Colored curable resin composition

Abstract

To provide a colored curable resin composition capable of forming a thin deep-color cured film.SOLUTION: The colored curable resin composition includes a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). The colorant (A) includes a compound represented by formula (a). The hydroxyl value of the polymerizable compound (C) is 100 mgKOH / g or more.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a colored curable resin composition, a color filter using the same, and a display device.

Background Art

[0002] Color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays, and solid-state imaging devices such as CCDs and CMOS sensors are manufactured from colored curable resin compositions. As a blue coloring material used in such a colored curable resin composition, C.I. Pigment Blue 24 represented by the formula (i) having a triarylmethane skeleton is known (Non-Patent Document 1).

[0003]

Chemical Formula

Prior Art Documents

Non-Patent Documents

[0004]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, when forming a thick cured film from a colored curable resin composition containing the above blue coloring material, the film thickness may become thick. Therefore, an object of the present invention is to provide a colored curable resin composition capable of forming a thin and dark cured film, a color filter formed from the colored curable resin composition, and a display device including the color filter.

Means for Solving the Problems

[0006] The gist of the present invention is as follows. [1] It contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), wherein the colorant (A) contains a compound represented by formula (a), a colored curable resin composition in which the hydroxyl value of the polymerizable compound (C) is 100 mgKOH / g or more. [Chemical formula] [In formula (a), R 41 ~R 44 each independently 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, and the substituent which the aromatic hydrocarbon group and the aralkyl group may have is -SO3 - or -SO2-N - -SO2-R f and when the saturated hydrocarbon group has 2 to 20 carbon atoms, -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent -CH2- is not simultaneously replaced by -O-, and terminal -CH2- is not replaced by -O- or -CO-. R 41 and R 42 may combine to form a ring together with the nitrogen atom to which they are attached, and R 43 and R 44 may combine to form a ring together with the nitrogen atom to which they are attached. R 47 ~R 54 each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, -SO3 - -SO2-N - -SO2-R f or a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, -CH2- constituting the saturated hydrocarbon group may be replaced by -O- or -CO-, and R 48 and R52 They may be combined with each other to form -NH-, -S-, or -SO2-. However, in the saturated hydrocarbon group, adjacent -CH2- is not simultaneously substituted with -O-, and the terminal -CH2- is not substituted with -O- or -CO-. Ring T 1 represents an aromatic heterocyclic ring having 3 to 10 carbon atoms, and the aromatic heterocyclic ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a substituted or unsubstituted amino group, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, -SO3 - or -SO2-N - -SO2-R f and may have. The substituent that the aromatic hydrocarbon group may have is -SO3 - or -SO2-N - -SO2-R f and may be. M r+ represents an r-valent metal ion. k is the sum of the number of -SO3 - in the compound represented by formula (a) and the number of -SO2-N - -SO2-R f and represents. r represents an integer of 1 or more. R f represents a fluoroalkyl group having 1 to 12 carbon atoms. However, the compound represented by formula (a) has at least one of -SO3 - or -SO2-N - -SO2-R f . [2] The colored curable resin composition according to [1], wherein the hydroxyl value of the polymerizable compound (C) is 200 mgKOH / g or more. [3] The colored curable resin composition according to [1] or [2], wherein the colorant (A) further contains a xanthene dye. [4] The colored curable resin composition according to [3], wherein the xanthene dye is a compound represented by formula (1).

Chemical formula

Advantages of the Invention

[0007] According to the present invention, it is possible to provide a colored curable resin composition capable of forming a thin and dark cured film, a color filter formed from the colored curable resin composition, and a display device including the color filter.

Embodiments for Carrying Out the Invention

[0008] The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). The colorant (A) contains a compound represented by the formula (a) (hereinafter sometimes referred to as compound (a)). The colored curable resin composition of the present invention preferably further contains a solvent (hereinafter sometimes referred to as solvent (E)). The colored curable resin composition of the present invention may contain a leveling agent (hereinafter sometimes referred to as leveling agent (F)). In this specification, the compounds exemplified as each component can be used alone or in combination of two or more without particular notice.

[0009] <Colorant (A)> <<Compound (a)>> The colorant (A) contains compound (a). Hereinafter, the present invention will be described in detail using the formula (a), but compound (a) also includes its tautomers and salts.

[0010]

Chemical formula

[0011] Ring T 1 The aromatic heterocyclic ring represented by may be a monocyclic ring or a condensed ring. Ring T 1 The number of carbon atoms of the aromatic heterocyclic ring represented by is preferably 3 to 10, more preferably 3 to 8. Further, the aromatic heterocyclic ring is preferably a 5- to 10-membered ring, more preferably a 5- to 9-membered ring. Examples of the monocyclic aromatic heterocyclic ring 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 not containing a nitrogen atom such as a furan ring and a thiophene ring; 6-membered rings containing a nitrogen atom such as a pyridine ring, a pyrimidine ring, a pyridazine ring, and a pyrazine ring; and the like. Examples of the condensed-ring aromatic heterocyclic ring include condensed rings containing a nitrogen atom such as an indole ring, a benzimidazole ring, a benzothiazole ring, and a quinoline ring; condensed rings not containing a nitrogen atom such as a benzofuran ring; and the like.

[0012] Ring T 1 Examples of the substituent that the aromatic heterocyclic ring of may optionally have include a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a substituted or unsubstituted amino group, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, -SO3 - or -SO2-N - -SO2-R f and the like, and preferably include a saturated hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted amino group, or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. Ring T 1 preferably has an amino group which may have a substituent, and examples of the substituent that the amino group may optionally have include a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, an aralkyl group having 7 to 30 carbon atoms which may have a substituent, and the like. Among them, Ring T 1As the aromatic heterocyclic ring, an aromatic heterocyclic ring containing a nitrogen atom is preferable, and a 5-membered aromatic heterocyclic ring containing a nitrogen atom is more preferable.

[0013] Ring T 1 is preferably a ring represented by formula (t1).

[0014] [Chemical formula]

[0015] [In formula (t1), X2 represents -O-, -N(R 57 )- or -S-. R 57 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R 45 and R 46 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. R 55 represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. In the above R 45 , R 46 and R 55 , when the saturated hydrocarbon group has 2 to 20 carbon atoms, -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent -CH2- is not simultaneously replaced by -O-, and terminal -CH2- is not replaced by -O- or -CO-. R 45 and R 46 may combine with each other to form a ring together with the nitrogen atom to which they are attached. * represents a bond to a carbocation.]

[0016] Also, ring T 1It is also preferable that it is a ring represented by the formula (t2).

[0017]

Chemical formula

[0018] [In the formula (t2), ring T 3 represents an aromatic heterocyclic ring having 3 to 10 carbon atoms and having a nitrogen atom. R 58 represents an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, -SO3 - , or -SO2-N - -SO2-R f represents. R 59 represents a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted aralkyl group having 7 to 30 carbon atoms. k2 represents 0, 1, or 2. * represents a bond with a carbocation.]

[0019] It is more preferable that the ring represented by the formula (t2) is a ring represented by the formula (t2-1).

[0020]

Chemical formula

[0021] [In the formula (t2-1), R 60 represents a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. R 61 represents -SO3 - , or -SO2-N - -SO2-R f represents. R 59 has the same meaning as above. * represents a bond with a carbocation.

[0022] Ring T 1 is preferably a ring represented by formula (t1) or formula (t2), and more preferably a ring represented by formula (t1).

[0023] R 41 ~R 55 and R 58 ~R 60 A saturated hydrocarbon group having 1 to 20 carbon atoms, represented by Ring T 1 A saturated hydrocarbon group having 1 to 20 carbon atoms that Ring T may have, and 1 A saturated hydrocarbon group having 1 to 20 carbon atoms that may have an amino group that Ring T may have may be linear, branched, or cyclic. Examples of the linear or branched saturated hydrocarbon group include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, icosyl group; and branched alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group. The number of carbon atoms of the saturated hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, and still more preferably 1 to 6.

[0024] The cyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include alicyclic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group. The number of carbon atoms of the cyclic saturated hydrocarbon group is preferably 3 to 10, more preferably 6 to 10.

[0025] R 41 ~R 55 and R 58 ~R 60 A saturated hydrocarbon group represented by Ring T 1 A saturated hydrocarbon group that Ring T may have, and 1Examples of the saturated hydrocarbon group which may have an amino group which may be present include a methyl group, an ethyl group, an isopropyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isobutyl group, a 2-ethylhexyl group, a cyclohexyl group, an adamantyl group, etc.

[0026] R 41 ~R 55 and R 58 ~R 60 The saturated hydrocarbon group represented by, ring T 1 The saturated hydrocarbon group which may be present, and ring T 1 The saturated hydrocarbon group which may have an amino group which may be present 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 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, 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.

[0027] Also, as the alkyl group having 1 to 10 carbon atoms represented by R 57 Examples include groups having 1 to 10 carbon atoms among the linear or branched saturated hydrocarbon groups exemplified as the saturated hydrocarbon group represented by R 41

[0028] R 41 ~R 55When the number of carbon atoms of the saturated hydrocarbon group represented by is 2 to 20, the -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent -CH2- is not simultaneously replaced by -O-, and the terminal -CH2- is not replaced by -O- or -CO-. In this case, as the saturated hydrocarbon group, a linear or branched saturated hydrocarbon group (i.e., a linear or branched alkyl group) is preferable, and a linear saturated hydrocarbon group (i.e., a linear alkyl group) is more preferable. The preferable number of carbon atoms of the saturated hydrocarbon group in which -CH2- may be replaced by -O- or -CO- is 2 to 10, and more preferably 2 to 8. When -CH2- is replaced by -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 1 or more, preferably 1 to 5, more preferably 2 to 3, and even more preferably 2.

[0029] Also, R 41 ~R 46 、R 55 and R 58 ~R 60 The number of carbon atoms of the aromatic hydrocarbon group represented by, the aromatic hydrocarbon group that the ring T 1 may have, and the aromatic hydrocarbon group that may have an amino group that the ring T 1 may have is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 12. 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, a terphenyl group, etc., and preferably a phenyl group, a naphthyl group, a tolyl group, a xylyl group. The aromatic hydrocarbon group may also have one or more substituents. Examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, an iodine atom, a bromine atom; alkoxy groups having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group; a hydroxy group; a sulfamoyl group; alkylsulfonyl groups having 1 to 6 carbon atoms such as a methylsulfonyl group; alkoxycarbonyl groups having 1 to 6 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group; -SO3- ;-SO2-N - -SO2-R f ; etc., including -SO3 - or -SO2-N - -SO2-R f may also be used. However, -SO3 - and -SO2-N - -SO2-R f are preferably directly bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group, that is, substituting the hydrogen atom bonded to the aromatic hydrocarbon ring. R 55 As the substituent in the aromatic hydrocarbon group represented by, a halogen atom is preferred.

[0030] Specific examples of the aromatic hydrocarbon group that may have a substituent include, for example, the groups represented by the following formula. The groups represented by the following formula may further have at least one of -SO3 - or -SO2-N - -SO2-R f In the following formula, * represents a bond to a nitrogen atom or a carbon atom.

[0031]

Chemical formula

[0032]

Chemical formula

[0033] R 41 ~R 46 、R 59 the aralkyl group represented by, and ring T 1Examples of the aralkyl group which may have an amino group which may be present include groups in which an alkanediyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms) such as a methylene group, an ethylene group, or a propylene group is bonded to the group described as the aromatic hydrocarbon group above. The number of carbon atoms of the aralkyl group is preferably 7 to 30, more preferably 7 to 20, and even more preferably 7 to 17. Further, the aralkyl 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 ; and the like.

[0034] R 41 and R 42 and the ring formed together with the nitrogen atom to which they are bonded, R 43 and R 44 and the ring formed together with the nitrogen atom to which they are bonded, and R 45 and R 46 Examples of the ring formed 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 4- to 7-membered rings having only one nitrogen atom as a heteroatom such as a pyrrolidine ring and a piperidine ring.

[0035] Among them, R 41 ~R 44 、R 55 、R 58 ~R 60 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 each independently is more preferably a saturated hydrocarbon group having 1 to 8 carbon atoms or a group represented by the following formula. In particular, R 41 and R 43is preferably, independently of each other, a saturated hydrocarbon group having 1 to 20 carbon atoms, and more preferably, independently of each other, a saturated hydrocarbon group having 1 to 8 carbon atoms. R 42 and R 44 are preferably, independently of each other, an aromatic hydrocarbon group which may have a substituent, and more preferably, independently of each other, a phenyl group which may have a substituent, a tolyl group which may have a substituent, or a xylyl group which may have a substituent. R 55 is more preferably an aromatic hydrocarbon group which may have a substituent. R 55 、R 58 ~R 60 is even more preferably a group represented by the following formula. The group represented by the following formula may further have at least one of -SO3 - or -SO2-N - -SO2-R f In the following formula, * represents a bond to a nitrogen atom or a carbon atom.

[0036]

Chemical formula

[0037]

Chemical formula

[0038] R 45 ~R 46 is, independently of each other, a saturated hydrocarbon group having 1 to 20 carbon atoms, a group in which at least one -CH2- constituting an alkyl group having 2 to 20 carbon atoms is replaced by -O- or -CO-, or an aromatic hydrocarbon group which may have a substituent, or R 45 and R 46 are preferably bonded to form a ring together with the nitrogen atom to which they are bonded. R 45 ~R 46 is, independently of each other, a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or a group represented by the following formula, or R 45 and R46 It is more preferable that they are combined to form a 4- to 7-membered ring having only one nitrogen atom as a heteroatom, and each is independently a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or a group represented by the following formula. The group represented by the following formula may further have -SO3 - or -SO2-N - -SO2-R f as at least one. In the following formula, * represents a bond to a nitrogen atom.

[0039]

Chemical formula

[0040]

Chemical formula

[0041] Among them, R 45 is a saturated hydrocarbon group having 1 to 4 carbon atoms, and R 46 is preferably an o-tolyl group.

[0042] R 47 ~R 54 are each independently preferably a hydrogen atom, a halogen atom, or a linear or branched saturated hydrocarbon 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 even more preferably each independently a hydrogen atom. Also, as R 57 , a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is preferable. As R 61 , a hydrogen atom is preferable.

[0043] M r+Examples of the r-valent metal ion represented by 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 preferably 1 or more, more preferably 2 or more, preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less. M r+ Among them, alkaline earth metal ions, typical metal ions, etc. are more preferable, alkaline earth metal ions and zinc ion are even more preferable, and alkaline earth metal ions are even more preferable.

[0044] In formula (a), M r+ The number of is one less than the sum (k) of the number of -SO3 - and the number of -SO2-N - -SO2-R f in the compound (a). Therefore, the compound (a) is a compound with a valence of 0, that is, an electrically neutral compound.

[0045] R f Examples of the fluoroalkyl group having 1 to 12 carbon atoms represented by include monofluoromethyl group, difluoromethyl group, perfluoromethyl group, monofluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, perfluoroethyl group, monofluoropropyl group, difluoropropyl group, trifluoropropyl group, tetrafluoropropyl group, pentafluoropropyl group, hexafluoropropyl group, perfluoropropyl group, monofluorobutyl group, difluorobutyl group, trifluorobutyl group, tetrafluorobutyl group, pentafluorobutyl group, hexafluorobutyl group, heptafluorobutyl group, octafluorobutyl group, perfluorobutyl group, etc. Among them, R fAs the fluoroalkyl group represented by [formula], a perfluoroalkyl group is preferred. Also, R f The number of carbon atoms of the fluoroalkyl group represented by [formula] is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.

[0046] In formula (a), R 41 ~R 44 、R 47 ~R 54 and ring T 1 have at least one of -SO3 - or -SO2-N - -SO2-R f . R 41 ~R 44 、R 47 ~R 54 and ring T 1 The sum (k) of the number of -SO3 - and -SO2-N - -SO2-R f they have is 1 or more, preferably 1 or more and 7 or less, more preferably 2 or more and 7 or less, even more preferably 2 or more and 4 or less, still more preferably 2 or 3, and particularly preferably 2.

[0047] -SO3 - or -SO2-N - -SO2-R f Preferably satisfies at least one or more conditions selected from the following (Ia) to (Id), and more preferably satisfies at least one or more conditions selected from (Ia) and (Ib). (Ia) Included as any of the above R 47 ~R 54 (Ib) Bonded to any of the aromatic hydrocarbon groups having 6 to 20 carbon atoms which may have a substituent represented by R 41 ~R 44 (Ic) Bonded to any of the aralkyl groups having 7 to 30 carbon atoms which may have a substituent represented by R 41 ~R 44 (Id) T 1bonded to any of the aromatic hydrocarbon groups having 6 to 20 carbon atoms that substitute the hydrogen atoms of the aromatic heterocyclic ring represented by

[0048] However, when -SO3 - or -SO2-N - -SO2-R f is bonded, -SO3 - or -SO2-N - -SO2-R f is preferably directly bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group or aralkyl group. That is, -SO3 - or -SO2-N - -SO2-R f preferably substitutes the hydrogen atom bonded to the aromatic hydrocarbon ring. -SO3 - or -SO2-N - -SO2-R f is a C6-C20 aromatic hydrocarbon group which may have a substituent representing R 41 ~R 44 or in the aromatic hydrocarbon ring (e.g., benzene ring) of an aralkyl group having 7 to 30 carbon atoms which may have a substituent representing R 41 ~R 44 is preferably bonded to the para position with respect to the bonding position to the nitrogen atom. When the compound (a) contains a plurality of -SO3 - or -SO2-N - -SO2-R f the plurality of -SO3 - or -SO2-N - -SO2-R f may be bonded to the same aromatic hydrocarbon ring, but is preferably bonded to different aromatic hydrocarbon rings.

[0049] The compound (a) preferably does not have an ethylenically unsaturated bond.

[0050] The compound (a) is R 41 and R 43is, independently of each other, a saturated hydrocarbon group having 1 to 10 carbon atoms (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 number of carbon atoms of the saturated hydrocarbon group is 2 to 10, -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-.), R 42 and R 44 is, independently of each other, a phenyl group which may have a substituent, a tolyl group which may have a substituent, or a xylyl group which may have a substituent (the substituent which the phenyl group, tolyl group, and xylyl group may have is -SO3 - or -SO2-N - -SO2-R f may be.). R 47 ~R 54 is a hydrogen atom, ring T 1 is a 5-membered ring containing a nitrogen atom (the 5-membered ring may have a saturated hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted amino group, or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. The substituent which the aromatic hydrocarbon group may have is -SO3 - or -SO2-N - -SO2-R f may be.), or a compound represented by formula (a-1) (hereinafter sometimes referred to as "compound (a-1)") is preferable.

[0051]

Chemical formula

[0052] [In formula (a-1), R 47A ~R 54A each independently represents a hydrogen atom, -SO3 - , or a saturated hydrocarbon group having 1 to 10 carbon atoms. R 41A and R 43AEach independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 10 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 - may be. R 11A ~R 20A Each independently represents -SO3 - , a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms or a halogen atom. R 45A , R 46A and R 55A Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and the substituent which the aromatic hydrocarbon group may have is -SO3 - may be. The above R 47A ~R 54A , R 41A , R 43A , R 11A ~R 20A , R 45A , R 46A and R 55A In, when the carbon number of the saturated hydrocarbon group is 2 to 10, -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. However, in the saturated hydrocarbon group having 2 to 10 carbon atoms, adjacent -CH2- is not simultaneously replaced by -O-, and terminal -CH2- is not replaced by -O- or -CO-. M r+ represents an r-valent metal ion. k represents the number of -SO3 - groups that the compound represented by the formula (a-1) has. However, the compound represented by the formula (a-1) has at least two -SO3 - groups. r represents an integer of 2 or more.

[0053] R 47A ~R 54A , R41A , R 43A , R 11A ~R 20A , R 45A , R 46A and R 55A Examples of the saturated hydrocarbon group having 1 to 10 carbon atoms represented by are the groups having 1 to 10 carbon atoms among the saturated hydrocarbon groups exemplified by R 41 Among the saturated hydrocarbon groups exemplified by, groups having 1 to 10 carbon atoms are included.

[0054] R 45A , R 46A and R 55A The substituent that the saturated hydrocarbon group having 1 to 10 carbon atoms represented by may have is the same as the group exemplified as the substituent that the saturated hydrocarbon group represented by R 41 may have.

[0055] R 41A , R 43A , R 45A , R 46A and R 55A Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by are the same as the groups exemplified as the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R 41 Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by are the same as the groups exemplified as the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R

[0056] R 41A and R 43A Examples of the aralkyl group having 7 to 30 carbon atoms represented by are the same as the groups exemplified as the aralkyl group having 7 to 30 carbon atoms represented by R 41 Examples of the aralkyl group having 7 to 30 carbon atoms represented by are the same as the groups exemplified as the aralkyl group having 7 to 30 carbon atoms represented by R

[0057] R 41A , R 43A , R 45A , R 46A and R 55A Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by, and R 41A and R 43AExamples of the substituent that the C7-C30 aralkyl group represented by may have include halogen atoms such as fluorine atom, chlorine atom, iodine atom, bromine atom; alkoxy groups having 1 to 6 carbon atoms such as methoxy group, ethoxy group; hydroxy group; sulfamoyl group; alkylsulfonyl groups having 1 to 6 carbon atoms such as methylsulfonyl group; alkoxycarbonyl groups having 1 to 6 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group; -SO3 - ; and the like.

[0058] R 11A ~R 20A Examples of the halogen atom represented by include fluorine atom, chlorine atom, bromine atom, iodine atom and the like, and fluorine atom is preferred.

[0059] R 47A ~R 54A are each independently more preferably a hydrogen atom, -SO3 - , or a methyl group, and even more preferably a hydrogen atom or a methyl group.

[0060] R 41A and R 43A are each independently preferably a saturated hydrocarbon group having 1 to 10 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, each independently preferably a saturated hydrocarbon group having 1 to 8 carbon atoms; phenyl group; tolyl group; naphthyl group; methylnaphthyl group; unsubstituted aralkyl group; or an aralkyl group substituted with one or more, particularly one, selected from halogen atom, methoxy group, ethoxy group, sulfamoyl group, methylsulfonyl group, methoxycarbonyl group, and ethoxycarbonyl group, each independently more preferably a linear alkyl group having 1 to 4 carbon atoms.

[0061] R 11A ~R 12AFrom the viewpoints of heat resistance and light resistance, at least one of them is preferably a halogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably at least one of them is a halogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms, and still more preferably at least one of them is a fluorine atom or a saturated hydrocarbon group having 1 to 4 carbon atoms.

[0062] R 13A ~R 14A From the viewpoints of heat resistance and light resistance, at least one of them is preferably a halogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably at least one of them is a halogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms, and still more preferably at least one of them is a fluorine atom or a saturated hydrocarbon group having 1 to 4 carbon atoms.

[0063] R 15A ~R 20A From the viewpoint of ease of synthesis, each is independently preferably a hydrogen atom, -SO3 - , or a saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom, -SO3 - , or a saturated hydrocarbon group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom, -SO3 - , or a methyl group.

[0064] R 45A R 46A and R 55A are each independently preferably a saturated hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with a halogen atom, an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, or a methylsulfonyl group; or a saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 8 carbon atoms or an aromatic hydrocarbon group represented by the following formula.

[0065] In particular, R 45 and R46 It is preferable that one of them is a saturated hydrocarbon group having 1 to 6 carbon atoms and the other is an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent; it is more preferable that one of them is a saturated hydrocarbon group having 1 to 6 carbon atoms and the other is an aromatic hydrocarbon group represented by the following formula. R 55 is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms having a halogen atom, and more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms having two or more halogen atoms. R 55 The number of halogen atoms in the aromatic hydrocarbon group represented by is preferably 1 to 6, more preferably 1 to 4, and even more preferably 2 to 3. The halogen atom is preferably a fluorine atom. R 55 is also preferably an aromatic hydrocarbon group represented by the following formula. In the following formula, * represents a bond to a carbon atom.

[0066]

Chemical formula

[0067]

Chemical formula

[0068] In formula (a-1), the number of -SO3 - is 2 or more, preferably 6 or less, and more preferably 4 or less.

[0069] -SO3 - is (ia) R 47A ~R 54A 、R 11A ~R 20A is included as any one of, (ib) R 41A 、R 43A an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent represented by, and R 41A 、R 43Ais attached to any of the aralkyl groups having 7 to 30 carbon atoms which may have a substituent represented by, (ic)R 45A 、R 46A 、R 55A is attached to any of the aromatic hydrocarbon groups having 6 to 20 carbon atoms which may have a substituent represented by, or it is preferably present as a combination of these (ia) to (ic), it is more preferably present as (ia), (ib) or a combination of (ia) to (ib), it is even more preferably present as (ia). Also, among R 47A ~R 54A 、R 11A ~R 20A 、it is particularly preferable that -SO3 16A and R 19A is included as. - is particularly preferably included.

[0070] In the above (ia) to (ic), -SO3 - is preferably directly attached to the aromatic hydrocarbon ring of the aromatic hydrocarbon group or aralkyl group. That is, -SO3 - preferably replaces the hydrogen atom attached to the aromatic hydrocarbon ring. Two or more -SO3 - may be attached to the same aromatic hydrocarbon ring, but are preferably attached to different aromatic hydrocarbon rings.

[0071] Examples of the compound (a) include compounds 1 to 514 represented by the formula (a-2) as shown in Tables 1 to 9 below.

[0072] However, the compound represented by the formula (a-2) has two -SO3 - and the -SO3 - replaces any two of the hydrogen atoms represented by R h 、R 11A ~R 14A and preferably R hTwo of the hydrogen atoms represented by are substituted, and more preferably, in the benzene ring bonded to the nitrogen atom, R is located at the para position with respect to the bonding position with the nitrogen atom. h is substituted.

[0073]

Chemical formula

[0074]

Table 1

[0075]

Table 2

[0076]

Table 3

[0077]

Table 4

[0078]

Table 5

[0079]

Table 6

[0080]

Table 7

[0081]

Table 8

[0082]

Table 9

[0083] In Tables 1 to 9, Me represents a methyl group, Et represents an ethyl group, iPr represents an isopropyl group, Bt represents an n-butyl group, and Ph1 to Ph10 each represent a group represented by the following formula. In Ph1 to Ph10, * represents a bond.

[0084]

Chemical formula

[0085] Among them, as the compound (a), Compounds 31 to 90, compounds 121 to 180, compounds 211 to 334, compounds 365 to 424, compounds 455 to 514 are preferred, Compounds 46 to 60, compounds 61 to 90, compounds 136 to 150, compounds 226 to 240, compounds 271 to 334, compounds 380 to 394, compounds 470 to 484 are more preferred, Compounds 46 to 60, compounds 61 to 90, compounds 136 to 150, compounds 226 to 240, compounds 271 to 304, compounds 380 to 394, compounds 470 to 484 are even more preferred, Compounds 46 to 60, compounds 61 to 90, compounds 136 to 150, compounds 226 to 240, compounds 271 to 294, compounds 380 to 394, compounds 470 to 484 are even more preferably, Compounds 46 to 60, compounds 61 to 90, compounds 136 to 150, compounds 226 to 240, compounds 279 to 294, compounds 380 to 394, compounds 470 to 484 are particularly more preferred. According to these compounds, particularly high heat resistance and light resistance can be achieved simultaneously, and further good brightness can be obtained.

[0086] -SO3 -Compound (a) having [a certain group] can be produced, for example, by sulfonating a compound represented by formula (aC) (hereinafter sometimes referred to as compound (aC)), and further reacting it with a halide (preferably chloride), acetate, phosphate, sulfate, silicate, cyanide, etc. containing an r-valent metal ion.

[0087] [Chemical formula]

[0088] [In formula (aC), R 1c ~R 4c each independently 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. When the number of carbon atoms of the saturated hydrocarbon group is 2 to 20, -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent -CH2- is not simultaneously replaced by -O-, and terminal -CH2- is not replaced by -O- or -CO-. R 1c and R 2c may combine to form a ring together with the nitrogen atom to which they are attached, and R 3c and R 4c may combine to form a ring together with the nitrogen atom to which they are attached. R 7c ~R 14c each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. When the number of carbon atoms of the saturated hydrocarbon group is 2 to 20, -CH2- constituting the saturated hydrocarbon group may be replaced by -O- or -CO-. However, in the saturated hydrocarbon group, adjacent -CH2- is not simultaneously replaced by -O-, and terminal -CH2- is not replaced by -O- or -CO-. R 8c and R 12cThey may be bonded to each other to form -NH-, -S-, or -SO2-. Ring T 10 represents an aromatic heterocyclic ring having 3 to 10 carbon atoms, and the aromatic heterocyclic ring may have 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. M 1c is Cl - , phosphate ion, perchlorate ion, BF4 - or PF6 - .

[0089] -SO2-N - -SO2-R f Compound (a) having -SO2-N - -SO2-R - is reacted with a compound represented by formula (IB) and further reacted with a halide (preferably chloride), acetate, phosphate, sulfate, silicate or cyanide containing an r-valent metal ion, etc., whereby it can be produced. f In formula (IB), R

[0090]

Chemical formula

[0091] [In formula (IB), R f is as defined above.

[0092] As the sulfonation method, various known methods can be used. For example, the methods described in Journal of Organic Chemistry, (1994), vol.59, #11, p.3232-3236 can be mentioned.

[0093] By adding a dispersant to compound (a) and performing a dispersion treatment, a dispersion in which compound (a) is uniformly dispersed in a solution can be obtained.

[0094] Examples of the dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These dispersants may be used alone or in combination of two or more. Examples of the dispersant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Ltd.), EFKA (manufactured by CIBA), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Inc.), Disperbyk (manufactured by BYK-Chemie GmbH), BYK (manufactured by BYK-Chemie GmbH), etc. under their trade names. When using a dispersant, the amount used is preferably 1% by mass or more and 100% by mass or less, more preferably 15% by mass or more and 100% by mass or less, based on the compound (a). When the amount of the dispersant used is within the above range, a dispersion liquid in a uniform dispersion state can be obtained.

[0095] In the dispersion liquid, the content of the compound (a) is preferably 1% by mass or more and 80% by mass or less, more preferably 1% by mass or more and 50% by mass or less, still more preferably 1% by mass or more and 30% by mass or less.

[0096] <<Xanthene Dye>> The colorant (A) preferably further contains a xanthene dye. As the xanthene dye, known xanthene dyes can be used, and among them, it is preferable to contain a compound represented by the formula (1) (hereinafter also referred to as "compound (1)") as a main component. In this specification, "containing as a main component" means preferably containing 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, particularly preferably 98% by mass or more, and the upper limit may be 100% by mass.

[0097] [Chemical formula] [In formula (1), R 1 ~R 4 are each independently a hydrogen atom, -R 8 or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, or R 1 and R2 and R 3 and R 4 together form a ring containing a nitrogen atom. The hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom, -OH, -OR 8 , -SO3 - , -SO3H, -SO3 - M + , -CO2H, -CO2R 8 , -SO3R 8 or -SO2NR 9 R 10 may be substituted. R 5 is -OH, -SO3 - , -SO3H, -SO3 - M + , -CO2H, -CO2 - M + , -CO2R 8 , -SO3R 8 or -SO2NR 9 R 10 represents. m represents an integer from 0 to 5. When m is an integer of 2 or more, a plurality of R 5 may be the same or different from each other. R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. M + is + N(R 11 )4, Na + or K + and X represents a halogen atom. a represents 0 or 1. R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms, a carboxy group or a halogen atom. The -CH2- contained in the saturated hydrocarbon group may be replaced with -S-, -O-, -CO- or -NR 11 -. However, in the saturated hydrocarbon group, adjacent -CH2- is not simultaneously replaced with -O-. R 11represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and R 11 When a plurality of them exist, all or some of them may be the same. R 9 and R 10 each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with -OH or a halogen atom, and -CH2- contained in the saturated aliphatic hydrocarbon group may be replaced with -S-, -O-, -CO-, -NH- or -NR 8 -. However, in the saturated hydrocarbon group, adjacent -CH2- is not simultaneously replaced with -O-. R 9 and R 10 may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom.]

[0098] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0099] R 1 ~R 4 Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R

[0100] R 1 and R 2 include, for example, a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group. 3 and R 4 Examples of the ring formed by R

[0101]

Chemical formula

[0102] R 8 ~R 11 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R41 Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by the formula include the same groups as those exemplified as the group.

[0103] R 8 Regarding R, examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms in which the hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms may be substituted include R 1 ~R 4 Examples of the group include the same groups as those exemplified as the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by the formula.

[0104] R in formula (1) 11 Examples of the aralkyl group having 7 to 10 carbon atoms in R include benzyl group, phenylethyl group, phenylbutyl group and the like.

[0105] M + is + N(R 11 )4, Na + or K + , and preferably + N(R 11 )4. + N(R 11 )4 is preferably such that at least two of the four Rs 11 are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. Further, the total number of carbon atoms of the four Rs 11 is preferably 20 to 80, more preferably 20 to 60.

[0106] The xanthene dye preferably contains, more preferably, a compound represented by formula (2) as a main component.

[0107] [Chemical formula]

[0108] [In formula (2), R 21 ~R 24 each independently represents a hydrogen atom, -R 26 or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is -CO2H, -SO3- 、 -SO3 - M a+ 、 -SO3H, -SO3R 26 or -SO2NHR 26 may be substituted. X represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. a1 represents 0 or 1. m1 represents an integer from 0 to 5. When m1 is an integer of 2 or more, a plurality of R 25 may be the same or different. M a+ is + N(R 27 )4, Na + or K + represents. R 25 represents -SO3 - 、 -SO3 - M a+ 、 -SO3H or -SO2NHR 26 represents. R 26 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a carboxyl group. Four R 27 independently of one another represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group.

[0109] In formula (2), R 21 ~R 24 Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include the same groups as those listed as the aromatic hydrocarbon groups in R 1 ~R 4 .

[0110] R 26 and R 27 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms include the same groups as those listed as the saturated hydrocarbon groups in R 8 ~R 11 . In formula (2), R 21 ~R 24 In -R 26is, independently of each other, preferably a linear alkyl group having 1 to 4 carbon atoms which may be substituted with a carboxy group, more preferably a methyl group or an ethyl group. Further, -SO3R 26 and -SO2NHR 26 in R 26 is preferably a branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 6 to 12 carbon atoms, and even more preferably a 2-ethylhexyl group.

[0111] M a+ is + N(R 27 )4, Na + or K + and is preferably + N(R 27 )4. + N(R 27 )4 is preferably such that at least two of the four Rs 27 are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. Further, the total number of carbon atoms of the four Rs 27 is preferably 20 to 80, and more preferably 20 to 60.

[0112] In formula (2), R 21 and R 23 are hydrogen atoms, and R 22 and R 24 are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms. When the hydrogen atoms contained in the aromatic hydrocarbon group are substituted, the substituting group is -SO3 - , -SO3 - M + , -SO3H, -SO3R 26 or -SO2NHR 26 is preferred. Further, R 21 and R 23 are hydrogen atoms, and R 22 and R 24 are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms (preferably a phenyl group, a toluyl group, or a xylyl group), and the hydrogen atoms contained in the aromatic hydrocarbon group are -SO3 - M + or -SO2NHR 26It is more preferable that it may be replaced by R 21 ~R 24 When these are these groups, it is advantageous for forming a color filter excellent in heat resistance.

[0113] In formula (2), R 25 is preferably -SO3 - or SO2NHR 26 is preferable.

[0114] In formula (2), a1 is preferably 0.

[0115] The xanthene dye preferably contains, as a main component, any one or more of the compounds represented by formulas (1-1) to (1-39). In the formula, Ra represents a 2-ethylhexyl group.

[0116]

Chemical formula

[0117]

Chemical formula

[0118]

Chemical formula

[0119]

Chemical formula

[0120]

Chemical formula

[0121] The compounds represented by formulas (1-1) to (1-16) are obtained, for example, by chlorinating a dye or a dye intermediate having -SO3H by a conventional method, and the resulting dye or dye intermediate having -SO2Cl is R 8It can be produced by reacting with an amine represented by -NH2. Also, the dye produced by the method described in the upper right column to the lower left column on page 3 of JP-A-3-78702 can also be produced by a method in which, after chlorination, it is reacted with an amine in the same manner as described above.

[0122] The compounds represented by Formula (1-17) to Formula (1-32) can be produced according to the method described in the upper right column to the lower left column on page 3 of JP-A-3-78702. As such a method, for example, a method of reacting a compound represented by Formula (1a) with a compound represented by Formula (1b) and a compound represented by Formula (1c) can be mentioned. In Formula (1b) and Formula (1c), R 1 ~R 4 each represents the same meaning as described above.

[0123] [Chemical formula]

[0124] The compounds represented by Formula (1-33) to Formula (1-39) can be produced according to the method described in JP-A-2017-226814.

[0125] [[Other colorants]] In addition to the compound (a) and the xanthene dye, the colorant (A) may contain one or both of other dyes (hereinafter sometimes referred to as dye (A1)) and other pigments (hereinafter sometimes referred to as pigment (A2)).

[0126] The dye (A1) is not particularly limited, and known dyes can be used, including solvent dyes, acid dyes, direct dyes, mordant dyes, etc. Examples of dyes 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 described in the Dyeing Notes (Color Dyeing Company). Also, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, etc. can be mentioned. Among these, organic solvent-soluble dyes are preferred.

[0127] Specifically, the following dyes with Color Index (C.I.) numbers can be mentioned. For example, C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; C.I. Solvent Yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; C.I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141; C.I. Disperse Yellow 51, 54, 76; C.I. Reactive Yellow 2, 76, 116; C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173; C.I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99; C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; C.I. Reactive Orange 16; C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 57, 66, 73, 76, 80, 88, 91, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426; C.I. Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247; C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; C.I. Mordant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95; C.I. Acid Violet 34; C.I. Disperse Violet 26, 27; C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; C.I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59:1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; C.I. Acid Blue 25, 27, 40, 45, 78, 80, 112; C.I. Direct Blue 40; C.I. Disperse Blue 1, 14, 56, 60; C.I. Solvent Green 1, 3, 5, 28, 29, 32, 33; C.I. Acid Green 3, 5, 9, 25, 27, 28, 41; C.I. Basic Green 1; C.I. Vat Green 1 etc. are exemplified.

[0128] As the pigment, known pigments can be used. For example, pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists) can be mentioned. Two or more kinds may be combined. Specifically, yellow pigments such as C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, etc.; Orange pigments such as C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; Red pigments such as C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273; Blue pigments such as C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60; Violet pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38; Examples of the green pigments include C.I. Pigment Green 7, 36, 58, 59.

[0129] The pigment (A2) may be subjected to surface treatment using rosin treatment, pigment derivatives into which acidic groups or basic groups are introduced, etc., graft treatment on the pigment surface with polymer compounds, etc., micronization treatment by the sulfuric acid micronization method, etc., or cleaning treatment with organic solvents, water, etc. for removing impurities, removal treatment by the ion exchange method of ionic impurities, etc., if necessary. The pigment (A2) preferably has a uniform particle size. By performing a dispersion treatment containing a dispersant, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

[0130] As the above-mentioned dispersant, the dispersants described above can be used. When using a dispersant, its usage amount is preferably 1% by mass or more and 100% by mass or less, more preferably 5% by mass or more and 50% by mass or less, based on the total amount of the pigment (A2). When the usage amount of the pigment dispersant is within the above range, a pigment dispersion with a uniform dispersion state can be obtained.

[0131] The content of the compound (a) in the colorant (A) is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, particularly preferably 80% by mass or more, and may be 100% by mass, or may be 98% by mass or less, or may be 95% by mass or less.

[0132] The content rate of the xanthene dye in the colorant (A) is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less.

[0133] The total content rate of the compound (a) and the xanthene dye in the colorant (A) is preferably 75% by mass or more, more preferably 85% by mass or more, still more preferably 95% by mass or more, particularly preferably 98% by mass or more, and may also be 100% by mass.

[0134] The content rate of the colorant (A) is preferably 5% by mass or more and 60% by mass or less, more preferably 8% by mass or more and 55% by mass or less, still more preferably 10% by mass or more and 50% by mass or less, with respect to the total amount of the solid content. When the content of the colorant (A) is within the above range, the color density when used as a color filter is sufficient, and a necessary amount of the resin (B) and the polymerizable compound (C) can be contained in the composition, so that a pattern with sufficient mechanical strength can be formed.

[0135] Here, the "total amount of the solid content" in this specification refers to the amount obtained by removing the content of the solvent from the total amount of the color-curable resin composition. The total amount of the solid content and the content of each component with respect thereto can be measured by known analytical means such as liquid chromatography or gas chromatography.

[0136] <Resin (B)> The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6] and the like. Resin [K1]; a copolymer having a structural unit derived from at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as "(a)") and a structural unit derived from a monomer (b) having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)"); Resin [K2]; a copolymer having a structural unit derived from (a), a structural unit derived from (b), and a structural unit derived from a monomer (c) copolymerizable with (a) (provided that it is different from (a) and (b)) (hereinafter sometimes referred to as "(c)"); Resin [K3]; a copolymer having a structural unit derived from (a) and a structural unit derived from (c); Resin [K4]; a copolymer having a structural unit obtained by adding (b) to the structural unit derived from (a) and a structural unit derived from (c); Resin [K5]; a copolymer having a structural unit obtained by adding (a) to the structural unit derived from (b) and a structural unit derived from (c); Resin [K6]; a copolymer having a structural unit obtained by adding (a) to the structural unit derived from (b) and further adding a carboxylic anhydride and a structural unit derived from (c).

[0137] Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, etc.; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic acid, etc.; Bicyclic unsaturated compounds containing a carboxy group such as methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; Unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; Unsaturated mono[(meth)acryloyloxyalkyl] esters of polyvalent carboxylic acids with a valency of 2 or more such as succinic acid mono[2-(meth)acryloyloxyethyl], phthalic acid mono[2-(meth)acryloyloxyethyl]; Unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule such as α-(hydroxymethyl)acrylic acid, etc. may be mentioned. Among these, from the viewpoints of copolymerization reactivity and solubility of the resulting resin in an aqueous alkali solution, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable.

[0138] (b) refers to a polymerizable compound having, for example, 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 an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group. In addition, in this specification, “(meth)acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Expressions such as “(meth)acryloyl” and “(meth)acrylate” also have the same meaning.

[0139] Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b2)”), and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”).

[0140] Examples of (b1) include a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-1)”), and a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).

[0141] Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, and the like.

[0142] Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Corporation), the compound represented by formula (I), the compound represented by formula (II), and the like.

[0143] [Chemical formula]

[0144] [In formula (I) and formula (II), R a and R b each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group. X a and X b each represent a single bond, *-R c -, *-R c -O-, *-R c -S- or *-R c -NH-. R c represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond to O.]

[0145] Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and the like. Examples of the alkyl group in which the hydrogen atom is substituted with hydroxy include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, a 4-hydroxybutyl group, and the like. Ra and R b Examples thereof preferably include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably include a hydrogen atom and a methyl group.

[0146] Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group. X a and X b Examples thereof preferably include a single bond, a methylene group, an ethylene group, *-CH2-O- and *-CH2CH2-O- (where * represents a bond to O), and more preferably include a single bond and *-CH2CH2-O-.

[0147] Examples of the compound represented by formula (I) include compounds represented by any of formula (I-1) to formula (I-15). Among them, compounds represented by formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) to formula (I-15) are preferred, and compounds represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15) are more preferred.

[0148] [Chemical formula]

[0149] [Chemical formula]

[0150] Examples of the compound represented by formula (II) include compounds represented by any of formula (II-1) to formula (II-15). Among them, compounds represented by formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15) are preferred, and compounds represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) are more preferred.

[0151] [Chemical formula]

[0152] [Chemical formula]

[0153] The compound represented by formula (I) and the compound represented by formula (II) may be used alone or in combination of two or more. When the compound represented by formula (I) and the compound represented by formula (II) are used in combination, their content ratios [compound represented by formula (I): compound represented by formula (II)] are preferably 5:95 to 95:5, more preferably 20:80 to 80:20, on a molar basis.

[0154] As (b2), a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane and the like.

[0155] As (b3), a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable. Specifically, examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate and the like.

[0156] (b) is preferably (b1) in that the reliability such as heat resistance and chemical resistance of the obtained color filter can be made higher. Further, (b1-2) is more preferable in that the storage stability of the coloring curable resin composition is excellent.

[0157] (c) includes methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 decane-8-yl (meth)acrylate (in the art, it is commonly referred to as "dicyclopentanyl (meth)acrylate". It may also be referred to as "tricyclodecyl (meth)acrylate".), tricyclo[5.2.1.0 2,6 decen-8-yl (meth)acrylate (in the art, it is commonly referred to as "dicyclopentenyl (meth)acrylate"), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate and other (meth)acrylic acid esters; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and other hydroxy group-containing (meth)acrylic acid esters; Diethyl maleate, diethyl fumarate, diethyl itaconate and other dicarboxylic acid diesters; Bicyclic unsaturated compounds such as bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, etc.; Dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl 3-maleimidobenzoate, N-succinimidyl 4-maleimidobutyrate, N-succinimidyl 6-maleimidocaproate, N-succinimidyl 3-maleimidopropionate, N-(9-acridinyl)maleimide, etc.; Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc. can be mentioned. Among these, from the viewpoints of copolymerization reactivity and heat resistance, 2-hydroxyethyl (meth)acrylate, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, etc. are preferable.

[0158] In resin [K1], the ratio of the structural units derived from each is among all the structural units constituting resin [K1], (a) The structural unit derived from; 2 to 60 mol% (b) The structural unit derived from; 40 to 98 mol% It is preferably that, (a) The structural unit derived from; 10 to 50 mol% (b) The structural unit derived from; 50 to 90 mol% It is more preferable that it is so. When the ratio of the structural units of the resin [K1] is within the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter can be excellent.

[0159] The resin [K1] can be produced, for example, with reference to the methods described in the literature "Experimental Methods of Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, issued on March 1, 1972) and the cited references described in the literature.

[0160] Specifically, examples of the method include putting predetermined amounts of (a) and (b), a polymerization initiator, a solvent, etc. into a reaction vessel, creating a deoxygenated atmosphere by replacing oxygen with nitrogen, for example, and heating and keeping warm while stirring. The polymerization initiator and solvent used here are not particularly limited, and those commonly used in the art can be used. For example, as the polymerization initiator, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) can be mentioned. As the solvent, any solvent that can dissolve each monomer may be used, and solvents such as the solvents described later as the solvent (E) of the colored curable resin composition of the present invention can be mentioned.

[0161] Note that the obtained copolymer may be used as the reaction solution as it is, or a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation may be used. In particular, by using the solvent contained in the colored curable resin composition of the present invention as the solvent during this polymerization, the reaction solution can be used as it is for the preparation of the colored curable resin composition of the present invention, so the manufacturing process of the colored curable resin composition of the present invention can be simplified.

[0162] In the resin [K2], the ratio of the structural units derived from each is among all the structural units constituting the resin [K2], (a) Structural units derived from; 2 to 45 mol% Structural unit derived from (b); 2 to 95 mol% Structural unit derived from (c); 1 to 65 mol% It is preferable that Structural unit derived from (a); 5 to 40 mol% Structural unit derived from (b); 5 to 80 mol% Structural unit derived from (c); 5 to 60 mol% it is more preferable that When the ratio of the structural units of resin [K2] is within the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance, heat resistance, and mechanical strength of the resulting color filter can be excellent.

[0163] Resin [K2] can be produced, for example, in the same manner as the method described as the production method of resin [K1].

[0164] In resin [K3], the ratio of the structural units derived from each is among all the structural units constituting resin [K3], Structural unit derived from (a); 2 to 60 mol% Structural unit derived from (c); 40 to 98 mol% it is preferable that Structural unit derived from (a); 10 to 50 mol% Structural unit derived from (c); 50 to 90 mol% it is more preferable that Resin [K3] can be produced, for example, in the same manner as the method described as the production method of resin [K1].

[0165] Resin [K4] can be produced by obtaining a copolymer of (a) and (c) and adding the cyclic ether having 2 to 4 carbon atoms that (b) has to the carboxylic acid and / or carboxylic anhydride that (a) has. First, a copolymer of (a) and (c) is produced in the same manner as the method described as the production method of resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same as that listed for resin [K3].

[0166] Next, a cyclic ether having 2 to 4 carbon atoms in (b) is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer. Following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b), a reaction catalyst for the reaction of the carboxylic acid or carboxylic anhydride with the cyclic ether (for example, tris(dimethylaminomethyl)phenol, etc.) and a polymerization inhibitor (for example, hydroquinone, etc.) are put into the flask, and then reacted at, for example, 60 to 130 °C for 1 to 10 hours to produce resin [K4]. The amount of (b) used is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). By setting it within this range, the storage stability of the colored curable resin composition, the developability when forming a pattern, and the balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern can be made good. Since the reactivity of the cyclic ether is high and unreacted (b) is less likely to remain, (b1) is preferred as (b) used in resin [K4], and further (b1-1) is preferred. The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b), and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b), and (c). The reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment, the heat generation amount due to polymerization, etc. Similar to the polymerization conditions, the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the heat generation amount due to polymerization, etc.

[0167] As a first step, resin [K5] is obtained in the same manner as the production method of resin [K1] described above to obtain a copolymer of (b) and (c). Similar to the above, the obtained copolymer may be used as the reaction solution as it is, or a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation may be used. The ratios of the structural units derived from (b) and (c) are respectively based on the total number of moles of all the structural units constituting the copolymer. Structural unit derived from (b); 5 to 95 mol% Structural unit derived from (c); 5 to 95 mol% It is preferably that Structural unit derived from (b); 10 to 90 mol% Structural unit derived from (c); 10 to 90 mol% It is more preferably that

[0168] Furthermore, under the same conditions as the production method of resin [K4], by reacting the cyclic ether derived from (b) in the copolymer of (b) and (c) with the carboxylic acid or carboxylic anhydride that (a) has, resin [K5] can be obtained. The usage amount of (a) to be reacted with the copolymer is preferably 5 to 80 mol with respect to 100 mol of (b). Since the cyclic ether has high reactivity and unreacted (b) hardly remains, (b1) is preferable as (b) used for resin [K5], and (b1-1) is more preferable.

[0169] Resin [K6] is a resin obtained by further reacting resin [K5] with a carboxylic anhydride. The carboxylic anhydride is reacted with the hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or carboxylic anhydride. Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride and the like. The usage amount of the carboxylic anhydride is preferably 0.5 to 1 mol with respect to 1 mol of the usage amount of (a).

[0170] Specific examples of resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6Resins such as decyl acrylate / (meth)acrylic acid copolymer [K1]; glycidyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, glycidyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 decyl acrylate / (meth)acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 decyl acrylate / (meth)acrylic acid / N-cyclohexylmaleimide / 2-hydroxyethyl (meth)acrylate copolymer, resins such as 3-methyl-3-(meth)acryloyloxymethyloxetane / (meth)acrylic acid / styrene copolymer [K2]; resins such as benzyl (meth)acrylate / (meth)acrylic acid copolymer, styrene / (meth)acrylic acid copolymer [K3]; resins such as resins obtained by adding glycidyl (meth)acrylate to benzyl (meth)acrylate / (meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer [K4]; resins such as resins obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate, resins obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / styrene / glycidyl (meth)acrylate [K5]; resins such as resins obtained by further reacting tetrahydrophthalic anhydride with a resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate [K6], etc. can be mentioned. Among them, as the resin (B), the resin [K1] and the resin [K2] are preferable, and the resin [K1] is particularly preferable.

[0171] The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 or more and 100,000 or less, more preferably 5,000 or more and 50,000 or less, and still more preferably 5,000 or more and 30,000 or less. When the molecular weight is within the above range, the hardness of the color filter can be improved, the residual film rate is high, the solubility in the developer of the unexposed portion is good, and the resolution of the colored pattern can be improved.

[0172] The dispersity [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 or more and 6 or less, and more preferably 1.2 or more and 4 or less.

[0173] The acid value of the resin (B) in terms of solid content is preferably 50 mg-KOH / g or more and 170 mg-KOH / g or less, more preferably 60 mg-KOH / g or more and 150 mg-KOH / g or less, and still more preferably 70 mg-KOH / g or more and 135 mg-KOH / g or less. Here, 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 using an aqueous potassium hydroxide solution.

[0174] The content of the resin (B) is preferably 7% by mass or more and 65% by mass or less, more preferably 13% by mass or more and 60% by mass or less, and still more preferably 17% by mass or more and 55% by mass or less with respect to the total amount of the solid content. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and residual film rate of the colored pattern can be improved.

[0175] <Polymerizable compound (C)> The polymerizable compound (C) is a compound that can be polymerized by active radicals and / or acids generated from the polymerization initiator (D), and its hydroxyl value is 100 mgKOH / g or more. According to the colored curable resin composition of the present invention containing the polymerizable compound (C), it is possible to make the cured film thinner. Also, in a preferred embodiment, the lightness of the obtained cured film can be good.

[0176] The polymerizable compound (C) may consist of one type of polymerizable compound having a hydroxyl value of 100 mgKOH / g or more, or may contain two or more types of polymerizable compounds having a hydroxyl value of 100 mgKOH / g or more. Further, the polymerizable compound (C) may be a mixture of one or more types of polymerizable compounds having a hydroxyl value of 100 mgKOH / g or more and one or more types of polymerizable compounds having a hydroxyl value of less than 100 mgKOH / g. When two or more types of polymerizable compounds are included as the polymerizable compound (C), the hydroxyl value of the polymerizable compound (C) refers to the hydroxyl value of the mixture. The hydroxyl value of the polymerizable compound (C) is measured according to the description of the examples described later.

[0177] The hydroxyl value of the polymerizable compound (C) is preferably 110 mgKOH / g or more, more preferably 180 mgKOH / g or more, still more preferably 200 mgKOH / g or more, and particularly preferably 250 mgKOH / g or more. When the hydroxyl value of the polymerizable compound (C) is within the above range, it becomes possible to thin the obtained cured film, and in a preferred embodiment, the lightness of the obtained cured film can be good. Further, from the viewpoint of easy availability, the hydroxyl value of the polymerizable compound (C) is preferably 500 mgKOH / g or less, more preferably 450 mgKOH / g or less, still more preferably 400 mgKOH / g or less, even more preferably 350 mgKOH / g or less, and particularly preferably 300 mgKOH / g or less.

[0178] Examples of the polymerizable compound (C) include compounds having a polymerizable ethylenically unsaturated bond and a hydroxyl group. The average number of double bonds of the polymerizable compound (C) is 1.0 or more, preferably 2.0 or more, still more preferably 2.5 or more, and preferably 4.0 or less, more preferably 3.5 or less, still more preferably 3.0 or less. The average number of double bonds of the polymerizable compound (C) can be measured by analytical means such as HPLC (high performance liquid chromatography).

[0179] Specific examples of the polymerizable compound having a hydroxyl value of 100 mgKOH / g or more include pentaerythritol tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol mono(meth)acrylate, ethylene glycol-modified pentaerythritol tri(meth)acrylate, propylene glycol-modified pentaerythritol triacrylate, trimethylolpropane di(meth)acrylate, ethylene glycol-modified trimethylolpropane di(meth)acrylate, ethylene glycol-modified glycerin di(meth)acrylate, propylene glycol-modified glycerin di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ethylene glycol-modified ditrimethylolpropane tri(meth)acrylate, propylene glycol-modified ditrimethylolpropane triacrylate, dipentaerythritol pentaacrylate, and the like. The polymerizable compound (C) preferably contains at least pentaerythritol tri(meth)acrylate, and more preferably contains pentaerythritol triacrylate. When the polymerizable compound (C) contains pentaerythritol tri(meth)acrylate (preferably pentaerythritol triacrylate), its content is preferably 10% by mass or more, more preferably 25% by mass or more, still more preferably 40% by mass or more in the polymerizable compound (C), and may be 100% by mass, may be 90% by mass or less, or may be 80% by mass or less.

[0180] The content of the polymerizable compound having a hydroxyl value of 100 mgKOH / g or more in the polymerizable compound (C) is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, may be 100% by mass, may be 98% by mass or less, or may be 93% by mass or less.

[0181] When the polymerizable compound (C) is a mixture of two or more polymerizable compounds, the polymerizable compound (C) may contain a polymerizable compound having a hydroxyl value of less than 100 mgKOH / g as long as the hydroxyl value of the mixture is not less than 100 mgKOH / g. Specific examples of the polymerizable compound having a hydroxyl value of less than 100 mgKOH / g include trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate.

[0182] The content of the polymerizable compound (C) is preferably 7% by mass or more, more preferably 13% by mass or more, still more preferably 20% by mass or more, and preferably 65% by mass or less, more preferably 55% by mass or less, still more preferably 45% by mass or less, based on the total amount of the solid content. When the content of the polymerizable compound (C) is within the above range, the obtained cured film can be thinned, and the residual film rate during coloring pattern formation and the chemical resistance of the color filter can be improved.

[0183] <Polymerization initiator (D)> The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. upon the action of light or heat and can initiate polymerization, and known polymerization initiators can be used. Examples of the polymerization initiator that generates active radicals include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyl oxime compounds, and biimidazole compounds.

[0184] The O-acyl oxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond.

[0185]

Chemical formula

[0186] Examples of the O-acyl oxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine, N-acyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine. Commercially available products such as Irgacure OXE01 and OXE02 (manufactured by BASF), N-1919 (manufactured by ADEKA), and PBG-327 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) may be used. Among them, the O-acyl oxime compound is preferably at least one selected from the group consisting of N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, and N-acyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine, and more preferably at least one selected from the group consisting of N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-acyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine.With these O-acyl oxime compounds, a high-brightness color filter can be obtained.

[0187] The alkylphenone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). In these partial structures, the benzene ring may have a substituent.

[0188]

Chemical formula

[0189] Examples of the compound having a partial structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one. Commercially available products such as Irgacure 369, 907, 379 (manufactured by BASF) may also be used. Examples of the compound having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, an oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyldimethyl ketal. In terms of sensitivity, as the alkylphenone compound, a compound having a partial structure represented by formula (d2) is preferred.

[0190] Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

[0191] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may also be used.

[0192] Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, JP-B-48-38403 and JP-A-62-174204), and biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboxyalkoxy groups (see, for example, JP-A-7-10913).

[0193] Furthermore, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation aid (D1) (particularly amines) described later.

[0194] Examples of the acid generator include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylates, benzoin tosylate, and the like.

[0195] As the polymerization initiator (D), a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyl oxime compound, and a biimidazole compound is preferable, and a polymerization initiator containing an O-acyl oxime compound is more preferable.

[0196] The content of the polymerization initiator (D) is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, the sensitivity can be increased and the exposure time can be shortened, so that the productivity of the color filter is improved.

[0197] <Polymerization initiation aid (D1)> The polymerization initiation aid (D1) is a compound or a sensitizer used to promote the polymerization of the polymerizable compound whose polymerization has been initiated by the polymerization initiator. When the polymerization initiation aid (D1) is included, it is usually used in combination with the polymerization initiator (D). Examples of the polymerization initiation aid (D1) include amine compounds, alkoxy anthracene compounds, thioxanthone compounds, carboxylic acid compounds, and the like.

[0198] Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc. Among them, 4,4'-bis(diethylamino)benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may also be used.

[0199] Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

[0200] Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, etc.

[0201] Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.

[0202] When using these polymerization initiation aids (D1), their content is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern with higher sensitivity can be formed, and the productivity of the color filter can be improved.

[0203] <Solvent (E)> The solvent (E) is not particularly limited, and solvents commonly used in the art can be used. For example, ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide can be mentioned.

[0204] Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0205] Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and methyl anisole, among others.

[0206] Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate, among others.

[0207] Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0208] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0209] Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

[0210] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0211] Among the above solvents, from the viewpoints of coatability and drying property, an organic solvent having a boiling point of 120°C or higher and 180°C or lower at 1 atm is preferred. Preferred solvents include propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, and N,N-dimethylformamide, and more preferred are propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, and 4-hydroxy-4-methyl-2-pentanone.

[0212] The content rate of the solvent (E) is preferably 70% by mass or more and 95% by mass or less, more preferably 75% by mass or more and 92% by mass or less, with respect to the total amount of the colored curable resin composition of the present invention. In other words, the total content rate of the solid content of the colored curable resin composition is preferably 5% by mass or more and 30% by mass or less, more preferably 8% by mass or more and 25% by mass or less. When the content rate of the solvent (E) is within the above range, the flatness during coating becomes good, and the display characteristics can be good because the color density is not insufficient when forming a color filter.

[0213] <Leveling agent (F)> Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms. These may have a polymerizable group in the side chain. Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan LLC) etc. can be mentioned.

[0214] Examples of the fluorosurfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), F-Top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surfynol (registered trademark) S381, S382, SC101, SC105 (manufactured by AGC Inc.), and E5844 (manufactured by Daikin Fine Chemical Research Institute Co., Ltd.) etc. can be mentioned.

[0215] Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation) etc. can be mentioned.

[0216] The content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.2% by mass or less, and still more preferably 0.01% by mass or more and 0.2% by mass or less with respect to the total amount of the colored curable resin composition. Incidentally, the dispersant is not included in this content. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

[0217] <Other components> The colored curable resin composition of the present invention may contain additives known in the art, such as a filler, other polymer compounds, an adhesion promoter, a light stabilizer, a chain transfer agent, etc., if necessary. Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane.

[0218] <Method for producing colored curable resin composition> The colored curable resin composition of the present invention can be prepared, for example, by mixing a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), a leveling agent (F), a polymerization initiation aid (D1), and other components used as necessary.

[0219] The colorant (A) may be mixed in advance with part or all of the solvent (E) and dispersed using a bead mill or the like until the average particle size is about 0.2 μm or less as necessary. At this time, the dispersant and part or all of the resin (B) may be blended as necessary. It is preferable to prepare the target colored composition by mixing the remaining components into the dispersion liquid thus obtained so as to have a predetermined concentration. When using a bead mill, the diameter of the beads is preferably 0.05 mm or more and 0.5 mm or less, and examples of the bead material include glass, ceramic, and metal.

[0220] <Method for manufacturing a color filter> As a method for manufacturing a colored pattern of a color filter from the colored curable resin composition of the present invention, a photolithography method, an inkjet method, a printing method, etc. can be mentioned. Among them, the photolithography method is preferable. The photolithography method is a method in which the colored curable resin composition is applied to a substrate, dried to form a composition layer, and the composition layer is exposed and developed through a photomask. In the photolithography method, a colored coating film that is a cured product of the composition layer can be formed by not using a photomask and / or not developing during exposure.

[0221] The film thickness of the color filter (cured film) is, for example, 0.1 μm or more and 30 μm or less, preferably 0.1 μm or more and 20 μm or less, and more preferably 0.5 μm or more and 6 μm or less.

[0222] As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, or soda lime glass with a silica-coated surface, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, silicon, or a substrate with an aluminum, silver, or silver / copper / palladium alloy thin film formed on the substrate is used. Another color filter layer, resin layer, transistor, circuit, etc. may be formed on these substrates. Also, a substrate subjected to HMDS treatment on a silicon substrate may be used.

[0223] The formation of each color pixel by photolithography can be carried out with known or conventional devices and conditions. For example, it can be produced as follows. First, a coloring composition is applied onto a substrate, and volatile components such as solvents are removed by heating and drying (pre-baking) and / or drying under reduced pressure to obtain a smooth composition layer. Examples of the coating method include spin coating method, slit coating method, slit and spin coating method, etc. When performing heating and drying, the temperature is preferably 30°C or higher and 120°C or lower, more preferably 50°C or higher and 110°C or lower. Also, the heating time is preferably 10 seconds or longer and 60 minutes or shorter, more preferably 30 seconds or longer and 30 minutes or shorter. When performing drying under reduced pressure, it is preferably carried out in a temperature range of 20 - 25°C under a pressure of 50 - 150 Pa. The film thickness of the composition layer is not particularly limited and may be appropriately selected according to the film thickness of the target color filter.

[0224] Next, the composition layer is exposed through a photomask for forming the target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the target application is used. Also, for forming a colored coating film, it is exposed without using a photomask. As the light source used for exposure, a light source that generates light with a wavelength of 250 - 450 nm is preferable. For example, light with a wavelength of less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, near 408 nm, or near 365 nm can be selectively extracted using a band-pass filter that extracts these wavelength ranges. Specifically, mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, etc. can be mentioned. Since it is possible to irradiate the entire exposure surface with parallel light rays uniformly or perform accurate alignment between the photomask and the substrate, it is preferable to use a reduction projection exposure apparatus such as a mask aligner and a stepper or a proximity exposure apparatus.

[0225] By bringing the composition layer after exposure into contact with a developer for development, a colored pattern is formed on the substrate. By development, the unexposed portion of the composition layer is dissolved and removed by the developer. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration in the aqueous solution of these alkaline compounds is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.03% by mass or more and 5% by mass or less. Further, the developer may contain a surfactant. The development method may be any of a paddle method, a dipping method, a spray method, etc. Further, the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to perform water washing.

[0226] Furthermore, it is preferable to perform post-baking on the obtained colored pattern and colored coating film. The post-baking temperature is preferably 80°C or higher and 250°C or lower, and more preferably 100°C or higher and 245°C or lower. The post-baking time is preferably 1 minute or longer and 120 minutes or shorter, and more preferably 2 minutes or longer and 30 minutes or shorter.

[0227] The colored pattern and colored coating film thus obtained are useful as a color filter, and the color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, etc.), electronic paper, a solid-state imaging device, etc.

Example

[0228] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples. In the examples, % and parts representing content or usage amount are based on mass unless otherwise specified.

[0229] In the following, the structure of the compound was confirmed by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type).

[0230] 〔Synthesis Example 1 of Colorant〕 The following reaction was carried out under a nitrogen atmosphere. 26.4 parts of potassium thiocyanate and 156 parts of acetonitrile were charged into a flask equipped with a cooling tube and a stirrer, and then stirred at room temperature for 30 minutes. 40.0 parts of 2,6-difluorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the flask over 30 minutes, and then stirred at room temperature for 1 hour. 30.6 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the flask over 30 minutes, and then stirred at room temperature for 1 hour. An aqueous solution prepared by dissolving 79.2 parts of sodium monochloroacetate in 120 parts of ion-exchanged water was added to the flask, and 60.4 parts of 30% aqueous sodium hydroxide solution was added, followed by stirring at room temperature for 18 hours. 600 parts of ion-exchanged water was further added to the flask, and then stirred for 1 hour. The precipitated yellowish-white solid was collected by filtration. The obtained yellowish-white solid was washed with 120 parts of acetonitrile and then with 560 parts of ion-exchanged water. The washed yellowish-white solid, 156 parts of ion-exchanged water, 35.0 parts of 99% acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.), and 156 parts of toluene were charged into a flask equipped with a stirrer, and stirred at room temperature for 2 hours. 80.8 parts of 30% aqueous sodium hydroxide solution was added dropwise thereto over 10 minutes, followed by stirring for 5 minutes, and the aqueous layer was removed by liquid separation operation. 156 parts of ion-exchanged water was added to the obtained organic layer for liquid separation washing, and then 156 parts of ion-exchanged water and 0.1 part of 35% hydrochloric acid were added for liquid separation washing. The obtained organic layer was concentrated by an evaporator and then dried under reduced pressure at 35 °C to obtain the compound represented by formula (B-I-1) as a white solid. The yield was 43.4 parts and the yield rate was 58.0%.

[0231] [Chemical formula]

[0232] The following reaction was carried out under a nitrogen atmosphere. After adding 13.2 parts of the compound represented by the formula (B-I-1), 19.0 parts of the compound represented by the formula (C-I-1) and 38 parts of toluene into a flask equipped with a cooling tube and a stirring device, 9.2 parts of phosphorus oxychloride was then added and the mixture was stirred at 100 °C for 7 hours. Then the reaction mixture was cooled to room temperature and diluted with 29 parts of methyl ethyl ketone. Next, a mixed solution of 114 parts of ion-exchanged water and 10 parts of 35% hydrochloric acid aqueous solution was poured into the diluted reaction mixture, and the aqueous layer was removed by liquid separation operation. After distilling off the solvent from the obtained organic layer with an evaporator, drying was carried out at 60 °C under reduced pressure to obtain the compound represented by the formula (X-II-1) as a blue-violet solid. The amount of the obtained blue-violet solid was 39.4 parts.

[0233]

Chemical formula

[0234]

Chemical formula

[0235] The following reaction was carried out under a nitrogen atmosphere. 38.4 parts of the compound represented by the formula (X-II-1) and 112 parts of methylene chloride were charged into a flask equipped with a cooling tube and a stirring device, and stirred for 30 minutes. The reaction solution was ice-cooled, and while maintaining the internal temperature at 10°C, 31.6 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. Then, the reaction solution was warmed to room temperature and stirred for 9 hours. Next, the reaction solution was ice-cooled, and while maintaining the internal temperature at 10°C, it was diluted with a mixed solution of 64 parts of N,N-dimethylformamide and 4.9 parts of ion-exchanged water. The diluted reaction solution was poured into 1120 parts of toluene, and after stirring for 30 minutes, a viscous solid precipitated. After discharging the oil layer by decantation, 320 parts of toluene was added to the obtained viscous solid and stirred for 30 minutes. After discharging the oil layer by decantation, 832 parts of 20% brine was added to the obtained viscous solid and stirred for 1 hour, and then the blue solid was collected by filtration. The obtained blue solid was washed with 576 parts of 20% brine and dried under reduced pressure at 35°C. The obtained solid and 128 parts of methanol were charged into a flask equipped with a stirring device, stirred for 30 minutes, and then filtered to separate into a solid and a filtrate. This filtrate was designated as filtrate A3. The solid collected by filtration was washed with 192 parts of methanol and separated into a solid and a filtrate by filtration. This filtrate was designated as filtrate B3. Filtrate A3 and filtrate B3 were mixed, the solvent was removed with an evaporator, and then dried under reduced pressure at 40°C to obtain the compound represented by the formula (X-I-1) as a blue-violet solid. The amount of the obtained blue-violet solid was 38.3 parts.

[0236] [Chemical formula]

[0237] 28.0 parts of the compound represented by the formula (X-I-1), 43.2 parts of barium chloride dihydrate, and 356 parts of ion-exchanged water were added to a flask equipped with a stirring device, stirred at 40°C for 2 hours, and then the reaction suspension was filtered. The solid collected by filtration and 350 parts of ion-exchanged water were charged into a flask equipped with a stirring device, stirred for 30 minutes, and then the suspension was filtered. The obtained solid was washed with 280 parts of ion-exchanged water and then dried under reduced pressure at 60°C to obtain the compound represented by the formula (A-I-1) as a blue-violet solid. The amount obtained was 24.5 parts, and the yield was 81.7%.

[0238]

Chem.

[0239] Identification of the compound represented by formula (A-I-1) (Mass spectrometry) Ionization mode = ESI-: m / z = 949.5 [M - Ba + 2H] - Exact Mass [M - Ba]: 947.28

[0240] 〔Synthesis Example 2 of Colorant〕 40.5 parts of the compound represented by formula (1a) and 60.5 parts of 2,6 - xylidine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed under light - shielding conditions, and the mixture was stirred at 150 °C for 8 hours in 200 parts of N - methylpyrrolidone. After the obtained reaction solution was cooled to room temperature, it was added to a mixed solution of 1200 parts of water and 75 parts of 35% hydrochloric acid and stirred at room temperature for 1 hour, and crystals precipitated. The precipitated crystals were obtained as the residue of suction filtration, washed with 100 parts of methanol, and dried under reduced pressure at 60 °C overnight to obtain 49 parts of the compound represented by formula (1 - 32). The yield was 85%.

[0241]

Chem.

[0242]

Chem.

[0243] 〔Synthesis Example 1 of Resin〕 An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the atmosphere was replaced with a nitrogen atmosphere. 280 parts of propylene glycol monomethyl ether acetate was put in, and the mixture was heated to 80 °C while stirring. Then, 38 parts of acrylic acid, 3,4 - epoxytricyclo[5.2.1.0 2,6 decane - 8 - yl acrylate and 3,4 - epoxytricyclo[5.2.1.0 2,6A mixed solution of 289 parts of a mixture of decan-9-yl acrylate (the content ratio is 1:1 in molar ratio) and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a solution prepared by dissolving 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was held at 80 °C for 4 hours and then cooled to room temperature to obtain a copolymer (resin B1) solution with a solid content of 35.1% and a viscosity of 125 mPas measured with a B-type viscometer (23 °C). The weight average molecular weight Mw of the produced copolymer was 9.2×10 3 , the dispersity was 2.08, and the acid value in terms of solid content was 77 mg-KOH / g. Resin B1 has the following structural units.

[0244]

Chemical formula

[0245] The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin in terms of polystyrene was carried out under the following conditions by the GPC method. Apparatus; HLC-8120GPC (manufactured by Tosoh Corporation) Column; TSK-GEL G2000HXL Column temperature; 40 °C Solvent; THF Flow rate; 1.0 mL / min Concentration of the test solution solid content; 0.001 - 0.01 mass% Injection volume; 50 μL Detector; RI Standard substance for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation) The ratio (Mw / Mn) of the weight average molecular weight and number average molecular weight in terms of polystyrene obtained above was defined as the dispersity.

[0246] 〔Preparation of Colorant Dispersion 1〕 23.1 parts of the compound represented by the formula (A-I-1), 28.8 parts of a dispersant (BYKLPN-6919 manufactured by BYK Chemie; 60% solution of propylene glycol monomethyl ether acetate), 5.8 parts of resin B1 (in terms of solid content), 28.9 parts of 4-hydroxy-4-methyl-2-pentanone, and 202 parts of propylene glycol monomethyl ether acetate were mixed, 600 parts of 0.4 μm zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to obtain a colorant dispersion liquid 1.

[0247] 〔Comparative Example 1〕 〔Preparation of Coloring Curing Resin Composition 1〕 The coloring curing resin composition 1 was obtained by mixing a colorant dispersion liquid 1, the compound represented by the formula (1-32), a resin, a polymerizable compound, a polymerization initiator, a solvent, and a leveling agent so as to have the composition shown below. The coloring curing resin composition 1 contains, as a colorant (A), 2.5 parts of the compound represented by the formula (A-I-1) and 0.2 part of the compound represented by the formula (1-32); as a dispersant, 1.9 parts (in terms of solid content) of BYKLPN-6919 (manufactured by BYK Chemie); as a resin (B), 7.8 parts (in terms of solid content) of resin B1; as a polymerizable compound (C), 5.2 parts of KAYARAD (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate, hydroxyl value: 10 mg KOH / g); as a polymerization initiator (D), 0.4 part of PBG-327 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd., N-acyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine, oxime compound); as a solvent (E), 78.9 parts of propylene glycol monomethyl ether acetate and 3.1 parts of 4-hydroxy-4-methyl-2-pentanone; and as a leveling agent (F), 0.01 part (in terms of solid content) of Toray Silicone SH8400 (manufactured by Toray Dow Corning Co., Ltd., polyether-modified silicone oil).

[0248] 〔Comparative Example 2〕 〔Preparation of Coloring Curing Resin Composition 2〕 The coloring agent dispersion liquid 1, the compound represented by the formula (1-32), the resin, the polymerizable compound, the polymerization initiator, the solvent, and the leveling agent were mixed so as to have the composition shown below to obtain a colored curable resin composition 2. The colored curable resin composition 2 contains, as the coloring agent (A), 2.5 parts of the compound represented by the formula (A-I-1) and 0.2 part of the compound represented by the formula (1-32); as the dispersant, 1.9 parts (in terms of solid content) of BYKLPN-6919 (manufactured by BYK Chemie); as the resin (B), 7.8 parts (in terms of solid content) of resin B1; as the polymerizable compound (C), 3.8 parts of KAYARAD (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate, hydroxyl value: 10 mgKOH / g), 1.5 parts of Aronix (registered trademark) M-933 (manufactured by Toagosei Co., Ltd., hydroxyl value: 280 mgKOH / g); as the polymerization initiator (D), 0.4 part of PBG-327 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd., N-acyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine, oxime compound); as the solvent (E), 78.9 parts of propylene glycol monomethyl ether acetate and 3.1 parts of 4-hydroxy-4-methyl-2-pentanone; as the leveling agent (F), 0.01 part (in terms of solid content) of Toray silicone SH8400 (manufactured by Toray Dow Corning Co., Ltd., polyether-modified silicone oil). The colored curable resin composition is composed of these components. The hydroxyl value of the mixture of the polymerizable compound (C) was 86 mgKOH / g.

[0249] 〔Comparative Example 3〕 〔Preparation of Colored Curable Resin Composition 3〕 The colorant dispersion liquid 1, resin, polymerizable compound, polymerization initiator, solvent, and leveling agent were mixed so as to have the composition shown below to obtain a colored curable resin composition 3. The colored curable resin composition 3 contains, as the colorant (A), 2.7 parts of the compound represented by the formula (A-I-1); as the dispersant, 2.0 parts (in terms of solid content) of BYKLPN-6919 (manufactured by BYK Chemie); as the resin (B), 7.7 parts (in terms of solid content) of resin B1; as the polymerizable compound (C), 5.2 parts of KAYARAD (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate, hydroxyl value: 10 mg KOH / g); as the polymerization initiator (D), 0.4 parts of PBG-327 (manufactured by Changzhou Strong New Materials Co., Ltd., N-acyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine, oxime compound); as the solvent (E), 78.6 parts of propylene glycol monomethyl ether acetate and 3.4 parts of 4-hydroxy-4-methyl-2-pentanone; as the leveling agent (F), 0.01 part (in terms of solid content) of Toray silicone SH8400 (manufactured by Toray Dow Corning Co., Ltd., polyether-modified silicone oil).

[0250] Example 1 Preparation of Colored Curable Resin Composition 4 The colorant dispersion liquid 1, the compound represented by the formula (1-32), the resin, the polymerizable compound, the polymerization initiator, the solvent, and the leveling agent were mixed so as to have the composition shown below to obtain a colored curable resin composition 4. The colored curable resin composition 4 contains, as the colorant (A), 2.5 parts of the compound represented by the formula (A-I-1) and 0.2 part of the compound represented by the formula (1-32); as the dispersant, 1.9 parts (in terms of solid content) of BYKLPN-6919 (manufactured by BYK Chemie GmbH); as the resin (B), 7.8 parts (in terms of solid content) of resin B1; as the polymerizable compound (C), 5.2 parts of A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical Co., Ltd., hydroxyl value: 110 mg KOH / g); as the polymerization initiator (D), 0.4 part of PBG-327 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd., N-acyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine, oxime compound); as the solvent (E), 78.9 parts of propylene glycol monomethyl ether acetate and 3.1 parts of 4-hydroxy-4-methyl-2-pentanone; and as the leveling agent (F), 0.01 part (in terms of solid content) of Toray silicone SH8400 (manufactured by Toray Dow Corning Co., Ltd., polyether-modified silicone oil).

[0251] [Example 2] [Preparation of Colored Curable Resin Composition 5] The coloring agent dispersion liquid 1, the compound represented by the formula (1-32), the resin, the polymerizable compound, the polymerization initiator, the solvent, and the leveling agent were mixed so as to have the composition shown below to obtain a colored curable resin composition 5. The colored curable resin composition 5 contains, as the coloring agent (A), 2.5 parts of the compound represented by the formula (A-I-1) and 0.2 parts of the compound represented by the formula (1-32); as the dispersant, 1.9 parts (in terms of solid content) of BYKLPN-6919 (manufactured by BYK Chemie); as the resin (B), 7.8 parts (in terms of solid content) of resin B1; as the polymerizable compound (C), 5.2 parts of Aronix (registered trademark) M-933 (manufactured by Toagosei Co., Ltd., hydroxyl value: 280 mgKOH / g); as the polymerization initiator (D), 0.4 parts of PBG-327 (manufactured by Changzhou Strong New Materials Co., Ltd., N-acyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine, oxime compound); as the solvent (E), 78.9 parts of propylene glycol monomethyl ether acetate and 3.1 parts of 4-hydroxy-4-methyl-2-pentanone; as the leveling agent (F), 0.01 part (in terms of solid content) of Toray silicone SH8400 (manufactured by Toray Dow Corning Co., Ltd., polyether-modified silicone oil); and is a colored curable resin composition composed of these components.

[0252] Example 3 Preparation of Colored Curable Resin Composition 6 The coloring agent dispersion liquid 1, the compound represented by the formula (1-32), the resin, the polymerizable compound, the polymerization initiator, the solvent, and the leveling agent were mixed so as to have the composition shown below to obtain a colored curable resin composition 6. The colored curable resin composition 6 contains, as the coloring agent (A), 2.5 parts of the compound represented by the formula (A-I-1) and 0.2 part of the compound represented by the formula (1-32); as the dispersant, 1.9 parts (in terms of solid content) of BYKLPN-6919 (manufactured by BYK Chemie GmbH); as the resin (B), 7.8 parts (in terms of solid content) of resin B1; as the polymerizable compound (C), 2.5 parts of A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical Co., Ltd., hydroxyl value: 110 mgKOH / g) and 2.8 parts of Aronix (registered trademark) M-933 (manufactured by Toagosei Co., Ltd., hydroxyl value: 280 mgKOH / g); as the polymerization initiator (D), 0.4 part of PBG-327 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd., N-acyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine, oxime compound); as the solvent (E), 78.9 parts of propylene glycol monomethyl ether acetate and 3.1 parts of 4-hydroxy-4-methyl-2-pentanone; as the leveling agent (F), 0.01 part (in terms of solid content) of Toray silicone SH8400 (manufactured by Toray Dow Corning Co., Ltd., polyether-modified silicone oil). The colored curable resin composition is composed of these components. The hydroxyl value of the mixture of the polymerizable compound (C) was 200 mgKOH / g.

[0253] 〔Example 4〕 〔Preparation of Colored Curable Resin Composition 7〕 The coloring curable resin composition 7 was obtained by mixing a coloring agent dispersion liquid 1, a resin, a polymerizable compound, a polymerization initiator, a solvent, and a leveling agent so as to have the composition shown below. The coloring curable resin composition 7 contains, as a coloring agent (A), 2.7 parts of a compound represented by the formula (A-I-1); as a dispersant, 2.0 parts (in terms of solid content) of BYKLPN-6919 (manufactured by BYK Chemie); as a resin (B), 7.7 parts (in terms of solid content) of resin B1; as a polymerizable compound (C), 5.2 parts of Aronix (registered trademark) M-933 (manufactured by Toagosei Co., Ltd., hydroxyl value: 280 mgKOH / g); as a polymerization initiator (D), 0.4 parts of PBG-327 (manufactured by Changzhou Strong New Materials Co., Ltd., N-acyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine, an oxime compound); as a solvent (E), 78.6 parts of propylene glycol monomethyl ether acetate and 3.4 parts of 4-hydroxy-4-methyl-2-pentanone; as a leveling agent (F), 0.01 part (in terms of solid content) of Toray silicone SH8400 (manufactured by Toray Dow Corning Co., Ltd., polyether-modified silicone oil).

[0254] [Measurement of the hydroxyl value of the polymerizable compound] In accordance with JIS K 0070-1992, an acetylating reagent was added to the sample, heated in a glycerin bath, allowed to cool, a phenolphthalein solution was added as an indicator, and titration was performed with a potassium hydroxide ethanol solution for measurement. The measurement results are as described above.

[0255] [Preparation of the colored coating film (color filter)] On a 5 cm square glass substrate (Eagle 2000; manufactured by Corning), the coloring curable resin compositions 1 to 7 were each spin-coated so that the film thickness after post-baking would be 2.5 μm, and then pre-baked at 100°C for 3 minutes to form a coloring composition layer. After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Corporation), the coloring composition layer was irradiated with light at an exposure dose of 80 mJ / cm 2 (based on 365 nm) in an air atmosphere. Thereafter, post-baking was performed in an oven at 230°C for 30 minutes to obtain a colored coating film.

[0256] 〔Measurement of film thickness change rate〕 The chromaticity and film thickness of the obtained colored coating film were measured, and film thickness 1, x value 1, and Y value 1 were calculated when the y value was adjusted to 0.092. Then, the colored coating film was heated in an oven at 230 °C for 3 hours. The chromaticity and film thickness of the colored coating film after heating were measured, film thickness 2, x value 2, and Y value 2 were calculated when the y value was adjusted to 0.092, and the film thickness change rate was calculated based on the following formula. The results are shown in Table 10. Film thickness change rate = (film thickness 2 / film thickness 1) × 100

[0257] In addition, for the film thickness measurement of the above-mentioned colored coating film, a film thickness measurement device (DEKTAK3; manufactured by Nippon Vacuum Technologies Co., Ltd.) was used. The chromaticity was obtained as xy chromaticity coordinates (x, y) and stimulus value Y in the CIE XYZ color system from the spectral data measured by a colorimeter (OSP-SP-200; manufactured by Olympus Corporation) and the characteristic function of the C light source. Also, the color difference ΔE*ab was calculated by the method described in JIS Z 8730:2009 (7. Calculation method of color difference) from the chromaticity measurement values before and after heating. The results are shown in Table 10.

[0258]

Table 10

[0259] From the above results, although the colored curable resin composition of the present invention tends to have an increase in film thickness upon heating, the film thickness change rate is small. That is, it can be said that the phenomenon of the color becoming lighter upon heating is suppressed and a dark color can be maintained. Also, the color change due to heating is small, and a color filter with high brightness can be obtained.

Industrial applicability

[0260] According to the colored curable resin composition of the present invention, a dark-colored cured film that is a thin film can be provided. The color filter formed from the colored curable resin composition of the present invention is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL display devices, electronic paper, etc.) and solid-state imaging elements.

Claims

1. A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), wherein the colorant (A) contains a compound represented by formula (a), and the colored curable resin composition wherein the hydroxyl value of the polymerizable compound (C) is 100 mgKOH / g or more. 【Chemical 1】 [In formula (a), R 41 to R 44 each independently 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, and the substituent which the aromatic hydrocarbon group and the aralkyl group may have is -SO 3 - or -SO 2 -N - -SO 2 -R f and may be, when the carbon number of the saturated hydrocarbon group is 2 to 20, -CH contained in the saturated hydrocarbon group 2 - may be replaced by -O- or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent -CH 2 - is not simultaneously replaced by -O-, and terminal -CH 2 - is not replaced by -O- or -CO-. R 41 and R 42 may combine to form a ring together with the nitrogen atom to which they are attached, and R 43 and R 44 may combine to form a ring together with the nitrogen atom to which they are attached. R 47 to R 54 each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, -SO 3 - -, -SO 2 -N - -SO 2 -R f or an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms. When the saturated hydrocarbon group has 2 to 20 carbon atoms, -CH 2 - constituting the saturated hydrocarbon group may be replaced by -O- or -CO-. R 48 and R 52 may be bonded to each other to form -NH-, -S-, or -SO 2 -. However, in the saturated hydrocarbon group, adjacent -CH 2 - is not simultaneously replaced by -O-, and the terminal -CH 2 - is not replaced by -O- or -CO-. Ring T 1 represents an aromatic heterocyclic ring having 3 to 10 carbon atoms, and the aromatic heterocyclic ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a substituted or unsubstituted amino group, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, -SO 3 - or -SO 2 -N - -SO 2 -R f The substituent that the aromatic hydrocarbon group may have may be -SO 3 - or -SO 2 -N - -SO 2 -R f and may be. M r+ represents an r-valent metal ion. k represents the number such that the compound represented by formula (a) becomes an electrically neutral compound. r represents an integer of 1 or more. R f represents a fluoroalkyl group having 1 to 12 carbon atoms. However, the compound represented by the formula (a) has at least one of -SO 3 - or -SO 2 -N - -SO 2 -R f .

2. The colored curable resin composition according to claim 1, wherein the hydroxyl value of the polymerizable compound (C) is 200 mgKOH / g or more.

3. The colored curable resin composition according to claim 1 or 2, wherein the colorant (A) further contains a xanthene dye.

4. The colored curable resin composition according to claim 3, wherein the xanthene dye is a compound represented by formula (1). 【Chemical 2】 [In formula (1), R 1 ~R 4 each independently represents a hydrogen atom, -R 8 or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, or R 1 and R 2 and R 3 and R 4 together form a ring containing a nitrogen atom. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, -OH, -OR 8 , -SO 3 - , -SO 3 H, -SO 3 - M + , -CO 2 H, -CO 2 R 8 , -SO 3 R 8 or -SO 2 NR 9 R 10 . R 5 is -OH, -SO 3 - , -SO 3 H, -SO 3 - M + , -CO 2 H, -CO 2 - M + , -CO 2 R 8 , -SO 3 R 8 or -SO 2 NR 9 R 10 represents. m represents an integer from 0 to 5, and when m is an integer of 2 or more, a plurality of Rs 5 may be the same or different from each other. R 6 and R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. M + teeth, + N (R 11 ) 4 , Na + Or K + and X represents a halogen atom. a represents 0 or 1. R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms, a carboxy group, or a halogen atom, and -CH 2 - in the saturated hydrocarbon group may be replaced by -S-, -O-, -CO- or -NR 11 -. However, in the saturated hydrocarbon group, adjacent -CH 2 - is not simultaneously replaced by -O-. 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, and when a plurality of R 11 are present, all or some of them may be the same. R 9 and R 10 each independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with -OH or a halogen atom, and -CH 2 - may be replaced with -S-, -O-, -CO-, -NH- or -NR 8 -. However, in the saturated hydrocarbon group, adjacent -CH 2 - is not simultaneously replaced with -O-. R 9 and R 10 may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom.

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

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

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