , -SO3H, -SO3 - Z + , -CO2H, -CO2 - Z + , -CO2R 8 , -SO3R 8 or -SO2NR 9 R 10 Represents. R 6 and R 7 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m represents an integer of 0 to 5. When m is 2 or more, a plurality of R 5 may be the same or different. a represents an integer of 0 or 1. X represents a halogen atom. Z + teeth, + N(R 11 )4, Na + or K + represents the four R's 11 may be the same or different. R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom. R 9 and R 10 each independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH2- contained in the saturated hydrocarbon group is not -O-, -CO-, -NH- or -NR 8 - may be replaced by R 9 and R 10 may be bonded to form a 3- to 10-membered heterocyclic ring together with the adjacent nitrogen atom. R 11 represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.]

[0121] R 1 ~R 4Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (I) include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and icosyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl. Of these, monovalent saturated hydrocarbon groups having 1 to 10 carbon atoms are preferred, monovalent saturated hydrocarbon groups having 1 to 5 carbon atoms are more preferred, and monovalent saturated hydrocarbon groups having 1 to 3 carbon atoms are even more preferred. R 1 ~R 4 The hydrogen atoms contained in the saturated hydrocarbon group in the formula may be substituted with, for example, a carboxy group, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom. R 1 ~R 4 Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in the formula (I) include a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group. Of these, a toluyl group, a xylyl group, and a mesityl group are preferred, and a xylyl group is more preferred.

[0122] The substituents that the saturated hydrocarbon group or aromatic hydrocarbon group may have include a halogen atom, -R 8 , -OH, -OR 8 , -SO3 - , -SO3H, -SO3 - Z + , -CO2H, -CO2R 8 , -SR 8 , -SO2R 8 , -SO3R 8 and -SO2NR 9 R 10 Among these, the substituents include -CO2H, -SO3 - , -SO3H, -SO3 - Z + and -SO2NR9 R 10 -SO3 is preferred. - Z + As for -SO3 - + N(R 11 )4 is preferred.

[0123] R 1 and R 2 is bonded to form a ring together with the adjacent nitrogen atom, and R 3 and R 4 Examples of the ring formed by bonding with the adjacent nitrogen atom include the following.

[0124] [ka]

[0125] R 8 ~R 11 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (I) include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and icosyl groups; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl groups; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl groups. R 9 and R 10 The substituents which the saturated hydrocarbon group may have in the formula (I) include a hydroxy group and a halogen atom.

[0126] -OR 8 Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, and an icosyloxy group.

[0127] -CO2R8 Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

[0128] -SR 8 Examples of the sulfanyl group include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group. -SO2R 8 Examples of the sulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group. -SO3R 8 Examples of the sulfonyl group include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

[0129] -SO2NR 9 R 10 Examples include a sulfamoyl group; N-Methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N-(1-ethylpropyl)sulfamoyl group, N-(1,1-dimethylpropyl)sulfamoyl group, N-(1,2-dimethylpropyl)sulfamoyl group, N-(2,2-dimethylpropyl)sulfamoyl group, N-(1-methylbutyl)sulfamoyl group, N-(2-methylbutyl)sulfamoyl group N-1-substituted sulfamoyl groups such as a sulfamoyl group, an N-(3-methylbutyl)sulfamoyl group, an N-cyclopentylsulfamoyl group, an N-hexylsulfamoyl group, an N-(1,3-dimethylbutyl)sulfamoyl group, an N-(3,3-dimethylbutyl)sulfamoyl group, an N-heptylsulfamoyl group, an N-(1-methylhexyl)sulfamoyl group, an N-(1,4-dimethylpentyl)sulfamoyl group, an N-octylsulfamoyl group, an N-(2-ethylhexyl)sulfamoyl group, an N-(1,5-dimethyl)hexylsulfamoyl group, and an N-(1,1,2,2-tetramethylbutyl)sulfamoyl group; Examples include N,N-disubstituted sulfamoyl groups such as N,N-dimethylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-propylmethylsulfamoyl group, N,N-isopropylmethylsulfamoyl group, N,N-tert-butylmethylsulfamoyl group, N,N-butylethylsulfamoyl group, N,N-bis(1-methylpropyl)sulfamoyl group and N,N-heptylmethylsulfamoyl group.

[0130] R 5 -CO2H, -CO2 - Z + , -CO2R 8 , -SO3 - , -SO3 - Z + , -SO3H or -SO2NHR 9 is preferred, -SO3 - , -SO3 -Z + , -SO3H or -SO2NHR 9 is more preferred. m is preferably 1 to 4, and more preferably 1 or 2.

[0131] R 6 and R 7 Examples of the alkyl group having 1 to 6 carbon atoms include the alkyl groups listed above, which have 1 to 6 carbon atoms.

[0132] R 11 Examples of the aralkyl group having 7 to 10 carbon atoms in the formula include a benzyl group, a phenylethyl group, and a phenylbutyl group.

[0133] Z + teeth, + N(R 11 )4, Na + or K + and preferably + N(R 11 )4. + N(R 11 ) 4 R's in 4 11 Among the four R, at least two are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. 11 The total number of carbon atoms is preferably 20 to 80, and more preferably 20 to 60.

[0134] Compound (1a) is preferably a compound represented by formula (2a) (hereinafter, sometimes referred to as "compound (2a)"). Compound (2a) may be a tautomer thereof.

[0135] [ka]

[0136] [In formula (2a), R 21 ~R 24 are each independently a hydrogen atom, -R 26a or represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent.21 and R 22 may be bonded to form a ring together with the adjacent nitrogen atom, and R 23 and R 24 may be bonded to form a ring together with the adjacent nitrogen atom. R 25 is -SO3 - , -SO3H, -SO3 - Z1 + or -SO2NHR 26 Represents. m1 represents an integer of 0 to 5. When m1 is 2 or more, a plurality of R 25 may be the same or different. a1 represents an integer of 0 or 1. X1 represents a halogen atom. R 26a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. R 26 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. Z1 + teeth, + N(R 27 )4, Na + or K + represents the four R's 27 may be the same or different. R 27 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group.]

[0137] R 21 ~R 24 The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R 1 ~R 4 The aromatic hydrocarbon group may be the same as the aromatic hydrocarbon group exemplified above. The hydrogen atoms contained in the aromatic hydrocarbon group may be -CO2H, -SO3 - , -SO3H, -SO3 - Z1 + , -SO3R 26 or -SO2NHR 26 may be substituted with. R 26aThe substituents that the saturated hydrocarbon group in 27 , -CO2H, -CO2R 27 and -SR 27 Examples include:

[0138] R 21 and R 22 is bonded to form a ring together with the adjacent nitrogen atom, and R 23 and R 24 The ring formed by bonding with the adjacent nitrogen atom is R 1 and R 2 Examples of the heterocyclic ring include the same rings as those formed by bonding with the adjacent nitrogen atom. Among these, an aliphatic heterocyclic ring is preferred. Examples of the aliphatic heterocyclic ring include the following:

[0139] [ka]

[0140] R 26 and R 27 In the above formula, the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms is R 8 ~R 11 Examples of the saturated hydrocarbon group include the same groups as those exemplified above. R 21 ~R 24 Ga-R 26 If -R 26 are each preferably independently a methyl group or an ethyl group. 26 and -SO2NHR 26 R in 26 As the alkyl group, a branched alkyl group having 3 to 20 carbon atoms is preferable, a branched alkyl group having 6 to 12 carbon atoms is more preferable, and a 2-ethylhexyl group is even more preferable.

[0141] Z1 + teeth, + N(R 27 )4, Na + or K + and preferably + N(R27 )4. The aforementioned + N(R 27 ) 4 R's in 4 27 Among the four R, at least two are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. 27 The total number of carbon atoms is preferably 20 to 80, and more preferably 20 to 60.

[0142] m1 is preferably 1 to 4, and more preferably 1 or 2.

[0143] Compound (1a) is also represented by the formula (2a) and R 21 ~R 24 are each independently a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms, or a compound represented by formula (3a) (hereinafter sometimes referred to as "compound (3a)"). Compound (3a) may be a tautomer thereof.

[0144] [ka]

[0145] [In formula (3a), R 31 and R 32 each independently represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, a hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms, and -CH2- contained in the saturated hydrocarbon group is -O-, -CO- or -NR 11 - may be replaced. R 33 and R 34 each independently represents a carboxy group, an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms. R 31 and R 33may be bonded to form a ring together with the adjacent nitrogen atom and the carbon atom on the benzene ring, and R 32 and R 34 may be bonded to form a ring together with the adjacent nitrogen atom and a carbon atom on the benzene ring. p and q each independently represent an integer of 0 to 5. When p is 2 or more, a plurality of R 33 may be the same or different, and when q is 2 or more, multiple R 34 may be the same or different. R 11 has the same meaning as above.]

[0146] R 31 and R 32 In the above formula, the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is R 8 Among the above, groups having 1 to 10 carbon atoms are exemplified. Two or more -CH2- groups contained in the saturated hydrocarbon group may be replaced consecutively. For example, one -CH2- group may be replaced with -CO- and another adjacent -CH2- group may be replaced with -O- to form -COOH. The aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted includes R 1 The same groups as in Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group. R 31 and R 32 are preferably each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

[0147] R 33 and R 34 Examples of the alkyl group having 1 to 4 carbon atoms in the formula include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. R 33 and R 34Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in the formula include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, and an isopropylsulfanyl group. R 33 and R 34 Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in the formula include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group. R 33 and R 34 is preferably each independently an alkyl group having 1 to 4 carbon atoms, and more preferably both are a methyl group.

[0148] p and q are each preferably an integer of 0 to 2, and more preferably 1 or 2.

[0149] Examples of the compound (1a) include compounds represented by formulas (1-1) to (1-70). 40 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group.

[0150] [ka]

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[0169] [ka]

[0170] Among the above compounds, the compounds represented by formulas (1-1) to (1-23) or (1-37) to (1-63) correspond to compound (2a), and the compounds represented by formulas (1-24) to (1-36) or (1-64) to (1-70) correspond to compound (3a). Among these, the compounds represented by any one of formulas (1-24) to (1-33), formulas (1-37) to (1-63), and formulas (1-64) to (1-70) are preferred, and the compounds represented by any one of formulas (1-24) to (1-33) are more preferred.

[0171] As the xanthene dye, commercially available xanthene dyes (for example, "Chugai Aminol Fast Pink RH / C" manufactured by Chugai Chemical Industry Co., Ltd. and "Rhodamin 6G" manufactured by Taoka Chemical Co., Ltd.) can be used. Alternatively, a xanthene dye can be synthesized using a commercially available xanthene dye as a starting material with reference to JP-A-2010-32999.

[0172] The content of compound (1a) is preferably 50 to 100 mass%, more preferably 70 to 100 mass%, even more preferably 90 to 100 mass%, even more preferably 95 to 100 mass%, and most preferably 100 mass%, based on 100 mass% of the total solid content of colorant (A).

[0173] In producing the curable coloring composition of the present invention, it is preferable to prepare a colorant dispersion by dispersing a salt-forming compound in a solvent. The colorant dispersion can be mixed with a resin (B), a silicone compound (C), a polymerizable compound (D), a polymerization initiator (E), etc. to prepare a colored resin composition. Alternatively, the colored resin composition may be prepared by mixing a dye with a resin (B), a silicone compound (C), a polymerizable compound (D), a polymerization initiator (E), etc. without preparing a colorant dispersion.

[0174] As the solvent for preparing the colorant dispersion, any solvent that can be used as the solvent (G) for a colored resin composition can be used. Examples of the solvent include the ether ester solvents and ketone solvents described below. The content of the solvent in the colorant dispersion is, for example, 1 to 50 parts by mass, preferably 2 to 30 parts by mass, and more preferably 3 to 15 parts by mass, per part by mass of the salt-forming compound.

[0175] When preparing a colorant dispersion by dispersing a salt-forming compound in a solvent, it is preferable to use a dispersant. Examples of dispersants include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These dispersants may be used alone or in combination of two or more. Examples of dispersants include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flourene (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Corporation), EFKA (manufactured by BASF), and Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.).

[0176] The content of the dispersant in the colorant dispersion liquid is, for example, 1 to 1000 parts by mass, preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass, and particularly preferably 10 to 50 parts by mass, relative to 100 parts by mass of the salt-forming compound.

[0177] The colorant dispersion may contain a resin. Examples of the resin include the resin (B) described below. When the colorant dispersion contains the resin (B), the content of the resin (B) is preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 15% by mass or less, more preferably 7% by mass or less, based on the total amount of the colorant dispersion. When the content of the resin (B) is within the above range, the dispersion state tends to be stable.

[0178] The content of the salt-forming compound is preferably 50 to 100 mass%, more preferably 70 to 100 mass%, even more preferably 90 to 100 mass%, still more preferably 95 to 100 mass%, and most preferably 100 mass%, relative to 100 mass% of the total solid content of the colorant (A).

[0179] The curable coloring composition of the present invention may contain, as the colorant (A), a dye (hereinafter sometimes referred to as dye (AA)) and / or a pigment (hereinafter sometimes referred to as pigment (AB)) other than the above-mentioned salt-forming compound. The colorant (A) preferably contains a salt-forming compound and / or a dye (AA), more preferably contains a salt-forming compound. These are easily reacted with by the silicone compound (C).

[0180] The content of the salt-forming compound and / or dye (AA) is preferably 50 to 100 mass%, more preferably 70 to 100 mass%, even more preferably 90 to 100 mass%, even more preferably 95 to 100 mass%, and most preferably 100 mass%, based on 100 mass% of the total solid content of the colorant (A). When the salt-forming compound and the dye (AA) are used in combination, this content is the total content of these.

[0181] The dye (AA) is not particularly limited and known dyes can be used, such as solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of the dye (AA) include compounds classified as having a hue other than pigments in the Color Index (published by The Society of Dyers and Colourists) and known dyes listed in Dyeing Notes (Shikisensha). Further, based on chemical structure, examples include azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Among these, organic solvent-soluble dyes are preferred.

[0182] The pigment (AB) is not particularly limited and any known pigment can be used, and examples thereof include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists). Examples of pigments (AB) include yellow pigments such as CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, and 214; Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; Blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60; CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 etc. Olet color pigment; Green pigments such as CI Pigment Green 7, 36, and 58; Brown pigments such as CI Pigment Brown 23 and 25; Examples include black pigments such as CI Pigment Black 1 and 7.

[0183] Among these, blue pigments and violet pigments are preferred, and blue pigments are more preferred.

[0184] When the curable coloring composition contains the pigment (AB), the content of the pigment (AB) is preferably 1 to 50 mass%, more preferably 1 to 20 mass%, and even more preferably 1 to 10 mass%, relative to 100 mass% of the total solid content of the colorant (A).

[0185] The pigment may be subjected, as necessary, to a rosin treatment, a surface treatment using a pigment derivative into which an acidic group or a basic group has been introduced, a graft treatment onto the pigment surface using a polymer compound or the like, a microparticle treatment using a sulfuric acid microparticle method or the like, a washing treatment using an organic solvent, water or the like to remove impurities, a treatment to remove ionic impurities using an ion exchange method or the like, or the like.

[0186] The pigment preferably has a uniform particle size, and by adding a pigment dispersant and carrying out a dispersion treatment, it is possible to obtain a pigment dispersion in which the pigment is uniformly dispersed in the solution.

[0187] Examples of the pigment dispersant include the same dispersants as those that can be used when preparing a colorant dispersion by dispersing the above-mentioned salt-forming compound in a solvent. The content of the pigment dispersant in the pigment dispersion is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less, based on the total amount of pigment. When the content of the pigment dispersant is within this range, a pigment dispersion in a uniformly dispersed state tends to be obtained.

[0188] The solid content of the colorant (A) in the curable coloring composition is preferably 2 to 60 mass %, more preferably 5 to 50 mass %, and even more preferably 8 to 40 mass %, of the total amount of solids. When the content of the colorant (A) is within the above range, the color density when made into a color filter is sufficient, and since the composition can contain the necessary amounts of resin and polymerizable compound, a pattern with sufficient mechanical strength can be formed.

[0189] Here, the "total amount of solids" in this specification refers to the amount obtained by subtracting the content of the solvent from the total amount of the colored resin composition. The total amount of solids and the content of each component can be measured by known analytical means such as liquid chromatography or gas chromatography.

[0190] <Resin (B)> Resin (B) is preferably an alkali-soluble resin, and more preferably a resin having a structural unit derived from at least one monomer (a) (hereinafter sometimes referred to as "monomer (a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. Resin (B) preferably has at least one structural unit selected from the group consisting of a structural unit derived from monomer (a), a structural unit derived from monomer (b) (hereinafter sometimes referred to as "monomer (b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond, a structural unit derived from monomer (c) (however different from monomer (a) and monomer (b)) (hereinafter sometimes referred to as "monomer (c)") copolymerizable with monomer (a), and a structural unit having an ethylenically unsaturated bond in its side chain; more preferably has at least one structural unit selected from the group consisting of structural units derived from monomer (a), structural units derived from monomer (b), and structural units derived from monomer (c); and even more preferably has structural units derived from monomer (a), structural units derived from monomer (b), and structural units derived from monomer (c).

[0191] Specific examples of the monomer (a) include acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, and mono[2-(meth)acryloyloxyethyl]succinate. Preferred are acrylic acid, methacrylic acid, and maleic anhydride, more preferred are acrylic acid and methacrylic acid, and even more preferred is acrylic acid.

[0192] The structural units derived from monomer (a) account for, for example, 2 parts by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and for example, 40 parts by mass or less, preferably 30 parts by mass or less, more preferably 25 parts by mass or less, of 100 parts by mass of all structural units.

[0193] The monomer (b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and a (meth)acryloyloxy group. In this specification, "(meth)acrylic acid" refers to at least one selected from the group consisting of acrylic acid and methacrylic acid. The terms "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

[0194] Examples of the monomer (b) include glycidyl (meth)acrylate, vinylbenzyl glycidyl ether, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl(meth)acrylate, 3-ethyl-3-(meth)acryloyloxymethyloxetane, tetrahydrofurfuryl(meth)acrylate, etc., and preferred are glycidyl(meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl(meth)acrylate, 3-ethyl-3-(meth)acryloyloxymethyloxetane, more preferably glycidyl(meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl (meth)acrylate, and more preferably 3,4-epoxytricyclo[5.2.1.0 2,6]decyl (meth)acrylate.

[0195] The amount of the structural units derived from monomer (b) is, for example, 1 part by mass or more, preferably 5 parts by mass or more, more preferably 7 parts by mass or more, and for example, 30 parts by mass or less, preferably 25 parts by mass or less, more preferably 20 parts by mass or less, per 100 parts by mass of all structural units.

[0196] Examples of the monomer (c) include methyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 Examples of suitable styrene-based monomers include (meth)acrylates such as decan-8-yl (meth)acrylate, benzyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate; maleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide; and styrene-based monomers such as styrene and vinyltoluene. Among these, preferred are styrene, vinyltoluene, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide, more preferred are 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, and N-cyclohexylmaleimide, and even more preferred are 2-hydroxyethyl (meth)acrylate and N-cyclohexylmaleimide. (Meth)acrylates, maleimides, and styrene-based monomers may be used in combination, with a combination of (meth)acrylates and maleimides being preferred.

[0197] The structural units derived from monomer (c) account for, for example, 30 parts by mass or more, preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and for example, 95 parts by mass or less, preferably 90 parts by mass or less, more preferably 80 parts by mass or less, of 100 parts by mass of all structural units.

[0198] The structural unit having an ethylenically unsaturated bond in the side chain can be constructed by adding a monomer (b) to a copolymer structure of a monomer (a) and a monomer (c), by adding a monomer (a) to a copolymer structure of a monomer (b) and a monomer (c), or by adding a monomer (a) to a copolymer structure of a monomer (b) and a monomer (c) and then reacting with a carboxylic acid anhydride.

[0199] The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000.

[0200] The polydispersity of the resin (B) [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably 1.1-6, and more preferably 1.2-4.

[0201] The acid value of the resin (B) is preferably 20 to 170 mg-KOH / g, more preferably 30 to 150 mg-KOH / g, and even more preferably 40 to 135 mg-KOH / g, calculated as solid content. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be determined, for example, by titration with an aqueous potassium hydroxide solution.

[0202] The resin (B) (solid content) is preferably 5 to 70 mass %, more preferably 10 to 50 mass %, and even more preferably 12 to 40 mass %, based on 100 mass % of the total solid content of the curable coloring composition.

[0203] <Silicone Compound (C)> The silicone compound (C) satisfies the condition (1) (hereinafter, may be referred to as silicone compound (C1)). <Condition (1)> A mixture (H) containing a resin (B-1) having a structural unit of formula (1), a silicone compound (C), a leveling agent (F), and a solvent (G), in which the content of the silicone compound (C) is 21% by mass based on 100% by mass of the total solid content, is spin-coated onto a glass substrate and baked at 230°C for 20 minutes to form a coating film, which has a contact angle of 70° or more with ion-exchanged water. When forming the coating film, the thickness may be adjusted to be 0.5 μm or more and 4 μm or less.

[0204] [ka]

[0205] The contact angle between the coating film and ion-exchanged water in accordance with condition (1) varies depending on the surface tension of the ion-exchanged water and the surface roughness of the coating film, and therefore there is a correlation between the contact angle and the arithmetic mean roughness Ra of the coating film surface. Therefore, by using a silicone compound (C1) capable of forming a coating film with a contact angle of 70° or more in accordance with condition (1), the surface roughness of the resulting cured film can be reduced. As described above, condition (1) is a condition for the silicone compound (C1) in relation to the mixture (H). By setting condition (1) in relation to the mixture (H), it is possible to more easily control the surface roughness of the resulting cured film than by setting the condition for the silicone compound (C) alone. Specifically, by using a silicone compound (C1) that satisfies condition (1), it is possible to reduce the occurrence of surface irregularities associated with the elution of the colorant into the developer, particularly during the development process.

[0206] The contact angle of condition (1) is preferably 73° or more, more preferably 80° or more, even more preferably 86° or more, and even more preferably 95° or more, and is preferably 120° or less, more preferably 110° or less, and even more preferably 100° or less.

[0207] In condition (1), in 100% by mass of mixture (H), the content of resin (B-1) is preferably 11 to 13% by mass, and more preferably 12% by mass, the content of silicone compound (C) is preferably 2 to 4% by mass, and more preferably 3% by mass, the content of leveling agent (F) is preferably 0.01 to 0.03% by mass, and more preferably 0.02% by mass, and the content of solvent (G) is preferably 84 to 86% by mass, and more preferably 85% by mass.

[0208] In the condition (1), the resin (B-1) may be any of the above-mentioned resins (B) having a structural unit of formula (1). The leveling agent (F) and the solvent (G) may be the leveling agent (F) and the solvent (G) described below.

[0209] The silicone compound (C1) may be a silicone compound (C) having a structural unit of formula (2), and preferably a polyether-modified polymethylalkylsiloxane. Specific examples include BYK-320, BYK-325N, BYK-330, and BYK-378 manufactured by BYK-Chemie Japan Co., Ltd.

[0210] [ka]

[0211] [In formula (2), R a1 , R a2 each independently represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, R ax each independently represents a saturated hydrocarbon group having 2 to 30 carbon atoms which may have a substituent, in which at least some of the -CH2- contained in the saturated hydrocarbon group are replaced with -O- or -COO-, but not all of the -CH2- are replaced with -O- or -COO-; R ay each independently represents a saturated hydrocarbon group having 1 to 20 carbon atoms, m and n are the —O—Si(Ra1 )(R ax )- and -O-Si(R a2 )(R ay )- represents the molar ratio. * represents a bond. However, it does not form a Si-Si bond, and it does not form an OO bond.]

[0212] R a1 , R a2 The saturated hydrocarbon group having 1 to 10 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, but is preferably linear. Examples of linear or branched saturated hydrocarbon groups include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, and decyl; and branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl. The saturated hydrocarbon group preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, even more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom. When a plurality of R a1 If there are multiple R a1 may be the same group or different groups, but are preferably the same group. a2 If there are multiple R a2 may be the same group or different groups, but are preferably the same group.

[0213] R ax The saturated hydrocarbon group having 2 to 30 carbon atoms and represented by the formula (I) and optionally having a substituent may be linear, branched or cyclic, but is preferably branched. a1 The saturated hydrocarbon group preferably has 1 to 25 carbon atoms, more preferably 3 to 20 carbon atoms, even more preferably 4 to 15 carbon atoms, and even more preferably 5 to 12 carbon atoms. Furthermore, R ax At least some of the -CH2- groups contained in the saturated hydrocarbon group represented by R are replaced with -O- or -COO-, and are preferably replaced with -O-. axAt least some of the -CH2- groups contained in the saturated hydrocarbon group represented by the formula (I) may be replaced with a divalent group other than -O- or -COO-. The number of carbon atoms is the number of carbon atoms after the replacement. ax Specific examples of R include a group having an oxyalkylene unit with 2 to 5 carbon atoms, a group containing polyester, etc. The number of carbon atoms in the oxyalkylene unit is preferably 2 to 4, more preferably 2 to 3. ax may be a group having a polyoxyalkylene in which two or more oxyalkylene units are consecutive. The number of repeating oxyalkylene units is preferably 2 to 8, more preferably 2 to 5, and even more preferably 2 to 3. In addition, R ax The saturated hydrocarbon group represented by may have a substituent. Examples of the substituent include -OH or -COOH, and -OH is preferred. The saturated hydrocarbon group preferably has a substituent at its terminal. In addition, when a plurality of R ax If there are multiple R ax may be the same group or different groups.

[0214] R ax Specific examples of the group include groups represented by the following formula (3).

[0215] [ka] [In formula (3), R x1 represents a hydrogen atom or a saturated hydrocarbon group having one carbon atom, R x2 represents a hydrogen atom or a saturated hydrocarbon group having 1 to 3 carbon atoms, p represents an integer of 0 to 6; q represents an integer of 1 to 7. * represents a bond.]

[0216] R x1 An example of the saturated hydrocarbon group having one carbon atom represented by the formula (1) is a methyl group. When q is 2 or more, a plurality of R x1may be the same group or different groups. When they are different groups, multiple R x1 A preferred combination is a combination of a hydrogen atom and a saturated hydrocarbon group having one carbon atom.

[0217] R x2 The saturated hydrocarbon group having 1 to 3 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, but is preferably linear. x1 The same groups as those shown in R x2 is preferably a hydrogen atom or a saturated hydrocarbon group having one carbon atom, and more preferably a hydrogen atom.

[0218] p is preferably 0 to 4, more preferably 0 to 2, even more preferably 0 to 1, and particularly preferably 0. q is preferably 1 to 6, more preferably 1 to 4, even more preferably 2 or 3, and particularly preferably 2.

[0219] In formula (2), R ay The saturated hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, but is preferably linear. Examples of linear or branched saturated hydrocarbon groups include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and icosyl; and branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl. The saturated hydrocarbon group preferably has 2 to 18 carbon atoms, more preferably 3 to 12 carbon atoms, even more preferably 6 to 10 carbon atoms, and particularly preferably 8 carbon atoms. Furthermore, R ay The number of carbon atoms in R a2 It is preferable that the number of carbon atoms in the R ay If there are multiple R ay may be the same group or different groups, but are preferably the same group.

[0220] In formula (2), m:n is 1-2:1-4, preferably 1:1-3, more preferably 1:1-2, and even more preferably 1:2. It is also preferable that n is larger than m. In addition, -O-Si(R a1 )(R ax The -O-Si(R)- units may be consecutive or discontinuous. a2 )(R ax The —O—Si(R )- units may be present consecutively or discontinuously. Of the structural units constituting the silicone compound (C1), the —O—Si(R )- units are present in a proportion of 100 mol % of all structural units excluding the terminal groups. a1 )(R ax )- and -O-Si(R a2 )(R ax The total of the structural units of )- is preferably 50 mol % or more, more preferably 70 mol % or more, even more preferably 80 mol % or more, and even more preferably 90 mol % or more.

[0221] The silicone compound (C1) preferably has a group represented by the following formula (4) at one end and a group represented by the following formula (5) at the other end.

[0222] [ka]

[0223] [In formulas (4) and (5), R a3 ~R a8 Each of the groups represented by the following formula (I) independently represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, and * represents a bond. However, they do not form an Si-Si bond, and they do not form an OO bond.]

[0224] R a3 ~R a8 is preferably a saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 3 carbon atoms, and even more preferably a saturated hydrocarbon group having 1 carbon atom. a1 , R a2Examples of the saturated hydrocarbon groups include the same groups as

[0225] The number average molecular weight of the silicone compound (C) is preferably 500 or more, and preferably 30,000 or less, more preferably 15,000 or less.

[0226] The content of the silicone compound (C) relative to the total amount of the curable coloring composition is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, even more preferably 0.3% by mass or less, and even more preferably 0.1% by mass or less. On the other hand, when the content of the silicone compound (C) is 0.001% by mass or more, the surface roughness of the cured film is reduced. It is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.008% by mass or more. The content of the silicone compound (C) is preferably 0.1 to 2.0 parts by mass, more preferably 0.2 to 1.0 parts by mass, and even more preferably 0.3 to 0.8 parts by mass relative to 100 parts by mass of the solid content of the colorant (A) in the curable coloring composition.

[0227] <Polymerizable compound (D)> The polymerizable compound (D) is a compound that can be polymerized by active radicals and / or acids generated from the polymerization initiator (E), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and are preferably (meth)acrylic acid ester compounds.

[0228] Among these, the polymerizable compound (D) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0229] The weight average molecular weight of the polymerizable compound (D) is preferably 150 or more and 2,900 or less, more preferably 250 or more and 1,500 or less.

[0230] The content of the polymerizable compound (D) is preferably 5 to 65 mass%, more preferably 15 to 60 mass%, and even more preferably 20 to 50 mass%, relative to 100 mass% of the total solid content of the curable coloring composition.

[0231] <Polymerization initiator (E)> The polymerization initiator (E) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. by the action of light or heat and initiate polymerization, and known polymerization initiators can be used. Examples of polymerization initiators that generate active radicals include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, and N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine. amine, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and the like.

[0232] The content of the polymerization initiator (E) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (D). When the content of the polymerization initiator (E) is within the above range, sensitivity tends to be increased and exposure time tends to be shortened, thereby improving productivity of the color filter.

[0233] <Polymerization initiator aid (E1)> The curable coloring composition of the present invention may contain a polymerization initiation aid (E1). The polymerization initiation aid (E1) is a compound used to promote the polymerization of a polymerizable compound whose polymerization has been initiated by a polymerization initiator, or a sensitizer. Examples of the polymerization initiation aid (E1) include 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone, and N-phenylglycine.

[0234] When these polymerization initiation aids (E1) are used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (D). When the content of the polymerization initiation aid (E1) is within this range, a color filter can be formed with even higher sensitivity, and the productivity of the color filter tends to improve.

[0235] <Leveling Agent (F)> The curable coloring composition preferably contains a leveling agent (F). Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms. Among these, fluorine surfactants are preferred. These may have a polymerizable group in the side chain.

[0236] Examples of silicone surfactants include surfactants having a siloxane bond in the molecule. Specific examples include Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (trade names: manufactured by Toray Dow Corning Co., Ltd.); KP321, KP322, KP323, KP324, KP326, KP340, and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); and TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan, LLC). Silicone surfactants do not include silicone compounds (C).

[0237] Examples of fluorine-based surfactants include surfactants having a fluorocarbon chain in the molecule, such as Fluorad (registered trademark) FC430 and FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, and RS-718-K (manufactured by DIC Corporation), F-Top (registered trademark) EF301, EF303, EF351, and EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, and SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Research Institute, Inc.).

[0238] Examples of silicone surfactants having fluorine atoms include surfactants having a siloxane bond and a fluorocarbon chain in the molecule, such as Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

[0239] When the leveling agent (F) is contained, the content of the leveling agent (F) is preferably 0.001 to 0.2 mass %, more preferably 0.005 to 0.1 mass %, of the total amount of the curable coloring composition. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

[0240] <Solvent (G)> The curable coloring composition preferably contains a solvent (G). The solvent (G) is not particularly limited, and a solvent commonly used in the field can be used. For example, ester solvents (solvents containing -COO- in the molecule but not containing -O-), ether solvents (solvents containing -O- in the molecule but not containing -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule but not containing -COO-), alcohol solvents (solvents containing OH in the molecule but not containing -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc. can be mentioned.

[0241] The solvent (G) may be: Ester solvents such as ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone (solvents that contain -COO- but not -O- in the molecule); Ether solvents such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether (solvents containing -O- but not -COO- in the molecule); ether ester solvents (solvents containing -COO- and -O- in the molecule) such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methoxypropyl acetate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and diethylene glycol monoethyl ether acetate; Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), heptanone, 4-methyl-2-pentanone, and cyclohexanone (solvents that contain -CO- but not -COO- in the molecule); Alcohol solvents such as butanol, cyclohexanol, and propylene glycol (solvents that contain OH in the molecule but do not contain -O-, -CO-, or -COO-); Preferred examples include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; and the like.

[0242] The solvent (G) is preferably an ester solvent, an ether solvent, an ether ester solvent, or a ketone solvent. Specifically, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, or methoxypropyl acetate is more preferred. The solvent (G) more preferably further contains ethyl lactate, 4-hydroxy-4-methyl-2-pentanone, or the like.

[0243] When the solvent (G) is contained, the content of the solvent (G) is preferably 30 to 95 mass%, more preferably 40 to 80 mass%, and even more preferably 45 to 70 mass% of the total amount of the curable coloring composition of the present invention. On the other hand, the total amount of the solid content of the curable coloring composition is preferably 5 to 30 mass%, more preferably 10 to 20 mass%, of the total amount (100 mass%) of the curable coloring composition of the present invention. When the content of the solvent (G) is within the above range, the flatness during application is good, and when a color filter is formed, the color density is not insufficient, so the display characteristics tend to be good.

[0244] <Other ingredients> The curable colored composition of the present invention may contain additives known in the technical field, such as fillers, polymeric compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents, as needed.

[0245] The curable coloring composition of the present invention is preferably capable of forming a cured film having an arithmetic mean roughness Ra of 6.0 or less. By ensuring that the arithmetic mean roughness Ra of the surface of the cured film is 6.0 or less, unevenness in brightness can be reduced. Furthermore, a high Ra on the surface of the cured film can lead to defects in the ITO vapor deposition process, but ensuring that Ra is 6.0 or less can reduce the occurrence of such defects. Ra is preferably 5.0 or less, more preferably 4.5 or less. On the other hand, the lower limit of Ra may be 0.1 or more, 0.5 or more, or 1.0 or more.

[0246] <Color filters, display devices> The present invention also includes a cured film, such as a color filter, formed from the curable coloring composition. Such a color filter has reduced surface roughness, which reduces unevenness in brightness. Furthermore, an Ra of 6.0 or less reduces the occurrence of defects in the ITO vapor deposition process. The color filter is useful as a filter for use in display devices (e.g., liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

[0247] <Method of producing curable colored composition> The curable colored composition of the present invention can be prepared by mixing the colorant (A), the resin (B), the silicone compound (C), the polymerizable compound (D), the polymerization initiator (E), and optionally the polymerization initiation aid (E1), the leveling agent (F), the solvent (G), and other components.

[0248] The colorant (A) may be prepared using the above-mentioned colorant dispersion or pigment dispersion. The desired colored resin composition can be prepared by mixing the remaining components with the colorant dispersion or pigment dispersion to a predetermined concentration.

[0249] <Color filter manufacturing method> Methods for producing a colored pattern (color filter) from the curable colored composition of the present invention include photolithography, inkjet printing, and printing. Among these, photolithography is preferred. The photolithography is a method in which the curable colored composition is applied to a substrate, dried to form a composition layer, and then exposed to light through a photomask and developed. In the photolithography, a colored coating film, which is a cured product of the colored composition layer, can be formed by not using a photomask during exposure and / or not developing. The colored pattern or colored coating film thus formed is an example of a color filter.

[0250] The thickness of the color filter (cured film) is preferably 20 μm or less, more preferably 6 μm or less, even more preferably 3 μm or less, and preferably 0.1 μm or more, more preferably 1.0 μm or more, even more preferably 1.5 μm or more.

[0251] The substrate may be a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, or silica-coated soda lime glass; a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate; silicon; or a substrate having a thin film of aluminum, silver, or a silver / copper / palladium alloy formed thereon. A separate color filter layer, a resin layer, a transistor, a circuit, or the like may be formed on these substrates. Alternatively, a silicon substrate treated with HMDS may be used.

[0252] Formation of each color pixel by photolithography can be carried out using known or conventional equipment and conditions. For example, it can be produced as follows. First, a curable coloring composition is applied to a substrate, and volatile components such as solvents are removed by heat drying (pre-baking) and / or vacuum drying to obtain a smooth composition layer. Examples of application methods include spin coating, slit coating, and slit and spin coating. When heat drying is performed, the temperature is preferably 30 to 120°C, more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. When vacuum drying is performed, it is preferably performed under a pressure of 50 to 150 Pa at a temperature in the range of 20 to 25°C. The film thickness of the composition layer is not particularly limited and may be appropriately selected depending on the film thickness of the desired color filter.

[0253] Next, the composition layer is exposed through a photomask to form a desired color pattern. The pattern on the photomask is not particularly limited, and a pattern appropriate for the intended application is used. The light source used for exposure is preferably a light source that emits light with a wavelength of 250 to 450 nm. For example, light less than 350 nm may be cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, and 365 nm may be selectively extracted using a bandpass filter that extracts these wavelength ranges. Specific examples include mercury lamps, light-emitting diodes, metal halide lamps, and halogen lamps. It is preferable to use a reduction projection exposure device or proximity exposure device such as a mask aligner or stepper, as this allows for uniform irradiation of the entire exposure surface with parallel light and allows for accurate alignment of the photomask and substrate.

[0254] A colored pattern is formed on the substrate by bringing the exposed composition layer into contact with a developer and developing it. The unexposed portions of the composition layer are dissolved and removed by development. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. The developer may further contain a surfactant. The development method may be any of a puddle method, a dipping method, a spray method, or the like. Furthermore, the substrate may be tilted at any angle during development. After development, the substrate is preferably washed with water.

[0255] Furthermore, it is preferable to post-bake the obtained colored pattern. The post-bake temperature is preferably 80 to 250° C., more preferably 100 to 245° C. The post-bake time is preferably 1 to 120 minutes, more preferably 2 to 30 minutes. [Example]

[0256] The present invention will be explained in more detail below with reference to examples. However, the present invention is not limited to the following examples, and can be practiced with appropriate modifications within the scope of the above and below-mentioned spirit, all of which are included in the technical scope of the present invention. In the examples, "%" and "parts" refer to mass % and mass parts unless otherwise specified. The structures of the compounds were identified by mass spectrometry (LC: Agilent 1200 model, MASS: Agilent LC / MSD model).

[0257] Production example 1: Resin (B-1) A flask equipped with a reflux condenser, a dropping funnel, and a stirrer was filled with nitrogen to replace the atmosphere, and 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added and heated to 85°C with stirring. Next, 38 parts of acrylic acid and 3,4-epoxytricyclo[5.2.1.0] were added. 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6A mixed solution of 25 parts of a mixture of decan-9-yl acrylate (content ratio 1:1 by molar ratio), 137 parts of N-cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate, and 338 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. Meanwhile, a solution of 5 parts of 2,2-azobisisobutyronitrile dissolved in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was maintained at 85°C for 4 hours and then cooled to room temperature to obtain a copolymer (Resin B-1) solution with a viscosity of 23 mPas measured with a Brookfield viscometer (23°C) and a solids content of 25.6% by mass. The weight-average molecular weight Mw of the resulting copolymer was 8.0 x 10 3 The resin B-1 had a polydispersity of 2.1 and an acid value of 109 mg-KOH / g in terms of solid content.

[0258] [ka]

[0259] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin B-1 obtained in Production Example 1 were measured using GPC under the following conditions. Equipment: K2479 (Shimadzu Corporation) Column: SHIMADZU Shim-pack GPC-80M Column temperature: 40°C Solvent: THF (tetrahydrofuran) Flow rate; 1.0mL / min Detector: RI Calibration standard material; TSK STANDARD POLYSTYRENE F-40, F-4, F-228, A-2500, A-500 (manufactured by Tosoh Corporation) The ratio of the weight average molecular weight and the number average molecular weight (Mw / Mn) calculated in terms of polystyrene obtained above was taken as the molecular weight distribution.

[0260] Production Example 2: Production of compound (1a-1) represented by formula (1a-1) Compound (1a-1) represented by the following formula (1a-1) was produced in the same manner as in Example 7 of JP 2018-127596 A.

[0261] [ka]

[0262] Production Example 3: Production of Resin (B-2) The atmosphere in a flask equipped with a reflux condenser, a dropping funnel, and a stirrer was replaced with nitrogen, and 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added and heated to 85°C with stirring. Next, 38 parts of acrylic acid and 3,4-epoxytricyclo[5.2.1.0] 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6 A mixed solution of 25 parts of a mixture of decan-9-yl acrylate, 137 parts of N-cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate, and 338 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. Meanwhile, a solution of 5 parts of 2,2-azobisisobutyronitrile dissolved in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the addition was completed, the mixture was held at 85°C for 4 hours and then cooled to room temperature to obtain a copolymer (hereinafter referred to as "Resin (B-2)") solution (solid content 25.6%). The viscosity of the Resin (B-2) solution measured at 23°C using a Brookfield viscometer was 23 mPa·s. The acid value (solid content equivalent) of Resin (B-2) was 111 mgKOH / g, and its weight-average molecular weight (Mw) was 8.0×10 3 The polydispersity (Mw / Mn) was 2.1.

[0263] Production Example 4: Production of colorant dispersion (A-1) containing compound (1a-1) 7 parts of compound (1a-1), 3 parts of dispersant (DISPERBYK®-2050 (BYK Japan)), 3 parts of resin (B-2) (solids content equivalent), 81 parts of propylene glycol monomethyl ether acetate, 6 parts of 4-hydroxy-4-methyl-2-pentanone, and 300 parts of 0.2 mm zirconia beads were mixed and shaken for 3 hours using a paint conditioner (LAU). The zirconia beads were then removed by filtration to obtain colorant dispersion (A-1).

[0264] Production Example 5: Production of compound (1a-2) represented by formula (1a-2) A compound (1a-2) represented by the following formula (1a-2) was produced by the method described in Synthesis Example 2 of JP 2016-176075 A.

[0265] [ka]

[0266] <Production of Mixture (H)> Mixtures (H-1) to (H-5) were obtained by mixing the following resin (B), silicone compound (C), leveling agent (F), and solvent (G) to obtain the compositions shown in Table 4. In Table 4, the values ​​for resin (B) and silicone compound (C) are calculated as solid contents.

[0267] <Resin (B)> (B-1): Resin (B-1) obtained in Production Example 1

[0268] <Silicone Compound (C)> (C-1): BYK-320 (manufactured by BYK Japan Co., Ltd.) (C-2): BYK-325N (manufactured by BYK Japan Co., Ltd.) (C-3): BYK-330 (manufactured by BYK Japan Co., Ltd.) (C-4): BYK-378 (manufactured by BYK Japan Co., Ltd.) (C-5): Toray Silicone SH8400 (manufactured by Toray Dow Corning Co., Ltd.)

[0269] <Leveling Agent (F)> (F-1): Fluorine-based surfactant (Megafac (registered trademark) F554; manufactured by DIC Corporation)

[0270] <Solvent (G)> (G-1): Propylene glycol monomethyl ether acetate (G-2): Methoxypropyl acetate (G-3): Ethyl lactate (G-4): 4-hydroxy-4-methyl-2-pentanone

[0271] <Formation of coating film of mixture (H)> The obtained mixture (H) was applied to a 2-inch square glass substrate (Eagle 2000; Corning) by spin coating to a thickness of 2 μm, and baked in an oven at 230°C for 20 minutes to obtain coating films formed from mixtures (H-1) to (H-5), respectively.

[0272] <Contact angle measurement> The contact angles of the coating films of the resulting mixtures (H-1) to (H-5) with ion-exchanged water were measured by the sessile drop method using a contact angle measuring device (PCA-1; manufactured by Kyowa Interface Science Co., Ltd.) The results of the static contact angles when a droplet with a diameter of 2 μm was dropped onto the coating film at room temperature of 23°C are shown in Table 4.

[0273] [Table 4]

[0274] As shown in Table 4, the coating films formed from mixtures (H-1) to (H-4) containing silicone compounds (C-1) to (C-4) had a contact angle of 70° or more between the coating film and ion-exchanged water, satisfying condition (1). On the other hand, when mixture (H-5) containing silicone compound (C-5) was used, aggregation occurred and a coating film could not be formed.

[0275] <Examples 1 to 7, Comparative Example 1> A curable colored composition was obtained by mixing the following colorant dispersion, colorant, resin (B), silicone compound (C), polymerizable compound (D), polymerization initiator (E), leveling agent (F), and solvent (G) to obtain the composition shown in Table 5. In Table 5, the values ​​for resin (B) and silicone compound (C) are values ​​converted into solid content.

[0276] <Colorant dispersion> Colorant dispersion (A-1) containing compound (1a-1)

[0277] <Coloring agent> Colorant (A-2) consisting of compound (1a-2)

[0278] <Polymerizable compound (D)> (D-1): Dipentaerythritol hexaacrylate ("KAYARAD (registered trademark) DPHA" manufactured by Nippon Kayaku Co., Ltd.)

[0279] <Polymerization initiator (E)> (E-1): A compound represented by the following formula (D-1) ("TR-PBG327" manufactured by Changzhou Strong Electronic New Materials Co., Ltd.)

[0280] [ka]

[0281] <Formation of hardened film> Each of the obtained curable colored compositions was applied by spin coating onto a 2-inch square glass substrate (Eagle 2000; manufactured by Corning Incorporated), and then prebaked at 100°C for 3 minutes to form a composition layer. After cooling, the composition was exposed to 60 mJ / cm2 under atmospheric conditions using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). 2The composition layer was irradiated with light at an exposure dose (365 nm standard) of 1000 kJ / cm2. The colored resin composition layer after light irradiation was immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24°C for 60 seconds, washed with water, and then post-baked in an oven at 230°C for 20 minutes to obtain a cured film.

[0282] <Film thickness measurement> The thickness of the resulting cured film was measured using a film thickness measuring device (DEKTAK3, manufactured by Nippon Shinku Gijutsu Co., Ltd.).

[0283] <Color evaluation> The resulting cured film was subjected to spectral measurement using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity coordinates (x, y) and Y in the CIE XYZ color system were measured using the characteristic function of illuminant C. A larger Y value indicates higher lightness.

[0284] <Contrast evaluation> The same procedure as for forming the cured film was carried out except that no development was carried out, to prepare a cured film on a glass substrate. The contrast of the cured film was measured using a contrast colorimeter (CT-1; manufactured by Tsubosaka Electric Co., Ltd., detector: BM-5A, light source: F-10) with a blank value of 30,000. The cured film on the glass substrate was sandwiched between polarizing films (POLAX-38S; manufactured by Luceo Co., Ltd.) to prepare a measurement sample.

[0285] <Evaluation of surface roughness of cured film> The arithmetic mean roughness Ra (nm) of the surface of the obtained cured film was measured using a scanning probe microscope (SPM; Dimension Icon, manufactured by Bruker). A smaller Ra indicates a smaller surface roughness. The results are shown in Table 5.

[0286] [Table 5]

[0287] From the results shown in Tables 4 and 5, the curable coloring compositions of Examples 1 to 7 containing the silicone compounds (C-1) to (C-4) that satisfy the above condition (1) were able to suppress the surface roughness of the cured film after post-baking without impairing chromaticity, compared to the curable resin composition of Comparative Example 1 containing the silicone compound (C-5) that does not satisfy the condition (1). Note that this evaluation was measured on a cured film, but those that show good results on a cured film also give similarly good results when measured on a colored pattern. [Industrial Applicability]

[0288] The curable coloring composition of the present invention can reduce surface roughness during the formation of a color filter (particularly post-baking). The cured film and color filter produced from the curable coloring composition of the present invention are useful as color filters for use in display devices (e.g., liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

Claims

1. A curable coloring composition comprising a colorant (A), a resin (B), a silicone compound (C), a polymerizable compound (D), and a polymerization initiator (E), the colorant (A) contains at least one dye selected from the group consisting of a triarylmethane salt-forming compound represented by formula (A1) and a xanthene dye, the content of the silicone compound (C) is 0.3 to 0.8 parts by mass relative to 100 parts by mass of the solid content of the colorant (A), A curable coloring composition characterized in that the silicone compound (C) satisfies condition (1). <Condition (1)> A mixture (H) containing a resin (B-1) having a structural unit of formula (1), the silicone compound (C), a leveling agent (F), and a solvent (G), wherein the content of the silicone compound (C) is 21% by mass relative to 100% by mass of the total amount of solids, is spin-coated onto a glass substrate and baked at 230°C for 20 minutes, and the contact angle of the formed coating film with ion-exchanged water is 70° or more. 【Chemistry 1】 【Chemistry 2】 [In formula (A1), R 41b to R 44b each independently represent a hydrogen atom, a saturated hydrocarbon group of 1 to 20 carbon atoms, an aromatic hydrocarbon group of 6 to 20 carbon atoms which may have a substituent, or an aralkyl group of 7 to 30 carbon atoms which may have a substituent, the substituents which the aromatic hydrocarbon group and the aralkyl group may have may be —SO 3 — or —SO 2 —N —SO 2 —R f , the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or a halogen atom, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, —CH 2 — contained in the saturated hydrocarbon group may be replaced with —O— or —CO—, provided that in the saturated hydrocarbon group of 2 to 20 carbon atoms, adjacent —CH 2 — are not simultaneously replaced with —O—. R 41b and R 42b may be bonded together to form a ring together with the nitrogen atom to which they are bonded, and R 43b and R 44b may be bonded together to form a ring together with the nitrogen atom to which they are bonded. R 47b to R 54b each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, —SO 3 —, —SO 2 —N —SO 2 —R f , or an alkyl group having 1 to 8 carbon atoms, and —CH 2 — constituting the alkyl group may be replaced by —O— or —CO—, and R 48b and R 52b may bond to each other to form —NH—, —S—, or —SO 2 —, provided that adjacent —CH 2 — in the alkyl group are not simultaneously replaced by —O—. Ring T 2b represents an aromatic heterocycle having 3 to 10 carbon atoms or an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and the aromatic heterocycle and aromatic hydrocarbon ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amino group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. The substituent which the aromatic hydrocarbon group may have may be —SO 3 — or —SO 2 —N —SO 2 —R f . M r+ represents a metal ion with a valence of r. k represents the sum of the number of —SO 3 − groups and the number of —SO 2 —N − —SO 2 —R f groups contained in R 41b to R 44b , R 47b to R 54b and ring T 2b . r represents an integer of 1 or more. R f represents a fluoroalkyl group having 1 to 12 carbon atoms. However, R 41b to R 44b , R 47b to R 54b and ring T 2b each have at least one —SO 3 — or —SO 2 —N —SO 2 —R f . When a single molecule contains a plurality of structures represented by the following formula, they may be the same structure or different structures. 【Transformation 3】 [In the formula, ring T 2b , R 41b to R 44b and R 47b to R 54b are each as defined above.]

2. The curable coloring composition according to claim 1, wherein the content of the silicone compound (C) relative to the total amount of the curable coloring composition is 2.0 mass % or less.

3. The curable colored composition according to claim 1 or 2, further comprising a leveling agent (F) containing a fluorine-based surfactant.

4. The curable colored composition according to any one of claims 1 to 3, which is capable of forming a cured film having an arithmetic mean roughness Ra of the surface of 6.0 or less.

5. A color filter formed from the curable coloring composition according to any one of claims 1 to 4.

6. A display device comprising the color filter according to claim 5 .

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