Method for producing compound, and colored resin composition containing same

Abstract

The present invention addresses the problem of providing a novel production method whereby a compound (I) can be stably synthesized at a predetermined yield or higher. In addition, the present invention addresses the problem of providing a colored resin composition capable of forming a color filter in which luminance unevenness can be suppressed even after long-term use. This production method is characterized by reacting compounds (II-1)-(II-4) in the presence of a base and a specific aluminum compound. Furthermore, the colored resin composition of the present invention is characterized by containing a colorant containing the compound (I) and an alkali-soluble resin. [In the formula, each of R1-R16 independently represents a hydrogen atom, a bromine atom, an iodine atom, an optionally substituted C1-6 hydrocarbon group, or a specific aryloxy group, and-CH2-contained in the hydrocarbon group may be substituted with-O-or-CO-. (In the formula, at least one of R1-R16 represents a specific aryloxy group]. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a method for producing a compound, and a colored resin composition, a color filter, a display device, and a solid-state imaging element containing the compound. Background Art

[0002] Phthalocyanine compounds are known as colorants such as dyes and pigments, and for example, a phthalocyanine compound represented by the following formula (I-e16) is disclosed in Non-Patent Document 1. Non-Patent Document 1 describes that the phthalocyanine compound represented by the following formula (I-e16) was synthesized with a yield of 52% by reacting a compound represented by the following formula (II-16) in the presence of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU).

[0003]

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2009-192661

[0007] Non-patent literature

[0008] Non-patent document 1: Dyes and Pigments 88 (2011) 187-194 Summary of the invention

[0009] However, the method described in Non-Patent Document 1 has low reproducibility, and the present inventors were unable to substantially obtain the target compound using the method, and were unable to reproduce the yield described in Non-Patent Document 1. Therefore, an object of the present invention is to provide a new production method capable of stably synthesizing a specific phthalocyanine compound at a predetermined yield or higher.

[0010] In addition, the color filter used in the display device such as liquid crystal display device, electroluminescent display device and plasma display, CCD, CMOS sensor and other solid-state imaging elements is manufactured by the colored resin composition. It is known that the colored resin composition used to make the green colored filter (green filter) in the color filter adopts CI pigment green 58 as a colorant (patent document 1). However, when the color filter formed by the colored resin composition containing CI pigment green 58 is applied to, for example, a display device, if it is used for a long time, it is sometimes uneven due to the brightness difference generated in the peripheral part and the central part of the colored filter. Therefore, the subject of the present invention is to provide a colored resin composition that can form a color filter that can suppress uneven brightness even after long-term use.

[0011] The gist of the present invention is as follows.

[0012] [1] A colored resin composition comprising a colorant and an alkali-soluble resin, wherein the colorant comprises a compound represented by formula (I).

[0013]

[0014] [In formula (I),

[0015] R 1 ~R 16 Each independently represents a hydrogen atom, a bromine atom, an iodine atom, a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, a group represented by formula (ia), a group represented by formula (ib) or a group represented by formula (ic), wherein -CH2- contained in the hydrocarbon group may be substituted by -O- or -CO-. 1 ~R 16 At least one of them represents a group represented by formula (ia), a group represented by formula (ib) or a group represented by formula (ic); when there are multiple groups represented by formula (ia), they may be the same or different; when there are multiple groups represented by formula (ib), they may be the same or different; when there are multiple groups represented by formula (ic), they may be the same or different]

[0016]

[0017] [In formula (ia),

[0018] R a1 ~R a5 Each independently represents a hydrogen atom, a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, wherein -CH2- contained in the hydrocarbon group may be substituted by -O- or -CO-. a1 ~R a5 At least one of represents a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. * represents a bonding site]

[0019]

[0020] [In formula (ib),

[0021] R b1 ~R b7 Each independently represents a hydrogen atom, a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, wherein -CH2- contained in the hydrocarbon group may be substituted by -O- or -CO-. b1 ~R b7 At least one of represents a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. * represents a bonding site]

[0022]

[0023] [In formula (ic),

[0024] R c1 ~R c7 Each independently represents a hydrogen atom, a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, wherein -CH2- contained in the hydrocarbon group may be substituted by -O- or -CO-. c1 ~R c7 At least one of represents a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. * represents a bonding site]

[0025] [2] The colored resin composition according to [1], wherein R 1 ~R 4 At least one of them is a group represented by formula (ia), formula (ib) or formula (ic), R 5 ~R 8 At least one of them is a group represented by formula (ia), formula (ib) or formula (ic), R 9 ~R 12 At least one of them is a group represented by formula (ia), formula (ib) or formula (ic), R 13 ~R 16 At least one of them is a group represented by formula (ia), formula (ib) or formula (ic).

[0026] [3] The colored resin composition according to [2], wherein R 2 and R 3 At least one of them is a group represented by formula (ia), formula (ib) or formula (ic), R 6 and R 7 At least one of them is a group represented by formula (ia), formula (ib) or formula (ic), R 10 and R 11 At least one of them is a group represented by formula (ia), formula (ib) or formula (ic), R 14 and R 15 At least one of them is a group represented by formula (ia), formula (ib) or formula (ic), R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 A hydrogen atom.

[0027] [4] The colored resin composition according to [3], wherein R 2 and R 3 Any one of them is a group represented by formula (ia), formula (ib) or formula (ic), R 6 and R 7 Any one of them is a group represented by formula (ia), formula (ib) or formula (ic), R 10 and R 11 Any one of them is a group represented by formula (ia), formula (ib) or formula (ic), R 14 and R 15 Any one of them is a group represented by formula (ia), formula (ib) or formula (ic), R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 is a hydrogen atom,

[0028] The four groups represented by the formula (ia), formula (ib) or formula (ic) in the formula (I) are the same groups.

[0029] [5] The colored resin composition according to [2], wherein R 1 , R 5 , R 9 and R 13 are each independently a group represented by formula (ia), formula (ib) or formula (ic), R 2 ~R 4 , R 6 ~R 8 , R 10 ~R 12 and R 14 ~R 16 A hydrogen atom.

[0030] [6] The colored resin composition according to any one of [1] to [5], further comprising a polymerizable compound and a polymerization initiator.

[0031] [7] A color filter formed from the colored resin composition according to any one of [1] to [6].

[0032] [8] A display device comprising the color filter described in [7].

[0033] [9] A solid-state imaging element comprising the color filter described in [7].

[0034]

[10] A method for producing a compound represented by formula (I), comprising reacting compounds represented by formulae (II-1) to (II-4) in the presence of a base and a compound represented by formula (III).

[0035]

[0036] [In formula (I),

[0037] R 1 ~R 16 Each independently represents a hydrogen atom, a bromine atom, an iodine atom, a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, a group represented by formula (ia), a group represented by formula (ib) or a group represented by formula (ic), wherein -CH2- contained in the hydrocarbon group may be substituted by -O- or -CO-. 1 ~R 16 At least one of them represents a group represented by formula (ia), a group represented by formula (ib) or a group represented by formula (ic); when there are multiple groups represented by formula (ia), they may be the same or different; when there are multiple groups represented by formula (ib), they may be the same or different; when there are multiple groups represented by formula (ic), they may be the same or different]

[0038]

[0039] [In formula (ia),

[0040] R a1 ~R a5 Each independently represents a hydrogen atom, a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, wherein -CH2- contained in the hydrocarbon group may be substituted by -O- or -CO-. a1 ~R a5 At least one of represents a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. * represents a bonding site]

[0041]

[0042] [In formula (ib),

[0043] R b1 ~R b7 Each independently represents a hydrogen atom, a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, wherein -CH2- contained in the hydrocarbon group may be substituted by -O- or -CO-. b1 ~R b7 At least one of represents a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. * represents a bonding site]

[0044]

[0045] [In formula (ic),

[0046] R c1 ~R c7 Each independently represents a hydrogen atom, a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, wherein -CH2- contained in the hydrocarbon group may be substituted by -O- or -CO-. c1 ~R c7 At least one of represents a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. * represents a bonding site]

[0047] AIX M 3 (III)

[0048] [In formula (III),

[0049] X M Represents a halogen atom, a hydroxyl group, or OR M Base. R M represents a hydrocarbon group having 1 to 6 carbon atoms]

[0050]

[0051] [In formulas (II-1) to (II-4),

[0052] R 1 ~R 16 Represents the same as above R 1 ~R 16 Same meaning]

[0053]

[11] The production method according to

[10] , wherein the amount of the compound represented by formula (III) used is 0.25 mol to 0.40 mol relative to 1 mol of the total amount of the compounds represented by formulae (II-1) to (II-4).

[0054] According to the production method of the present invention, a specific phthalocyanine compound can be stably synthesized at a predetermined yield or higher. In addition, according to the production method of the present invention, a specific phthalocyanine compound can be synthesized in a short reaction time.

[0055] Moreover, according to the colored resin composition of this invention which contains a specific phthalocyanine compound as a coloring agent, even after long-term use, it is possible to form a color filter which can suppress brightness unevenness. DETAILED DESCRIPTION

[0056] [Colored resin composition]

[0057] The present invention includes a colored resin composition comprising a colorant (hereinafter, sometimes referred to as colorant (A)) and an alkali-soluble resin (hereinafter, sometimes referred to as resin (B)), wherein the colorant (A) comprises a compound represented by formula (I) described below.

[0058] The colored resin composition of the present invention preferably further contains at least one (preferably both) of a polymerizable compound (hereinafter, sometimes referred to as a polymerizable compound (C)) and a polymerization initiator (hereinafter, sometimes referred to as a polymerization initiator (D)).

[0059] It is preferred that the colored resin composition of the present invention further contains a solvent (hereinafter, sometimes referred to as a solvent (E)).

[0060] The colored resin composition of the present invention may contain a leveling agent (hereinafter, sometimes referred to as a leveling agent (F)).

[0061] In the present specification, unless otherwise specified, the compounds exemplified as the components may be used alone or in combination of two or more.

[0062] <Colorant (A)>

[0063] The colored resin composition of the present invention contains a compound represented by formula (I) (hereinafter, sometimes referred to as compound (I)) as a colorant. The colored filter formed from the colored resin composition containing compound (I) as a colorant can reduce the brightness difference between the peripheral part and the central part even after long-term use, that is, it can form a color filter in which brightness unevenness is suppressed. Below, the partial structure of compound (I) is given to explain the present invention in more detail.

[0064]

[0065] [In formula (I),

[0066] R 1 ~R 16 Each independently represents a hydrogen atom, a bromine atom, an iodine atom, a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, a group represented by formula (ia), a group represented by formula (ib) or a group represented by formula (ic), wherein -CH2- contained in the hydrocarbon group may be substituted by -O- or -CO-. 1 ~R 16 At least one of them represents a group represented by formula (ia), a group represented by formula (ib) or a group represented by formula (ic); when there are multiple groups represented by formula (ia), they may be the same or different; when there are multiple groups represented by formula (ib), they may be the same or different; when there are multiple groups represented by formula (ic), they may be the same or different]

[0067]

[0068] [In formula (ia),

[0069] R a1 ~R a5 Each independently represents a hydrogen atom, a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, wherein -CH2- contained in the hydrocarbon group may be substituted by -O- or -CO-. a1 ~R a5 At least one of represents a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. * represents a bonding site]

[0070]

[0071] [In formula (ib),

[0072] R b1 ~R b7 Each independently represents a hydrogen atom, a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, wherein -CH2- contained in the hydrocarbon group may be substituted by -O- or -CO-. b1 ~R b7 At least one of represents a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. * represents a bonding site]

[0073]

[0074] [In formula (ic),

[0075] R c1 ~R c7 Each independently represents a hydrogen atom, a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, wherein -CH2- contained in the hydrocarbon group may be substituted by -O- or -CO-. c1 ~R c7 At least one of represents a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. * represents a bonding site]

[0076] R 1 ~R 16 The hydrocarbon group having 1 to 6 carbon atoms represented by may be any of an aliphatic hydrocarbon group and a phenyl group. The aliphatic hydrocarbon group may be saturated or unsaturated and may be chain-shaped or cyclic (alicyclic hydrocarbon group).

[0077] Examples of the saturated chain hydrocarbon group (hereinafter sometimes referred to as an alkyl group) include straight-chain alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl; and branched-chain alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, 1,3-dimethylbutyl, 2-methyl-2-pentyl, and 2-ethylbutyl.

[0078] The alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms.

[0079] Examples of the unsaturated chain hydrocarbon group include alkenyl groups such as ethenyl, propenyl (e.g., 1-propenyl, 2-propenyl) and butenyl (e.g., 1-butenyl, 3-butenyl); alkynyl groups such as ethynyl, propynyl (e.g., 1-propynyl, 2-propynyl) and butynyl (e.g., 1-butynyl, 3-butynyl); and the like.

[0080] The unsaturated chain hydrocarbon group preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms.

[0081] Examples of the saturated alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0082] Examples of the unsaturated alicyclic hydrocarbon group include cycloalkenyl groups such as cyclohexenyl (e.g., cyclohex-1-en-1-yl, cyclohex-2-en-1-yl, cyclohex-3-en-1-yl) and the like.

[0083] The alicyclic hydrocarbon group preferably has 3 to 6 carbon atoms.

[0084] R 1 ~R 16 The hydrocarbon group having 1 to 6 carbon atoms represented by may have a substituent. Examples of the substituent include halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms; hydroxyl groups; carboxyl groups; unsubstituted amino groups; substituted amino groups such as N-methylamino groups, N,N-dimethylamino groups, N-ethylamino groups, N,N-diethylamino groups, n-propylamino groups, N,N-dipropylamino groups, N-isopropylamino groups, N,N-diisopropylamino groups, N-phenylamino groups, N,N-diphenylamino groups, and N,N-ethylmethylamino groups; and cyano groups. Among these, halogen atoms are preferred, and chlorine atoms are more preferred.

[0085] In R 1 ~R 16 When the number of carbon atoms of the hydrocarbon group represented is 2 to 6 and the hydrocarbon group has -CH2-, the -CH2- may be substituted by -O- or -CO-. However, in the hydrocarbon group having 1 to 6 carbon atoms, adjacent -CH2- will not be substituted by -O- at the same time, and the terminal -CH2- will not be substituted by -O- or -CO-.

[0086] It should be noted that in the present specification, when -CH2- in a hydrocarbon group is substituted with -O- or -CO-, the number of carbon atoms in the group substituted with -O- or -CO- refers to the number of carbon atoms in the hydrocarbon group before being substituted with -O- or -CO-. For example, a *-O-CH2-CH2-CH3 group is a group in which -CH2- in a hydrocarbon group having 4 carbon atoms (*-CH2-CH2-CH2-CH3) is substituted with -O-.

[0087] In addition, if there are multiple substitutable -CH2- in the hydrocarbon group, the number of substitutions is not necessarily limited to 1. For example, two -CH2- in the hydrocarbon group with 4 carbon atoms (*-CH2-CH2-CH2-CH3) may be substituted by -O- to become *-O-CH2-O-CH3, or one -CH2- may be substituted by -O- and the other -CH2- may be substituted by -CO- to become *-O-CO-CH2-CH3 or *-CO-O-CH2-CH3. That is, groups in which two or more -CH2- are substituted by -O- or -CO-, such as *-O-CH2-O-CH3, *-O-CO-CH2-CH3 and *-CO-O-CH2-CH3, are also included in the "group in which -CH2- is substituted by -O- or -CO- in the hydrocarbon group with 1 to 6 carbon atoms which may have a substituent".

[0088] As R 1 ~R 16 The hydrocarbon group having 1 to 6 carbon atoms which may have a substituent is preferably an alkyl group.

[0089] R a1 ~R a5 , R b1 ~R b7 and R c1 ~R c7 The hydrocarbon group having 1 to 20 carbon atoms represented may be any of an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof. The aliphatic hydrocarbon group may be saturated or unsaturated, and may be chain-like or cyclic (alicyclic hydrocarbon group).

[0090] Examples of the saturated chain hydrocarbon group (alkyl group) include straight-chain alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl; and branched-chain alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, 1,3-dimethylbutyl, 2-ethylbutyl, 2-methyl-2-pentyl and 2-ethylhexyl.

[0091] The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 8, further preferably 1 to 4, particularly preferably 1 to 3.

[0092] Examples of the unsaturated chain hydrocarbon group include alkenyl groups such as ethenyl, propenyl (e.g., 1-propenyl, 2-propenyl) and butenyl (e.g., 1-butenyl, 3-butenyl); alkynyl groups such as ethynyl, propynyl (e.g., 1-propynyl, 2-propynyl) and butynyl (e.g., 1-butynyl, 3-butynyl); and the like.

[0093] The unsaturated chain hydrocarbon group has preferably 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and further preferably 2 to 4 carbon atoms.

[0094] Examples of the saturated alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and 2-methylcyclohexyl.

[0095] Examples of the unsaturated alicyclic hydrocarbon group include cyclohexenyl (e.g., cyclohex-1-en-1-yl, cyclohex-2-en-1-yl, cyclohex-3-en-1-yl), cycloheptenyl, cyclooctenyl and other cycloalkenyl groups.

[0096] Examples of the alicyclic hydrocarbon group include polycyclic saturated alicyclic hydrocarbon groups such as norbornyl, adamantyl, and bicyclo[2.2.2]octyl; and polycyclic unsaturated alicyclic hydrocarbon groups such as norbornenyl.

[0097] The alicyclic hydrocarbon group has preferably 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms.

[0098] Examples of the aromatic hydrocarbon group include phenyl, o-tolyl, m-tolyl, p-tolyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,4-diisopropylphenyl, 2,6-diisopropylphenyl, 4-vinylphenyl, o-tert-butylphenyl, m-tert-butylphenyl, p-tert-butylphenyl, 2,6-di(tert-butyl)phenyl, 3,5-di(tert-butyl)phenyl, 1-naphthyl, 2-naphthyl, and a group obtained by removing one hydrogen atom from tetralin.

[0099] The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 12, and even more preferably 6 to 10.

[0100] R a1 ~R a5 , R b1 ~R b7 and R c1 ~R c7 The hydrocarbon group represented may be a group composed of the above-mentioned hydrocarbon groups as long as the total number of carbon atoms is 20 or less. Examples of the group composed of the above-mentioned hydrocarbon groups include an aralkyl group and an alkyl group bonded to an alicyclic hydrocarbon group.

[0101] Examples of the aralkyl group include benzyl, (2-methylphenyl)methyl, (3-methylphenyl)methyl, (4-methylphenyl)methyl, (2-ethylphenyl)methyl, (3-ethylphenyl)methyl, (4-ethylphenyl)methyl, (2-(tert-butyl)phenyl)methyl, (3-(tert-butyl)phenyl)methyl, (4-(tert-butyl)phenyl)methyl, (3,5-dimethylphenyl)methyl, 1-phenylethyl, 1-methyl-1-phenylethyl, 1,1-diphenylethyl, (1-naphthyl)methyl, (2-naphthyl)methyl, and 9-fluorenylmethyl. The aralkyl group preferably has 7 to 18 carbon atoms, and more preferably 7 to 12 carbon atoms.

[0102] Examples of the alkyl group bonded with an alicyclic hydrocarbon group include cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclohexylmethyl, cyclohexylethyl, and adamantylmethyl. The alkyl group bonded with an alicyclic hydrocarbon group preferably has 4 to 20 carbon atoms, more preferably 4 to 15, and even more preferably 4 to 10 carbon atoms.

[0103] As R a1 ~R a5 , R b1 ~R b7 and R c1 ~R c7 The substituents that the hydrocarbon group having 1 to 20 carbon atoms represented by 1 ~R 16 The substituents that the hydrocarbon group having 1 to 6 carbon atoms represented by are the same as those exemplified above. Among them, a halogen atom is preferred, and a chlorine atom is more preferred.

[0104] In R a1 ~R a5 , R b1 ~R b7 and R c1 ~R c7 When the number of carbon atoms of the hydrocarbon group represented is 2 to 20 and the hydrocarbon group has -CH2-, the -CH2- may be substituted by -O- or -CO-. However, in the hydrocarbon group having 1 to 20 carbon atoms, adjacent -CH2- will not be substituted by -O- at the same time, and the terminal -CH2- will not be substituted by -O- or -CO-. In particular, as the group in which -CH2- is substituted by -O- or -CO-, alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and tert-butoxy are preferred, alkoxy groups having 1 to 10 carbon atoms are more preferred, and alkoxy groups having 1 to 4 carbon atoms are further preferred.

[0105] As R a1 ~R a5 , R b1 ~R b7 and R c1 ~R c7The hydrocarbon group having 1 to 20 carbon atoms which may have a substituent is preferably an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, further preferably an alkyl group having 1 to 8 (particularly 1 to 4) carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.

[0106] R a1 ~R a5 , R b1 ~R b7 and R c1 ~R c7 Each independently is preferably a hydrogen atom, a bromine atom, an alkoxy group having 1 to 10 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom, a bromine atom, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, further preferably a hydrogen atom, a bromine atom, an alkyl group having 1 to 8 (particularly 1 to 4) carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0107] In the group represented by formula (ia), R a1 ~R a5 The total number of bromine atoms and iodine atoms is preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1.

[0108] In the group represented by formula (ib), R b1 ~R b7 The total number of bromine atoms and iodine atoms is preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1.

[0109] In the group represented by formula (ic), R c1 ~R c7 The total number of bromine atoms and iodine atoms is preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1.

[0110] In the group represented by formula (ia), R a1 ~R a5 At least one of them is preferably a bromine atom, an iodine atom, a carboxyl group, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 10 carbon atoms, and R a1 ~R a5More preferably, at least one of the above is a bromine atom, a hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and R a1 ~R a5 At least one of them is more preferably a bromine atom, an alkyl group having 1 to 8 (particularly 1 to 4) carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0111] Especially R. a1 ~R a5 Preferably, 1 to 3 of them are independently a bromine atom, an iodine atom, a carboxyl group, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 10 carbon atoms, and the rest are hydrogen atoms. a1 ~R a5 More preferably, 1 to 3 of them are independently bromine atoms, hydrocarbon groups having 1 to 20 carbon atoms, or alkoxy groups having 1 to 4 carbon atoms, and the rest are hydrogen atoms. a1 ~R a5 Among them, it is further preferred that 1 to 3 each independently be a bromine atom, an alkyl group having 1 to 8 carbon atoms (especially 1 to 4), a cycloalkyl group having 4 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and the rest are hydrogen atoms.

[0112] In the group represented by formula (ib), R b1 ~R b7 At least one of them is a bromine atom, an iodine atom, a carboxyl group or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R b1 ~R b7 At least one of them is preferably a bromine atom or a hydrocarbon group having 1 to 20 carbon atoms, and R b1 ~R b7 More preferably, at least one of them is a bromine atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.

[0113] Especially R. b1 ~R b7 Preferably, 1 to 3 of them are independently bromine atoms, iodine atoms, carboxyl groups or hydrocarbon groups having 1 to 20 carbon atoms which may have a substituent, and the rest are hydrogen atoms. b1 ~R b7 More preferably, 1 to 3 of them are independently bromine atoms or hydrocarbon groups having 1 to 20 carbon atoms, and the rest are hydrogen atoms. b1 ~R b7Among them, it is more preferred that 1 to 3 of them are each independently a bromine atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and the rest are hydrogen atoms.

[0114] In the group represented by formula (ic), R c1 ~R c7 At least one of them is a bromine atom, an iodine atom, a carboxyl group or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R c1 ~R c7 At least one of them is preferably a bromine atom or a hydrocarbon group having 1 to 20 carbon atoms, and R c1 ~R c7 More preferably, at least one of them is a bromine atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.

[0115] Especially R. c1 ~R c7 Preferably, 1 to 3 of them are independently bromine atoms, iodine atoms, carboxyl groups or hydrocarbon groups having 1 to 20 carbon atoms which may have a substituent, and the rest are hydrogen atoms. c1 ~R c7 More preferably, 1 to 3 of them are independently bromine atoms or hydrocarbon groups having 1 to 20 carbon atoms, and the rest are hydrogen atoms. c1 ~R c7 Among them, it is more preferred that 1 to 3 of them are each independently a bromine atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and the rest are hydrogen atoms.

[0116] Specific examples of the group represented by the formula (ia) include groups represented by the following formulae (i-a1) to (i-a17).

[0117]

[0118] Specific examples of the group represented by the formula (ib) include groups represented by the following formulae (i-b1) to (i-b4).

[0119]

[0120] Specific examples of the group represented by the formula (ic) include groups represented by the following formulae (i-c1) to (i-c5).

[0121]

[0122] R 1 ~R 16Each independently is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a group represented by formula (ia), and more preferably a hydrogen atom or a group represented by formula (ia).

[0123] In compound (I), R 1 ~R 16 At least one of R represents a group represented by formula (ia), formula (ib) or formula (ic) (hereinafter, sometimes collectively referred to as "aryloxy group (i)"). 1 ~R 16 In the formula (I), the total number of aryloxy groups (i) is, for example, 2 to 16, preferably 4 to 16, more preferably 4 to 8, and even more preferably 4. When compound (I) has a plurality of groups represented by formula (ia), the plurality of groups represented by formula (ia) may be the same or different, but are preferably the same; when compound (I) has a plurality of groups represented by formula (ib), the plurality of groups represented by formula (ib) may be the same or different, but are preferably the same; when compound (I) has a plurality of groups represented by formula (ic), the plurality of groups represented by formula (ic) may be the same or different, but are preferably the same.

[0124] When compound (I) has a plurality of aryloxy groups (i), they are more preferably the same.

[0125] As the aryloxy group (i), a group represented by the formula (ia) or the formula (ib) is preferred, and a group represented by the formula (ia) is more preferred.

[0126] R 1 ~R 16 In the formula (a), the position of the aryloxy group (i) is not particularly limited.

[0127] Method (1): Optimize R 1 ~R 4 At least one of them is an aryloxy group (i), R 5 ~R 8 At least one of them is an aryloxy group (i), R 9 ~R 12 At least one of them is an aryloxy group (i), and R 13 ~R 16 At least one of them is an aryloxy group (i),

[0128] Mode (2): More preferably R 2 and R 3 At least one of them is an aryloxy group (i), R 6 and R 7 At least one of them is an aryloxy group (i), R 10 and R 11 At least one of them is an aryloxy group (i), and R 14 and R 15At least one of them is an aryloxy group (i), R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 is a hydrogen atom, or (3): R 1 and R 4 At least one of them is an aryloxy group (i), R 5 and R 8 At least one of them is an aryloxy group (i), R 9 and R 12 At least one of them is an aryloxy group (i), and R 13 and R 16 At least one of them is an aryloxy group (i), R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 is a hydrogen atom,

[0129] Method (4): Further optimization of R 2 and R 3 Any one of which is an aryloxy group (i), R 6 and R 7 Any one of which is an aryloxy group (i), R 10 and R 11 Any one of is an aryloxy group (i), and R 14 and R 15 Any one of which is an aryloxy group (i), R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 is a hydrogen atom, or (5): R 1 and R 4 Any one of which is an aryloxy group (i), R 5 and R 8 Any one of which is an aryloxy group (i), R 9 and R 12 Any one of is an aryloxy group (i), and R 13 and R 16 Any one of which is an aryloxy group (i), R 2 , R 3 , R 6 , R7 , R 10 , R 11 , R 14 and R 15 is a hydrogen atom,

[0130] Mode (6): R is particularly preferred 2 and R 3 One of them is an aryloxy group (i) and the other is a hydrogen atom, R 6 and R 7 One of them is an aryloxy group (i) and the other is a hydrogen atom, R 10 and R 11 is an aryloxy group (i) and the other is a hydrogen atom, and R 14 and R 15 One of them is an aryloxy group (i) and the other is a hydrogen atom, R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 is a hydrogen atom, or (7): R 1 , R 5 , R 9 and R 13 is an aryloxy group (i), and R 2 ~R 4 , R 6 ~R 8 , R 10 ~R 12 and R 14 ~R 16 A hydrogen atom.

[0131] In each of the above embodiments (1) to (7), the plurality of aryloxy groups (i) contained in the compound (I) may be the same or different, but are preferably the same.

[0132] From the viewpoint of further reducing uneven brightness of the obtained color filter after long-term use, the embodiment (2) is preferred, the embodiment (4) is more preferred, and the embodiment (6) is still more preferred.

[0133] As compound (I), a compound represented by formula (IA) (hereinafter, compound (IA)) and / or a compound represented by formula (IB) (hereinafter, compound (IB)) is preferred. From the viewpoint of further suppressing uneven brightness of the obtained color filter after long-term use, compound (IA) is preferred.

[0134]

[0135] [In formula (IA),

[0136] R 2A and R 3A Any one of them is a group represented by formula (iA-a), formula (iA-b) or formula (iA-c) and the other is a hydrogen atom,

[0137] R 6A and R 7A Any one of them is a group represented by formula (iA-a), formula (iA-b) or formula (iA-c) and the other is a hydrogen atom,

[0138] R 10A and R 11A Any one of them is a group represented by formula (iA-a), formula (iA-b) or formula (iA-c) and the other is a hydrogen atom,

[0139] R 14A and R 15A Any one of them is a group represented by formula (iA-a), formula (iA-b) or formula (iA-c) and the other is a hydrogen atom,

[0140] R 1A , R 4A , R 5A , R 8A , R 9A , R 12A , R 13A and R 16A A hydrogen atom.

[0141] In formula (IB),

[0142] R 1B , R 5B , R 9B and R 13B are each independently a group represented by formula (iA-a), formula (iA-b) or formula (iA-c), and R 2B ~R 4B , R 6B ~R 8B , R 10B ~R 12B and R 14B ~R 16B for hydrogen atoms]

[0143]

[0144] [In formula (iA-a),

[0145] R a1A ~R a5AEach independently represents a hydrogen atom, a bromine atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. a1A ~R a5A At least one of represents a bromine atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. * represents a bonding site.

[0146] In formula (iA-b),

[0147] R b1A ~R b7A Each independently represents a hydrogen atom, a bromine atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. b1A ~R b7A At least one of represents a bromine atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. * represents a bonding site.

[0148] In formula (iA-c),

[0149] R c1A ~R c7A Each independently represents a hydrogen atom, a bromine atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. c1A ~R c7A At least one of them represents a bromine atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. * represents a bonding site]

[0150] The four groups represented by the formula (iA-a), formula (iA-b) or formula (iA-c) possessed by compound (IA) may be the same or different, but are preferably the same.

[0151] The four groups represented by the formula (iA-a), formula (iA-b) or formula (iA-c) possessed by compound (IB) may be the same or different, but are preferably the same.

[0152] In compound (IA), preferably R 2A and R 3A , R6A and R 7A , R 10A and R 11A , and R 14A and R 15A Any one of them is independently a group represented by formula (iA-a) and the other is a hydrogen atom, or any one of them is a group represented by formula (iA-b) and the other is a hydrogen atom, and more preferably any one of them is a group represented by formula (iA-a) and the other is a hydrogen atom.

[0153] In compound (IB), R 1B , R 5B , R 9B and R 13B Each independently is preferably a group represented by formula (iA-a) or formula (iA-b), and more preferably a group represented by formula (iA-a).

[0154] As R a1A ~R a5A , R b1A ~R b7A and R c1A ~R c7A The alkyl group having 1 to 8 carbon atoms represented by R a1 ~R a5 , R b1 ~R b7 and R c1 ~R c7 The alkyl group represented by the group described herein is a group having 1 to 8 carbon atoms.

[0155] As R a1A ~R a5A , R b1A ~R b7A and R c1A ~R c7A The cycloalkyl group having 3 to 10 carbon atoms represented by R a1 ~R a5 , R b1 ~R b7 and R c1 ~R c7 The cycloalkyl group represented by the group described herein is a group having 3 to 10 carbon atoms.

[0156] As R a1A ~R a5A , R b1A ~R b7A and R c1A ~R c7A The aromatic hydrocarbon group having 6 to 12 carbon atoms represented by R is exemplified by a1 ~R a5 , Rb1 ~R b7 and R c1 ~R c7 The aromatic hydrocarbon group represented by is a group having 6 to 12 carbon atoms among the groups described above.

[0157] As R a1A ~R a5A , R b1A ~R b7A and R c1A ~R c7A The aralkyl group having 7 to 12 carbon atoms represented by R is exemplified by a1 ~R a5 , R b1 ~R b7 and R c1 ~R c7 The aralkyl group represented by the above group is a group having 7 to 12 carbon atoms.

[0158] As R a1A ~R a5A , R b1A ~R b7A and R c1A ~R c7A Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and tert-butoxy.

[0159] R a1A ~R a5A , R b1A ~R b7A and R c1A ~R c7A Each independently preferably is a hydrogen atom, a bromine atom, an alkyl group having 1 to 8 (particularly 1 to 4) carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

[0160] In the group represented by formula (iA-a), R a1A ~R a5A The number of bromine atoms is preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1.

[0161] In the group represented by formula (iA-b), R b1A ~R b7A The number of bromine atoms is preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1.

[0162] In the group represented by formula (iA-c), R c1A ~R c7AThe number of bromine atoms is preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1.

[0163] In the group represented by formula (iA-a), R a1A ~R a5A At least one of them is preferably a bromine atom, an alkyl group having 1 to 8 (particularly 1 to 4) carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0164] Especially R. a1A ~R a5A In the above, preferably 1 to 3 of them are independently bromine atoms, alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aromatic hydrocarbon groups having 6 to 12 carbon atoms, aralkyl groups having 7 to 12 carbon atoms, or alkoxy groups having 1 to 4 carbon atoms, and the rest are hydrogen atoms, R a1A ~R a5A Among them, more preferably 1 to 3 each independently represent a bromine atom, an alkyl group having 1 to 8 carbon atoms (especially 1 to 4), a cycloalkyl group having 4 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and the rest are hydrogen atoms.

[0165] In the group represented by formula (iA-b), R b1A ~R b7A At least one of them is preferably a bromine atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.

[0166] Especially R. b1A ~R b7A In the above, preferably 1 to 3 of them are independently bromine atoms, alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aromatic hydrocarbon groups having 6 to 12 carbon atoms, or aralkyl groups having 7 to 12 carbon atoms, and the rest are hydrogen atoms, R b1A ~R b7A More preferably, 1 to 3 of them are each independently a bromine atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and the rest are hydrogen atoms.

[0167] In the group represented by formula (iA-c), R c1A ~R c7A At least one of them is preferably a bromine atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and R c1A ~R c7AMore preferably, at least one of them is a bromine atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.

[0168] Especially R. c1A ~R c7A In the above, preferably 1 to 3 of them are independently bromine atoms, alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aromatic hydrocarbon groups having 6 to 12 carbon atoms, or aralkyl groups having 7 to 12 carbon atoms, and the rest are hydrogen atoms, R c1A ~R c7A More preferably, 1 to 3 of them are each independently a bromine atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and the rest are hydrogen atoms.

[0169] As the group represented by formula (iA-a), specifically, there are groups represented by the above-mentioned formulas (i-a1) to (i-a17), etc., as the group represented by formula (iA-b), specifically, there are groups represented by the above-mentioned formulas (i-b1) to (i-b4), etc., as the group represented by formula (iA-c), specifically, there are groups represented by the above-mentioned formulas (i-c1) to (i-c5), etc.

[0170] Specific examples of compound (I) include compounds (Ia-1) to (Ia-136) and compounds (Ib-1) to (Ib-17) shown in Tables 1 to 5.

[0171] [Table 1]

[0172] <![CDATA[R 1 ]]> <![CDATA[R 2 ]]> <![CDATA[R 3 ]]> <![CDATA[R 4 ]]> <![CDATA[R 5 ]]> <![CDATA[R 6 ]]> <![CDATA[R 7 ]]> <![CDATA[R 8 ]]> <![CDATA[R 9 ]]> <![CDATA[R 10 ]]> <![CDATA[R 11 ]]> <![CDATA[R 12 ]]> <![CDATA[R 13 ]]> <![CDATA[R 14 ]]> <![CDATA[R 15 ]]> <![CDATA[R 16 ]]> Ia-1 H i-a1 H H H i-a1 H H H i-a1 H H H H i-a1 H Ia-2 H i-a1 H H H i-a1 H H H H i-a1 H H H i-a1 H Ia-3 H i-a1 H H H H i-a1 H H i-a1 H H H H i-a1 H Ia-4 H i-a1 H H H H i-a1 H H H i-a1 H H H i-a1 H Ia-5 H H i-a1 H H i-a1 H H H i-a1 H H H H i-a1 H Ia-6 H H i-a1 H H i-a1 H H H H i-a1 H H H i-a1 H Ia-7 H H i-a1 H H H i-a1 H H i-a1 H H H H i-a1 H Ia-8 H H i-a1 H H H i-a1 H H H i-a1 H H H i-a1 H Ia-9 H i-a2 H H H i-a2 H H H i-a2 H H H H i-a2 H Ia-10 H i-a2 H H H i-a2 H H H H i-a2 H H H i-a2 H Ia-11 H i-a2 H H H H i-a2 H H i-a2 H H H H i-a2 H Ia-12 H i-a2 H H H H i-a2 H H H i-a2 H H H i-a2 H Ia-13 H H i-a2 H H i-a2 H H H i-a2 H H H H i-a2 H Ia-14 H H i-a2 H H i-a2 H H H H i-a2 H H H i-a2 H Ia-15 H H i-a2 H H H i-a2 H H i-a2 H H H H i-a2 H Ia-16 H H i-a2 H H H i-a2 H H H i-a2 H H H i-a2 H Ia-17 H i-a3 H H H i-a3 H H H i-a3 H H H H i-a3 H Ia-18 H i-a3 H H H i-a3 H H H H i-a3 H H H i-a3 H Ia-19 H i-a3 H H H H i-a3 H H i-a3 H H H H i-a3 H Ia-20 H i-a3 H H H H i-a3 H H H i-a3 H H H i-a3 H Ia-21 H H i-a3 H H i-a3 H H H i-a3 H H H H i-a3 H Ia-22 H H i-a3 H H i-a3 H H H H i-a3 H H H i-a3 H Ia-23 H H i-a3 H H H i-a3 H H i-a3 H H H H i-a3 H Ia-24 H H i-a3 H H H i-a3 H H H i-a3 H H H i-a3 H Ia-25 H i-a4 H H H i-a4 H H H i-a4 H H H H i-a4 H Ia-26 H i-a4 H H H i-a4 H H H H i-a4 H H H i-a4 H Ia-27 H i-a4 H H H H i-a4 H H i-a4 H H H H i-a4 H Ia-28 H i-a4 H H H H i-a4 H H H i-a4 H H H i-a4 H Ia-29 H H i-a4 H H i-a4 H H H i-a4 H H H H i-a4 H Ia-30 H H i-a4 H H i-a4 H H H H i-a4 H H H i-a4 H Ia-31 H H i-a4 H H H i-a4 H H i-a4 H H H H i-a4 H Ia-32 H H i-a4 H H H i-a4 H H H i-a4 H H H i-a4 H Ia-33 H i-a5 H H H i-a5 H H H i-a5 H H H H i-a5 H Ia-34 H i-a5 H H H i-a5 H H H H i-a5 H H H i-a5 H Ia-35 H i-a5 H H H H i-a5 H H i-a5 H H H H i-a5 H Ia-36 H i-a5 H H H H i-a5 H H H i-a5 H H H i-a5 H Ia-37 H H i-a5 H H i-a5 H H H i-a5 H H H H i-a5 H Ia-38 H H i-a5 H H i-a5 H H H H i-a5 H H H i-a5 H Ia-39 H H i-a5 H H H i-a5 H H i-a5 H H H H i-a5 H Ia-40 H H i-a5 H H H i-a5 H H H i-a5 H H H i-a5 H

[0173] [Table 2]

[0174] <![CDATA[R 1 ]]> <![CDATA[R 2 ]]> <![CDATA[R 3 ]]> <![CDATA[R 4 ]]> <![CDATA[R 5 ]]> <![CDATA[R 6 ]]> <![CDATA[R 7 ]]> <![CDATA[R 8 ]]> <![CDATA[R 9 ]]> <![CDATA[R 10 ]]> <![CDATA[R 11 ]]> <![CDATA[R 12 ]]> <![CDATA[R 13 ]]> <![CDATA[R 14 ]]> <![CDATA[R 15 ]]> <![CDATA[R 16 ]]> Ia-41 H i-a6 H H H i-a6 H H H i-a6 H H H H i-a6 H Ia-42 H i-a6 H H H i-a6 H H H H i-a6 H H H i-a6 H Ia-43 H i-a6 H H H H i-a6 H H i-a6 H H H H i-a6 H Ia-44 H i-a6 H H H H i-a6 H H H i-a6 H H H i-a6 H Ia-45 H H i-a6 H H i-a6 H H H i-a6 H H H H i-a6 H Ia-46 H H i-a6 H H i-a6 H H H H i-a6 H H H i-a6 H Ia-47 H H i-a6 H H H i-a6 H H i-a6 H H H H i-a6 H Ia-48 H H i-a6 H H H i-a6 H H H i-a6 H H H i-a6 H <h2 style=";text-align:left;direction:ltr">Ia-49 H <h2 style=";text-align:left;direction:ltr"> i-a7 H H H <h2 style=";text-align:left;direction:ltr"> i-a7 H H H <h2 style=";text-align:left;direction:ltr"> i-a7 H H H H <h2 style=";text-align:left;direction:ltr"> i-a7 H <h2 style=";text-align:left;direction:ltr"> Ia-50 H <h2 style=";text-align:left;direction:ltr"> i-a7 H H H <h2 style=";text-align:left;direction:ltr"> i-a7 H H H H <h2 style=";text-align:left;direction:ltr"> i-a7 H H H <h2 style=";text-align:left;direction:ltr"> i-a7 H <h2 style=";text-align:left;direction:ltr"> Ia-51 H <h2 style=";text-align:left;direction:ltr"> i-a7 H H H H <h2 style=";text-align:left;direction:ltr"> i-a7 H H <h2 style=";text-align:left;direction:ltr"> i-a7 H H H H <h2 style=";text-align:left;direction:ltr"> i-a7 H <h2 style=";text-align:left;direction:ltr"> Ia-52 H <h2 style=";text-align:left;direction:ltr"> i-a7 H H H H <h2 style=";text-align:left;direction:ltr"> i-a7 H H H <h2 style=";text-align:left;direction:ltr"> i-a7 H H H <h2 style=";text-align:left;direction:ltr"> i-a7 H <h2 style=";text-align:left;direction:ltr"> Ia-53 H H <h2 style=";text-align:left;direction:ltr"> i-a7 H H <h2 style=";text-align:left;direction:ltr"> i-a7 H H H <h2 style=";text-align:left;direction:ltr"> i-a7 H H H H <h2 style=";text-align:left;direction:ltr"> i-a7 H <h2 style=";text-align:left;direction:ltr"> Ia-54 H H <h2 style=";text-align:left;direction:ltr"> i-a7 H H <h2 style=";text-align:left;direction:ltr"> i-a7 H H H H <h2 style=";text-align:left;direction:ltr"> i-a7 H H H <h2 style=";text-align:left;direction:ltr"> i-a7 H <h2 style=";text-align:left;direction:ltr"> Ia-55 H H <h2 style=";text-align:left;direction:ltr"> i-a7 H H H <h2 style=";text-align:left;direction:ltr"> i-a7 H H <h2 style=";text-align:left;direction:ltr"> i-a7 H H H H <h2 style=";text-align:left;direction:ltr"> i-a7 H <h2 style=";text-align:left;direction:ltr"> Ia-56 H H <h2 style=";text-align:left;direction:ltr"> i-a7 H H H <h2 style=";text-align:left;direction:ltr"> i-a7 H H H <h2 style=";text-align:left;direction:ltr"> i-a7 H H H <h2 style=";text-align:left;direction:ltr"> i-a7 H <h2 style=";text-align:left;direction:ltr"> Ia-57 H <h2 style=";text-align:left;direction:ltr"> i-a8 H H H <h2 style=";text-align:left;direction:ltr"> i-a8 H H H <h2 style=";text-align:left;direction:ltr"> i-a8 H H H H <h2 style=";text-align:left;direction:ltr"> i-a8 H <h2 style=";text-align:left;direction:ltr"> Ia-58 H <h2 style=";text-align:left;direction:ltr"> i-a8 H H H <h2 style=";text-align:left;direction:ltr"> i-a8 H H H H <h2 style=";text-align:left;direction:ltr"> i-a8 H H H <h2 style=";text-align:left;direction:ltr"> i-a8 H <h2 style=";text-align:left;direction:ltr"> Ia-59 H <h2 style=";text-align:left;direction:ltr"> i-a8 H H H H <h2 style=";text-align:left;direction:ltr"> i-a8 H H <h2 style=";text-align:left;direction:ltr"> i-a8 H H H H <h2 style=";text-align:left;direction:ltr"> i-a8 H <h2 style=";text-align:left;direction:ltr"> Ia-60 H <h2 style=";text-align:left;direction:ltr"> i-a8 H H H H <h2 style=";text-align:left;direction:ltr"> i-a8 H H H <h2 style=";text-align:left;direction:ltr"> i-a8 H H H <h2 style=";text-align:left;direction:ltr"> i-a8 H <h2 style=";text-align:left;direction:ltr"> Ia-61 H H <h2 style=";text-align:left;direction:ltr"> i-a8 H H <h2 style=";text-align:left;direction:ltr"> i-a8 H H H <h2 style=";text-align:left;direction:ltr"> i-a8 H H H H <h2 style=";text-align:left;direction:ltr"> i-a8 H <h2 style=";text-align:left;direction:ltr"> Ia-62 H H <h2 style=";text-align:left;direction:ltr"> i-a8 H H <h2 style=";text-align:left;direction:ltr"> i-a8 H H H H <h2 style=";text-align:left;direction:ltr"> i-a8 H H H <h2 style=";text-align:left;direction:ltr"> i-a8 H <h2 style=";text-align:left;direction:ltr"> Ia-63 H H <h2 style=";text-align:left;direction:ltr"> i-a8 H H H <h2 style=";text-align:left;direction:ltr"> i-a8 H H <h2 style=";text-align:left;direction:ltr"> i-a8 H H H H <h2 style=";text-align:left;direction:ltr"> i-a8 H <h2 style=";text-align:left;direction:ltr"> Ia-64 H H <h2 style=";text-align:left;direction:ltr"> i-a8 H H H <h2 style=";text-align:left;direction:ltr"> i-a8 H H H <h2 style=";text-align:left;direction:ltr"> i-a8 H H H <h2 style=";text-align:left;direction:ltr"> i-a8 H <h2 style=";text-align:left;direction:ltr"> Ia-65 H <h2 style=";text-align:left;direction:ltr"> i-a9 H H H <h2 style=";text-align:left;direction:ltr"> i-a9 H H H <h2 style=";text-align:left;direction:ltr"> i-a9 H H H H <h2 style=";text-align:left;direction:ltr"> i-a9 H <h2 style=";text-align:left;direction:ltr"> Ia-66 H <h2 style=";text-align:left;direction:ltr"> i-a9 H H H <h2 style=";text-align:left;direction:ltr"> i-a9 H H H H <h2 style=";text-align:left;direction:ltr"> i-a9 H H H <h2 style=";text-align:left;direction:ltr"> i-a9 H <h2 style=";text-align:left;direction:ltr"> Ia-67 H <h2 style=";text-align:left;direction:ltr"> i-a9 H H H H <h2 style=";text-align:left;direction:ltr"> i-a9 H H <h2 style=";text-align:left;direction:ltr"> i-a9 H H H H <h2 style=";text-align:left;direction:ltr"> i-a9 H <h2 style=";text-align:left;direction:ltr"> Ia-68 H <h2 style=";text-align:left;direction:ltr"> i-a9 H H H H <h2 style=";text-align:left;direction:ltr"> i-a9 H H H <h2 style=";text-align:left;direction:ltr"> i-a9 H H H <h2 style=";text-align:left;direction:ltr"> i-a9 H <h2 style=";text-align:left;direction:ltr"> Ia-69 H H <h2 style=";text-align:left;direction:ltr"> i-a9 H H <h2 style=";text-align:left;direction:ltr"> i-a9 H H H <h2 style=";text-align:left;direction:ltr"> i-a9 H H H H <h2 style=";text-align:left;direction:ltr"> i-a9 H <h2 style=";text-align:left;direction:ltr"> Ia-70 H H <h2 style=";text-align:left;direction:ltr"> i-a9 H H <h2 style=";text-align:left;direction:ltr"> i-a9 H H H H <h2 style=";text-align:left;direction:ltr"> i-a9 H H H <h2 style=";text-align:left;direction:ltr"> i-a9 H <h2 style=";text-align:left;direction:ltr"> Ia-71 H H <h2 style=";text-align:left;direction:ltr"> i-a9 H H H <h2 style=";text-align:left;direction:ltr"> i-a9 H H <h2 style=";text-align:left;direction:ltr"> i-a9 H H H H <h2 style=";text-align:left;direction:ltr"> i-a9 H <h2 style=";text-align:left;direction:ltr"> Ia-72 H H <h2 style=";text-align:left;direction:ltr"> i-a9 H H H <h2 style=";text-align:left;direction:ltr"> i-a9 H H H <h2 style=";text-align:left;direction:ltr"> i-a9 H H H <h2 style=";text-align:left;direction:ltr"> i-a9 H <h2 style=";text-align:left;direction:ltr"> Ia-73 H <h2 style=";text-align:left;direction:ltr"> i-a10 H H H <h2 style=";text-align:left;direction:ltr"> i-a10 H H H <h2 style=";text-align:left;direction:ltr"> i-a10 H H H H <h2 style=";text-align:left;direction:ltr"> i-a10 H <h2 style=";text-align:left;direction:ltr"> Ia-74 H <h2 style=";text-align:left;direction:ltr"> i-a10 H H H <h2 style=";text-align:left;direction:ltr"> i-a10 H H H H <h2 style=";text-align:left;direction:ltr"> i-a10 H H H <h2 style=";text-align:left;direction:ltr"> i-a10 H <h2 style=";text-align:left;direction:ltr"> Ia-75 H <h2 style=";text-align:left;direction:ltr"> i-a10 H H H H <h2 style=";text-align:left;direction:ltr"> i-a10 H H <h2 style=";text-align:left;direction:ltr"> i-a10 H H H H <h2 style=";text-align:left;direction:ltr"> i-a10 H <h2 style=";text-align:left;direction:ltr"> Ia-76 H <h2 style=";text-align:left;direction:ltr"> i-a10 H H H H <h2 style=";text-align:left;direction:ltr"> i-a10 H H H <h2 style=";text-align:left;direction:ltr"> i-a10 H H H <h2 style=";text-align:left;direction:ltr"> i-a10 H <h2 style=";text-align:left;direction:ltr"> Ia-77 H H <h2 style=";text-align:left;direction:ltr"> i-a10 H H <h2 style=";text-align:left;direction:ltr"> i-a10 H H H <h2 style=";text-align:left;direction:ltr"> i-a10 H H H H <h2 style=";text-align:left;direction:ltr"> i-a10 H <h2 style=";text-align:left;direction:ltr"> Ia-78 H H <h2 style=";text-align:left;direction:ltr"> i-a10 H H <h2 style=";text-align:left;direction:ltr"> i-a10 H H H H <h2 style=";text-align:left;direction:ltr"> i-a10 H H H <h2 style=";text-align:left;direction:ltr"> i-a10 H <h2 style=";text-align:left;direction:ltr"> Ia-79 H H <h2 style=";text-align:left;direction:ltr"> i-a10 H H H <h2 style=";text-align:left;direction:ltr"> i-a10 H H <h2 style=";text-align:left;direction:ltr"> i-a10 H H H H <h2 style=";text-align:left;direction:ltr"> i-a10 H <h2 style=";text-align:left;direction:ltr"> Ia-80 H H <h2 style=";text-align:left;direction:ltr"> i-a10 H H H <h2 style=";text-align:left;direction:ltr"> i-a10 H H H <h2 style=";text-align:left;direction:ltr"> i-a10 H H H <h2 style=";text-align:left;direction:ltr"> i-a10 H

[0175] [Table 3]

[0176] <![CDATA[R 1 ]]> <![CDATA[R 2 ]]> <![CDATA[R 3 ]]> <![CDATA[R 4 ]]> <![CDATA[R 5 ]]> <![CDATA[R 6 ]]> <![CDATA[R 7 ]]> <![CDATA[R 8 ]]> <![CDATA[R 9 ]]> <![CDATA[R 10 ]]> <![CDATA[R 11 ]]> <![CDATA[R 12 ]]> <![CDATA[R 13 ]]> <![CDATA[R 14 ]]> <![CDATA[R 15 ]]> <![CDATA[R 16 ]]> <h2 style=";text-align:left;direction:ltr"> Ia-81 H <h2 style=";text-align:left;direction:ltr"> i-a11 H H H <h2 style=";text-align:left;direction:ltr"> i-a11 H H H <h2 style=";text-align:left;direction:ltr"> i-a11 H H H H <h2 style=";text-align:left;direction:ltr"> i-a11 H <h2 style=";text-align:left;direction:ltr"> Ia-82 H <h2 style=";text-align:left;direction:ltr"> i-a11 H H H <h2 style=";text-align:left;direction:ltr"> i-a11 H H H H <h2 style=";text-align:left;direction:ltr"> i-a11 H H H <h2 style=";text-align:left;direction:ltr"> i-a11 H <h2 style=";text-align:left;direction:ltr"> Ia-83 H <h2 style=";text-align:left;direction:ltr"> i-a11 H H H H <h2 style=";text-align:left;direction:ltr"> i-a11 H H <h2 style=";text-align:left;direction:ltr"> i-a11 H H H H <h2 style=";text-align:left;direction:ltr"> i-a11 H <h2 style=";text-align:left;direction:ltr"> Ia-84 H <h2 style=";text-align:left;direction:ltr"> i-a11 H H H H <h2 style=";text-align:left;direction:ltr"> i-a11 H H H <h2 style=";text-align:left;direction:ltr"> i-a11 H H H <h2 style=";text-align:left;direction:ltr"> i-a11 H <h2 style=";text-align:left;direction:ltr"> Ia-85 H H <h2 style=";text-align:left;direction:ltr"> i-a11 H H <h2 style=";text-align:left;direction:ltr"> i-a11 H H H <h2 style=";text-align:left;direction:ltr"> i-a11 H H H H <h2 style=";text-align:left;direction:ltr"> i-a11 H <h2 style=";text-align:left;direction:ltr"> Ia-86 H H <h2 style=";text-align:left;direction:ltr"> i-a11 H H <h2 style=";text-align:left;direction:ltr"> i-a11 H H H H <h2 style=";text-align:left;direction:ltr"> i-a11 H H H <h2 style=";text-align:left;direction:ltr"> i-a1l H <h2 style=";text-align:left;direction:ltr"> Ia-87 H H <h2 style=";text-align:left;direction:ltr"> i-a11 H H H <h2 style=";text-align:left;direction:ltr"> i-a11 H H <h2 style=";text-align:left;direction:ltr"> i-a11 H H H H <h2 style=";text-align:left;direction:ltr"> i-a11 H <h2 style=";text-align:left;direction:ltr"> Ia-88 H H <h2 style=";text-align:left;direction:ltr"> i-a11 H H H <h2 style=";text-align:left;direction:ltr"> i-a11 H H H <h2 style=";text-align:left;direction:ltr"> i-a11 H H H <h2 style=";text-align:left;direction:ltr"> i-a11 H <h2 style=";text-align:left;direction:ltr"> Ia-89 H <h2 style=";text-align:left;direction:ltr"> i-a12 H H H <h2 style=";text-align:left;direction:ltr"> i-a12 H H H <h2 style=";text-align:left;direction:ltr"> i-a12 H H H H <h2 style=";text-align:left;direction:ltr"> i-a12 H <h2 style=";text-align:left;direction:ltr"> Ia-90 H <h2 style=";text-align:left;direction:ltr"> i-a12 H H H <h2 style=";text-align:left;direction:ltr"> i-a12 H H H H <h2 style=";text-align:left;direction:ltr"> i-a12 H H H <h2 style=";text-align:left;direction:ltr"> i-a12 H 18-91 H <h2 style=";text-align:left;direction:ltr"> i-a12 H H H H <h2 style=";text-align:left;direction:ltr"> i-a12 H H <h2 style=";text-align:left;direction:ltr"> i-a12 H H H H <h2 style=";text-align:left;direction:ltr"> i-a12 H <h2 style=";text-align:left;direction:ltr"> Ia-92 H <h2 style=";text-align:left;direction:ltr"> i-a12 H H H H <h2 style=";text-align:left;direction:ltr"> i-a12 H H H <h2 style=";text-align:left;direction:ltr"> i-a12 H H H <h2 style=";text-align:left;direction:ltr"> i-a12 H Ia-93 H H i-a12 H H i-a12 H H H i-a12 H H H H i-a12 H Ia-94 H H i-a12 H H i-a12 H H H H i-a12 H H H i-a12 H Ia-95 H H i-a12 H H H i-a12 H H i-a12 H H H H i-a12 H Ia-96 H H i-a12 H H H i-a12 H H H i-a12 H H H i-a12 H Ia-97 H i-a13 H H H i-a13 H H H i-a13 H H H H i-a13 H Ia-98 H i-a13 H H H i-a13 H H H H i-a13 H H H i-a13 H Ia-99 H i-a13 H H H H i-a13 H H i-a13 H H H H i-a13 H Ia-100 H i-a13 H H H H i-a13 H H H i-a13 H H H i-a13 H Ia-101 H H i-a13 H H i-a13 H H H i-a13 H H H H i-a13 H Ia-102 H H i-a13 H H i-a13 H H H H i-a13 H H H i-a13 H Ia-103 H H i-a13 H H H i-a13 H H i-a13 H H H H i-a13 H Ia-104 H H i-a13 H H H i-a13 H H H i-a13 H H H i-a13 H Ia-105 H i-a14 H H H i-a14 H H H i-a14 H H H H i-a14 H Ia-106 H i-a14 H H H i-a14 H H H H i-a14 H H H i-a14 H Ia-107 H i-a14 H H H H i-a14 H H i-a14 H H H H i-a14 H Ia-108 H i-a14 H H H H i-a14 H H H i-a14 H H H i-a14 H Ia-109 H H i-a14 H H i-a14 H H H i-a14 H H H H i-a14 H Ia-110 H H i-a14 H H i-a14 H H H H i-a14 H H H i-a14 H Ia-111 H H i-a14 H H H i-a14 H H i-a14 H H H H i-a14 H Ia-112 H H i-a14 H H H i-a14 H H H i-a14 H H H i-a14 H Ia-113 H i-a15 H H H i-a15 H H H i-a15 H H H H i-a15 H Ia-114 H i-a15 H H H i-a15 H H H H i-a15 H H H i-a15 H Ia-115 H i-a15 H H H H i-a15 H H i-a15 H H H H i-a15 H Ia-116 H i-a15 H H H H i-a15 H H H i-a15 H H H i-a15 H Ia-117 H H i-a15 H H i-a15 H H H i-a15 H H H H i-a15 H Ia-118 H H i-a15 H H i-a15 H H H H i-a15 H H H i-a15 H Ia-119 H H i-a15 H H H i-a15 H H i-a15 H H H H i-a15 H Ia-120 H H i-a15 H H H i-a15 H H H i-a15 H H H i-a15 H

[0177] [Table 4]

[0178] <![CDATA[R 1 ]]> <![CDATA[R 2 ]]> <![CDATA[R 3 ]]> <![CDATA[R 4 ]]> <![CDATA[R 5 ]]> <![CDATA[R 6 ]]> <![CDATA[R 7 ]]> <![CDATA[R 8 ]]> <![CDATA[R 9 ]]> <![CDATA[R 10 ]]> <![CDATA[R 11 ]]> <![CDATA[R 12 ]]> <![CDATA[R 13 ]]> <![CDATA[R 14 ]]> <![CDATA[R 15 ]]> <![CDATA[R 16 ]]> Ia-121 H i-a16 H H H i-a16 H H H i-a16 H H H H i-a16 H Ia-122 H i-a16 H H H i-a16 H H H H i-a16 H H H i-a16 H Ia-123 H i-a16 H H H H i-a16 H H i-a16 H H H H i-a16 H Ia-124 H i-a16 H H H H i-a16 H H H i-a16 H H H i-a16 H Ia-125 H H i-a16 H H i-a16 H H H i-a16 H H H H i-a16 H Ia-126 H H i-a16 H H i-a16 H H H H i-a16 H H H i-a16 H Ia-127 H H i-a16 H H H i-a16 H H i-a16 H H H H i-a16 H Ia-128 H H i-a16 H H H i-a16 H H H i-a16 H H H i-a16 H Ia-129 H i-a17 H H H i-a17 H H H i-a17 H H H H i-a17 H Ia-130 H i-a17 H H H i-a17 H H H H i-a17 H H H i-a17 H Ia-131 H i-a17 H H H H i-a17 H H i-a17 H H H H i-a17 H Ia-132 H i-a17 H H H H i-a17 H H H i-a17 H H H i-a17 H Ia-133 H H i-a17 H H i-a17 H H H i-a17 H H H H i-a17 H Ia-134 H H i-a17 H H i-a17 H H H H i-a17 H H H i-a17 H Ia-135 H H i-a17 H H H i-a17 H H i-a17 H H H H i-a17 H Ia-136 H H i-a17 H H H i-a17 H H H i-a17 H H H i-a17 H

[0179] [Table 5]

[0180] <![CDATA[R 1 ]]> <![CDATA[R 2 ]]> <![CDATA[R 3 ]]> <![CDATA[R 4 ]]> <![CDATA[R 5 ]]> <![CDATA[R 6 ]]> <![CDATA[R 7 ]]> <![CDATA[R 8 ]]> <![CDATA[R 9 ]]> <![CDATA[R 10 ]]> <![CDATA[R 11 ]]> <![CDATA[R 12 ]]> <![CDATA[R 13 ]]> <![CDATA[R 14 ]]> <![CDATA[R 15 ]]> <![CDATA[R 16 ]]> Ib-1 i-a1 H H H i-a1 H H H i-a1 H H H i-a1 H H H Ib-2 i-a2 H H H i-a2 H H H i-a2 H H H i-a2 H H H Ib-3 i-a3 H H H i-a3 H H H i-a3 H H H i-a3 H H H Ib-4 i-a4 H H H i-a4 H H H i-a4 H H H i-a4 H H H Ib-5 i-a5 H H H i-a5 H H H i-a5 H H H i-a5 H H H Ib-6 i-a6 H H H i-a6 H H H i-a6 H H H i-a6 H H H Ib-7 i-a7 H H H i-a7 H H H i-a7 H H H i-a7 H H H Ib-8 i-a8 H H H i-a8 H H H i-a8 H H H i-a8 H H H Ib-9 i-a9 H H H i-a9 H H H i-a9 H H H i-a9 H H H Ib-10 i-a10 H H H i-a10 H H H i-a10 H H H i-a10 H H H Ib-11 i-a11 H H H i-a11 H H H i-a11 H H H i-a11 H H H Ib-12 i-a12 H H H i-a12 H H H i-a12 H H H i-a12 H H H Ib-13 i-a13 H H H i-a13 H H H i-a13 H H H i-a13 H H H Ib-14 i-a14 H H H i-a14 H H H i-a14 H H H i-a14 H H H Ib-15 i-a15 H H H i-a15 H H H i-a15 H H H i-a15 H H H Ib-16 i-a16 H H H i-a16 H H H i-a16 H H H i-a16 H H H Ib-17 i-a17 H H H i-a17 H H H i-a17 H H H i-a17 H H H

[0181] In Tables 1 to 5, i-a1 to i-a17 represent groups represented by the above-mentioned formulae (i-a1) to (i-a17), and H represents a hydrogen atom.

[0182] [Method for producing compound (I)]

[0183] As a method for producing compound (I), it is preferred to react compounds represented by formulae (II-1) to (II-4) in the presence of a base and a compound represented by formula (III). Hereinafter, such a production method may be referred to as the production method of the present invention.

[0184] AIX M 3 (III)

[0185] [In formula (III),

[0186] X M Represents a halogen atom, a hydroxyl group, or OR M Base. R M represents a hydrocarbon group having 1 to 6 carbon atoms]

[0187]

[0188] [In formulas (II-1) to (II-4), R 1 ~R 16 Represents the same as above R 1 ~R 16 Same meaning]

[0189] The present inventors studied the technique of reacting compounds represented by formula (II-1) to (II-4) (hereinafter, sometimes collectively referred to as phthalonitrile compound (II)) in the presence of a base as in the above-mentioned non-patent document 1 when manufacturing compound (I), and found that the reproducibility of the method was insufficient and the yield of the target compound (I) was reduced. In particular, when the above-mentioned aryloxy group (i) was present, there was a tendency for the yield to decrease. Furthermore, the present inventors found that by reacting phthalonitrile compound (II) in the presence of a base and a compound represented by formula (III) (hereinafter, sometimes referred to as an aluminum compound (III)), even when the compound (I) was present, the target compound (I) could be stably obtained at a predetermined yield or above.

[0190] It should be noted that, generally speaking, when a phthalonitrile compound is reacted in the presence of an aluminum compound (III), aluminum phthalocyanine whose central metal is an aluminum atom is preferentially obtained. However, when a phthalonitrile compound (II) having the above-mentioned aryloxy group (i) is reacted, unexpectedly, a metal-free phthalocyanine compound (I) is preferentially generated over aluminum phthalocyanine represented by the following formula (IV) (hereinafter, sometimes referred to as aluminum phthalocyanine (IV) or compound (IV)), that is, the selectivity of compound (I) as the target compound is good. Therefore, by adopting the production method of the present invention, the yield of compound (I) as the target compound can be increased. In addition, by adopting the production method of the present invention, compound (I) can be produced in a short time, which is also preferred in this regard.

[0191]

[0192] [In formula (IV), R 1 ~R 16 and X M Represents the same as above R 1 ~R 16 and X M Same meaning]

[0193] Hereinafter, the production method of the present invention will be described in detail.

[0194] In formula (III), X M Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a chlorine atom is preferred.

[0195] As R M The hydrocarbon group having 1 to 6 carbon atoms represented by R includes 1 ~R 16 The same groups as described for the hydrocarbon group having 1 to 6 carbon atoms are also applicable, and preferred embodiments thereof are also the same.

[0196] As OR M The group specifically includes alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and phenoxy groups. Among them, alkoxy groups having 1 to 6 carbon atoms are preferred, and alkoxy groups having 1 to 4 carbon atoms are more preferred.

[0197] In formula (III), X M , preferably a halogen atom, a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms, more preferably a chlorine atom or a hydroxyl group, and particularly preferably a chlorine atom.

[0198] In the phthalonitrile compound (II), R 1 ~R 16 represents the same as R in compound (I) 1 ~R16 The four compounds represented by formulae (II-1) to (II-4) may be the same or different from each other, but are preferably the same compound.

[0199] The amount of the aluminum compound (III) used is preferably 0.25 to 0.40 moles, more preferably 0.27 to 0.34 moles, relative to 1 mole of the total amount of the phthalonitrile compound (II). By adjusting the amount of the aluminum compound (III) relative to the phthalonitrile compound (II) to a predetermined value or more, the yield of the compound (I) can be further increased, and the reaction time can be further shortened. In addition, by adjusting the amount of the aluminum compound (III) relative to the phthalonitrile compound (II) to a predetermined value or less, it is easy to preferentially generate the compound (I) compared to the aluminum phthalocyanine (IV), that is, the selectivity of the compound (I) is higher.

[0200] As the base, an inorganic base and / or an organic base can be used.

[0201] Examples of the inorganic base include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal phosphates such as trisodium phosphate and tripotassium phosphate; and alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide.

[0202] Examples of the organic base include trialkylamines such as triethylamine and N,N-diisopropylethylamine; and nitrogen-containing heterocyclic compounds such as pyridine, picoline, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN).

[0203] Among them, an organic base is preferred, a nitrogen-containing heterocyclic compound is more preferred, and 1,8-diazabicyclo[5.4.0]-7-undecene is further preferred.

[0204] The amount of the base used is preferably 1.0 to 5.0 mol, more preferably 1.3 to 2.0 mol, based on 1 mol of the total amount of the phthalonitrile compounds (II).

[0205] The reaction of the phthalonitrile compound (II) may be carried out in the presence of a solvent or in the absence of a solvent. However, from the viewpoint of improving the reaction efficiency, it is preferably carried out in the presence of a solvent.

[0206] As the above-mentioned solvent, an organic solvent is preferred, and examples thereof include:

[0207] Ester solvents such as methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone;

[0208] Ether solvents such as 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, phenethyl ether and methyl anisole;

[0209] Alcohol solvents such as methanol, ethanol, propanol, butanol, heptanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol and glycerol, etc.

[0210] Among them, from the viewpoint of further improving the reaction efficiency, the above-mentioned solvent is preferably an alcohol solvent, more preferably a polyol solvent such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, glycerol, etc., and particularly preferably a polyol solvent having a boiling point of 160°C or above (preferably 200°C or above).

[0211] The amount of the solvent used is not particularly limited, and is, for example, 1 to 500 parts by mass, preferably 3 to 100 parts by mass, and more preferably 5 to 50 parts by mass, relative to 1 part by mass of the total amount of the phthalonitrile compound (II).

[0212] The reaction temperature is, for example, 50 to 200°C, preferably 90 to 180°C, and more preferably 120 to 160°C.

[0213] In the production method of the present invention, since the reaction is carried out in the presence of an aluminum compound (III), the yield of compound (I) can be increased even if the reaction time is short. From the viewpoint of productivity, the reaction time is preferably 30 minutes to 50 hours, more preferably 1 to 40 hours, further preferably 3 to 35 hours, and may be less than 20 hours or less than 15 hours.

[0214] The reaction mixture obtained by the above reaction contains the target compound (I). It should be noted that in the production method of the present invention in which the reaction is carried out in the presence of an aluminum compound (III), the above-mentioned aluminum phthalocyanine (IV) is sometimes generated as a by-product, but since the synthesis is carried out using a phthalonitrile compound (II) having at least one aryloxy group (i), the compound (I) is synthesized preferentially over the aluminum phthalocyanine (IV).

[0215] Therefore, in the production method of the present invention, the amount of compound (I) obtained is preferably 1.5 mol or more, more preferably 2.0 mol or more, and may be 3.0 mol or more or 4.0 mol or more per 1 mol of aluminum phthalocyanine (IV).

[0216] The amount of compound (I) relative to aluminum phthalocyanine (IV) can be calculated by isolating compound (I) and aluminum phthalocyanine (IV) from the reaction mixture and measuring the yields.

[0217] The method for separating compound (I) and aluminum phthalocyanine (IV) from the reaction mixture is not particularly limited, and various known methods can be used. For example, the reaction mixture can be cooled to room temperature (e.g., 18 to 24° C.), and water or ethyl acetate can be added as needed to precipitate compound (I). At this time, when aluminum phthalocyanine (IV) is contained in the reaction mixture, aluminum phthalocyanine (IV) is also precipitated together with compound (I). Thereafter, the precipitate can be washed with water, acetone, methanol, etc. as needed, and purified, for example, by column chromatography, thereby separating compound (I) and aluminum phthalocyanine (IV).

[0218] In the above-mentioned column chromatography, silica gel column chromatography is preferably used. The mobile phase (developing solvent) used in the column chromatography is not particularly limited, and can be appropriately selected according to the compound to be separated, but aromatic hydrocarbon solvents and ether solvents are preferably used, and a gradient method of extracting while changing the aromatic hydrocarbon solvent: ether solvent (mass ratio) from 100:0 to 0:100 is more preferably used.

[0219] Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene, among which toluene is preferred.

[0220] Examples of the ether solvent include those described as the solvent used in the reaction of the phthalonitrile compound (II), and tetrahydrofuran is preferred among them.

[0221] By adopting the production method of the present invention, the yield of compound (I) synthesized from phthalonitrile compound (II) can be improved. The yield of compound (I) in the reaction of synthesizing compound (I) from phthalonitrile compound (II) is preferably 5% or more, more preferably 15% or more, further preferably 20% or more, and may also be 30% or more or 40% or more.

[0222] The content of compound (I) in the total amount of colorant (A) is, for example, 20 to 100 mass %, preferably 30 to 100 mass %, more preferably 40 to 90 mass %, and further preferably 50 to 80 mass %. If the content of compound (I) in colorant (A) is within the above range, it is easier to obtain a desired spectrum, and it is easier to suppress uneven brightness after long-term use.

[0223] The colorant (A) may further contain a colorant different from the compound (I) (hereinafter, sometimes referred to as a colorant (A1)). The colorant (A1) may be any of a dye and a pigment, but a pigment is preferred from the viewpoint of further suppressing uneven brightness after long-term use.

[0224] Examples of the dye include substances having a hue that are classified as other than pigments in the Color Index (published by The Society of Dyers and Colourists) and known dyes described in the Dyeing Guide (published by the Color Dyeing Co., Ltd.).

[0225] Examples of the dye include azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, thiazole dyes, oxazine dyes, quinophthalone dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, Dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, phthalocyanine dyes, etc. Among these, organic solvent-soluble dyes are preferred.

[0226] Specific examples of dyes include:

[0227] CI Solvent Yellow 4 (hereinafter, CI Solvent Yellow is omitted and only the number is recorded. The same applies to other dyes), 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 117, 162, 163, 167, 189,

[0228] CI Solvent Red 24, 45, 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, 218, 222, 227, 230, 245, 247,

[0229] CI Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 77, 86, 99,

[0230] CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60,

[0231] CI Solvent Blue 4, 5, 14, 18, 35, 36, 37, 38, 44, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139,

[0232] CI solvent dyes such as CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35;

[0233] CI 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, 156 7, 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,

[0234] CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 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, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, ​​383, 388, 394, 401, 412, 417, 418, 422, 426,

[0235] CI 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,

[0236] CI Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102,

[0237] CI Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 1 26, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 249, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340,

[0238] CI acid green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109 and other CI acid dyes;

[0239] CI 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,

[0240] CI 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,

[0241] CI Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107,

[0242] CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104,

[0243] CI Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 87, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 1 67, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293,

[0244] CI direct dyes such as CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82;

[0245] CI Disperse Yellow 51, 54, 76,

[0246] CI Disperse Violet 26, 27,

[0247] CI disperse dyes such as CI disperse blue 1, 14, 56, 60;

[0248] CI Basic Red 1, 9, 10,

[0249] CI Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89, CI Basic Violet 2,

[0250] CI basic dyes such as CI Basic Green 1;

[0251] CI Reactive Yellow 2, 76, 116,

[0252] CI Reactive Orange 16,

[0253] CI reactive dyes such as CI Reactive Red 36;

[0254] CI Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65,

[0255] CI Mordant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 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,

[0256] CI Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48,

[0257] CI Mordant Violet 1, 1: 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58,

[0258] CI Mordant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84,

[0259] CI mordant green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53 and other CI mordant dyes;

[0260] CI vat dyes such as CI vat green 1, etc.

[0261] These dyes may be used alone or in combination of a plurality of dyes of each color.

[0262] Examples of the pigment include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

[0263] Examples of pigments classified as pigments include:

[0264] CI 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, 231 and other yellow pigments,

[0265] CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments,

[0266] CI Pigment Red 9, 97, 105, 122, 144, 166, 168, 176, 177, 180, 190, 192, 209, 215, 216, 224, 242, 246, 254, 255, 264, 265, 266, 268, 269, 273, 291 and other red pigments,

[0267] CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60 and other blue pigments,

[0268] CI Pigment Violet 1, 19, 23, 32, 36, 38 and other purple pigments,

[0269] CI Pigment Green 7, 36, 58, 59, 62, 63 and other green pigments,

[0270] CI Pigment Brown 23, 25 and other brown pigments,

[0271] Black pigments such as CI Pigment Black 1, 7, etc.

[0272] These pigments may be used alone or in combination of different colors.

[0273] The pigment may be subjected to rosin treatment, surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, grafting treatment on the pigment surface using a polymer compound, micronization treatment using a sulfuric acid micronization method, etc., washing treatment using an organic solvent or water to remove impurities, removal treatment of ionic impurities using an ion exchange method, etc. The particle size of the pigment is preferably substantially uniform.

[0274] The colorant (A1) can be appropriately selected and used according to the desired spectrum. For example, when a green filter in a color filter is formed, the colorant (A1) is preferably a yellow pigment, more preferably at least one selected from CI Pigment Yellow 138, 150 and 185, and further preferably CI Pigment Yellow 138 and / or 185.

[0275] When a yellow pigment is used as the colorant (A1), the content of the yellow pigment is, for example, 1 to 200 parts by mass, preferably 5 to 150 parts by mass, more preferably 10 to 100 parts by mass, and further preferably 15 to 80 parts by mass, relative to 100 parts by mass of the compound (I). If the content of the yellow pigment is within the above range, it is easy to obtain a desired spectrum.

[0276] The content of the colorant (A) in the colored resin composition is, for example, 0.5 to 80% by mass, preferably 2 to 70% by mass, more preferably 8 to 55% by mass, and further preferably 25 to 50% by mass relative to the total amount of the solid content. If the content of the colorant (A) is within the above range, it is easier to obtain a desired spectrum and color concentration.

[0277] In this specification, the "total amount of solid content" refers to the total amount of components obtained by removing the solvent from the colored resin composition of the present invention. The total amount of solid content and the content of each component relative to the total amount can be measured by a known analytical method such as liquid chromatography and gas chromatography.

[0278] <Resin (B)>

[0279] The resin (B) is an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].

[0280] Resin [K1]: a copolymer of at least one monomer (a) selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as "(a)") and a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)");

[0281] Resin [K2]: a copolymer of (a), (b) and a monomer (c) copolymerizable with (a) (which is different from (a) and (b)) (hereinafter sometimes referred to as "(c)");

[0282] Resin [K3]: a copolymer of (a) and (c);

[0283] Resin [K4]: a resin obtained by reacting (b) with a copolymer of (a) and (c);

[0284] Resin [K5]: a resin obtained by reacting (a) with a copolymer of (b) and (c);

[0285] Resin [K6]: A resin obtained by reacting (a) with a copolymer of (b) and (c) and further reacting a polyvalent carboxylic acid and / or a carboxylic anhydride.

[0286] Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, and p-vinylbenzoic acid;

[0287] 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.;

[0288] Bicyclic unsaturated compounds containing a carboxyl 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, and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;

[0289] Unsaturated dicarboxylic 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;

[0290] Unsaturated mono-(meth)acryloyloxyalkyl) esters of divalent or higher polycarboxylic acids such as mono-(2-(meth)acryloyloxyethyl) succinate and mono-(2-(meth)acryloyloxyethyl) phthalate;

[0291] Unsaturated acrylic acid esters containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid, etc.

[0292] Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferred from the viewpoint of copolymerization reactivity and solubility of the obtained resin in an aqueous alkali solution.

[0293] (b) refers to a polymerizable compound having, for example, a cyclic ether structure having 2 to 4 carbon atoms (e.g., at least one selected from 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.

[0294] In addition, in this specification, "(meth)acrylic acid" means at least one selected from acrylic acid and methacrylic acid. Expressions such as "(meth)acryloyl" and "(meth)acrylate" have the same meaning.

[0295] As (b), for example, there can be mentioned a monomer (b1) having an ethylene oxide group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b2)"), a monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), and the like.

[0296] As (b1), for example, there can be mentioned a monomer (b1-1) having a structure in which a straight-chain or branched unsaturated aliphatic 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)").

[0297] Examples of (b1-1) include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α-methyl-p-vinyl benzyl glycidyl ether, 2,3-bis(glycidyloxymethyl) 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.

[0298] Examples of (b1-2) include vinylcyclohexene monoxide, 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), 3,4-epoxytricyclo[5.2.1.0](meth)acrylate. 2,6 ]decyl ester, a compound represented by formula (R1), and a compound represented by formula (R2), etc.

[0299]

[0300] [In formula (R1) and formula (R2), R ra and Rrb It represents 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 by a hydroxyl group.

[0301] X ra and X rb Indicates a single bond, *-R rc -,*-R rc -O-, *-R rc -S- or *-R rc -NH-.

[0302] R rc It represents an alkanediyl group having 1 to 6 carbon atoms.

[0303] * indicates the bonding site with O]

[0304] Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.

[0305] Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxy group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl and 4-hydroxybutyl.

[0306] As R ra and R rb , preferably, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are mentioned, and more preferably, a hydrogen atom and a methyl group are mentioned.

[0307] 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.

[0308] As X ra and X rb , preferably include a single bond, methylene, ethylene, *-CH2-O- and *-CH2CH2-O-, and more preferably include a single bond and *-CH2CH2-O- (* represents a bonding site with O).

[0309] Examples of the compound represented by formula (R1) include compounds represented by any one of formula (R1-1) to formula (R1-15). Among them, preferred are compounds represented by formula (R1-1), formula (R1-3), formula (R1-5), formula (R1-7), formula (R1-9) or formula (R1-11) to formula (R1-15), and more preferred are compounds represented by formula (R1-1), formula (R1-7), formula (R1-9) or formula (R1-15).

[0310]

[0311] Examples of the compound represented by formula (R2) include compounds represented by any one of formula (R2-1) to formula (R2-15). Among them, preferred are compounds represented by formula (R2-1), formula (R2-3), formula (R2-5), formula (R2-7), formula (R2-9) or formula (R2-11) to formula (R2-15), and more preferred are compounds represented by formula (R2-1), formula (R2-7), formula (R2-9) or formula (R2-15).

[0312]

[0313] As (b2), a monomer having an oxetane group and a (meth)acryloyloxy group is more preferred. As (b2), 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-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, etc. can be mentioned.

[0314] As (b3), a monomer having a tetrahydrofuranyl group and a (meth)acryloyloxy group is more preferred. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

[0315] As (b), (b1) is preferred from the viewpoint of further improving the reliability of the obtained color filter, such as heat resistance and chemical resistance. Furthermore, (b1-2) is more preferred from the viewpoint of excellent storage stability of the colored resin composition.

[0316] Examples of (c) include 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](meth)acrylate, 2,6] decane-8-yl ester (in the technical field, it is commonly known as "dicyclopentanyl (meth)acrylate". In addition, it is sometimes called "tricyclodecyl (meth)acrylate"), tricyclo[5.2.1.0 2,6 (Meth)acrylates such as decen-8-yl ester (in the technical field, it is commonly known as "dicyclopentenyl (meth)acrylate"), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

[0317] (Meth)acrylates containing a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

[0318] Diethyl maleate, diethyl fumarate, diethyl itaconate and other dicarboxylic acid diesters;

[0319] 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, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene Bicyclic unsaturated compounds such as cyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene;

[0320] Dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide;

[0321] 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.

[0322] As (c), 2-ethylhexyl (meth)acrylate, dicyclopentyl (meth)acrylate, benzyl (meth)acrylate, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene and the like are preferred, and styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene and the like are more preferred from the viewpoint of copolymerization reactivity and heat resistance.

[0323] In the resin [K1], the ratio of the structural units derived from each monomer in all the structural units constituting the resin [K1] is preferably:

[0324] Structural unit derived from (a): 2 to 60 mol%

[0325] Structural unit derived from (b): 40 to 98 mol %

[0326] More preferably:

[0327] Structural unit derived from (a): 10 to 50 mol%

[0328] Structural unit derived from (b): 50 to 90 mol %.

[0329] When the ratio of the structural unit of the resin [K1] is within the above range, the storage stability of the colored resin composition, the developability when forming a colored pattern, and the solvent resistance of the obtained color filter tend to be more excellent.

[0330] The resin [K1] can be produced, for example, by referring to the method described in the document "Experimental Methods for Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Doujin Co., Ltd., 1st edition, 1st printing, published on March 1, 1972) and the references described in the document.

[0331] Specifically, the following method can be cited: a predetermined amount of (a) and (b), a polymerization initiator, and a solvent are placed in a reaction container, for example, oxygen is replaced by nitrogen to form a deoxygenated atmosphere, and heating and heat preservation are performed while stirring. It should be noted that the polymerization initiator and solvent used here are not particularly limited, and polymerization initiators and solvents commonly used in this field can be used. For example, as a polymerization initiator, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile)), an organic peroxide (benzoyl peroxide, etc.) can be cited, as a solvent, any solvent that dissolves each monomer can be used, and as a solvent (E), the solvents described later can be cited.

[0332] It should be noted that the obtained copolymer may be used as a solution after the reaction, a concentrated or diluted solution, or a substance taken out as a solid (powder) by a method such as reprecipitation. In particular, by using the solvent contained in the colored resin composition as a solvent during the polymerization, the solution after the reaction can be used directly for preparing the colored resin composition, so that the production process of the colored resin composition can be simplified.

[0333] In the resin [K2], the ratio of the structural units derived from each monomer in all the structural units constituting the resin [K2] is preferably:

[0334] Structural unit derived from (a): 2 to 45 mol%

[0335] Structural unit derived from (b): 2 to 95 mol%

[0336] Structural unit derived from (c): 1 to 65 mol %

[0337] More preferably:

[0338] Structural unit derived from (a): 5 to 40 mol%

[0339] Structural unit derived from (b): 5 to 80 mol%

[0340] Structural unit derived from (c): 5 to 60 mol %.

[0341] When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the colored resin composition, the developability when forming a colored pattern, and the solvent resistance, heat resistance, and mechanical strength of the obtained color filter tend to be more excellent.

[0342] The resin [K2] can be produced, for example, in the same manner as described as the method for producing the resin [K1].

[0343] In the resin [K3], the ratio of the structural units derived from each monomer in all the structural units constituting the resin [K3] is preferably:

[0344] Structural unit derived from (a): 2 to 60 mol%

[0345] Structural unit derived from (c): 40 to 98 mol %

[0346] More preferably:

[0347] Structural unit derived from (a): 10 to 50 mol%

[0348] Structural unit derived from (c): 50 to 90 mol %.

[0349] The resin [K3] can be produced, for example, in the same manner as described as the method for producing the resin [K1].

[0350] The resin [K4] can be produced by obtaining a copolymer of (a) and (c), and adding a cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and / or carboxylic anhydride contained in (a).

[0351] First, a copolymer of (a) and (c) is produced in the same manner as described as the method for producing resin [K1]. In this case, the ratio of the structural units derived from each monomer is preferably the same as the ratio given for resin [K3].

[0352] Next, the cyclic ether having 2 to 4 carbon atoms contained in (b) is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the above copolymer.

[0353] After producing the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, (b), a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (e.g., tris(dimethylaminomethyl)phenol, etc.), and a polymerization inhibitor (e.g., hydroquinone, etc.) are placed in the flask, and the reaction is carried out at, for example, 60 to 130° C. for 1 to 10 hours, thereby producing resin [K4].

[0354] The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, relative to 100 mol of (a). By falling within this range, there is a tendency for the storage stability of the colored resin composition, the developability when forming a pattern, and the balance of the solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained pattern to become good. From the perspective that the reactivity of the cyclic ether is high and it is not easy to leave unreacted (b), as the (b) used in the resin [K4], (b1) is preferred, and (b1-1) is more preferred.

[0355] The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass relative 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 relative to 100 parts by mass of the total amount of (a), (b) and (c).

[0356] The reaction conditions such as the feeding method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the calorific value of polymerization, etc. It should be noted that, similarly to the polymerization conditions, the feeding method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the calorific value of polymerization, etc.

[0357] As a first step, the resin [K5] is subjected to the same method as the above-mentioned method for producing the resin [K1] to obtain a copolymer of (b) and (c). As described above, the obtained copolymer may be used directly as a solution after the reaction, or may be used as a concentrated or diluted solution, or may be used as a solid (powder) obtained by a method such as reprecipitation.

[0358] The ratio of the structural units derived from (b) and (c) relative to the total number of moles of all structural units constituting the above-mentioned copolymer is preferably:

[0359] Structural unit derived from (b): 5 to 95 mol%

[0360] Structural unit derived from (c): 5 to 95 mol %

[0361] More preferably:

[0362] Structural unit derived from (b): 10 to 90 mol%

[0363] Structural unit derived from (c): 10 to 90 mol %.

[0364] Furthermore, resin [K5] can be obtained by reacting the carboxylic acid or carboxylic anhydride contained in (a) with the cyclic ether derived from (b) contained in the copolymer of (b) and (c) under the same conditions as in the method for producing resin [K4].

[0365] The amount of (a) to be reacted with the copolymer is preferably 5 to 100 mol relative to 100 mol of (b). Since the cyclic ether has high reactivity and unreacted (b) is less likely to remain, (b1) is preferred as (b) to be used in the resin [K5], and (b1-1) is more preferred.

[0366] The resin [K6] is obtained by further reacting the resin [K5] with a carboxylic acid anhydride. The carboxylic acid anhydride is reacted with the hydroxyl group generated by the reaction of the cyclic ether with the carboxylic acid or the carboxylic acid anhydride.

[0367] Examples of the carboxylic anhydride include succinic anhydride, 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, etc. The amount of the carboxylic anhydride used is preferably 0.1 to 1 mol relative to 1 mol of the amount of (a) used.

[0368] Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate / (meth)acrylic acid copolymers, 3,4-epoxytricyclo[5.2.1.0 2.6 ] decyl ester / (meth) acrylic acid copolymer resin [K1]; acrylic acid 3,4-epoxy tricyclic [5.2.1.0 2.6 ] decyl ester / benzyl (meth)acrylate / (meth)acrylic acid copolymer, 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 ester / (meth)acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl ester / (meth)acrylic acid / vinyl toluene copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6] decyl ester / (meth)acrylic acid / N-cyclohexylmaleimide / 2-hydroxyethyl (meth)acrylate copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane / (meth)acrylic acid / styrene copolymer and the like resins [K2]; benzyl (meth)acrylate / (meth)acrylic acid copolymer, styrene / (meth)acrylic acid copolymer and the like resins [K3]; 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 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, etc. [K5]; resins obtained by further reacting a resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate with tetrahydrophthalic anhydride, resins obtained by further reacting a resin obtained by reacting (meth)acrylic acid with a copolymer of 2-ethylhexyl (meth)acrylate / glycidyl (meth)acrylate / dicyclopentanyl (meth)acrylate with succinic anhydride, etc. [K6], etc.

[0369] Among them, as resin (B), at least one selected from copolymers containing a structural unit derived from at least one selected from unsaturated carboxylic acid and unsaturated carboxylic anhydride and a structural unit having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (resin [K1], resin [K2]) and resin [K6] is preferred, and resin [K1] and / or resin [K2] are more preferred.

[0370] The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 500 to 100000, more preferably 1000 to 50000, and further preferably 3000 to 30000. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film rate is high, the solubility of the unexposed portion in the developer is good, and the resolution of the colored pattern tends to be improved.

[0371] The dispersion degree [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1-6, more preferably 1.2-4.

[0372] The acid value of the resin (B) is preferably 10 to 170 mg-KOH / g, more preferably 30 to 155 mg-KOH / g, and further preferably 50 to 140 mg-KOH / g, based on solid content. Here, the acid value refers to 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 a potassium hydroxide aqueous solution.

[0373] The content of the resin (B) is preferably 7 to 80% by mass, more preferably 13 to 70% by mass, further preferably 17 to 60% by mass, and further preferably 20 to 50% by mass relative to the total solid content of the colored resin composition. 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 tend to be improved.

[0374] In addition, the content of the resin (B) is, for example, 30 to 200 parts by mass, preferably 50 to 180 parts by mass, and more preferably 80 to 150 parts by mass relative to 100 parts by mass of the compound (I). By adjusting the content of the resin (B) to be within the above range, there is a tendency to easily improve the above-mentioned brightness unevenness suppression effect.

[0375] <Polymerizable compound (C)>

[0376] The polymerizable compound (C) is a compound that can be polymerized by active radicals and / or acids generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and are preferably (meth)acrylate compounds.

[0377] Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol poly(meth)acrylate (e.g., pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate), dipentaerythritol poly(meth)acrylate (e.g., dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate), tripentaerythritol poly(meth)acrylate (e.g., tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate), tetrapentaerythritol poly(meth)acrylate (e.g., tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate), tris(2-(meth)acryloyloxyethyl)isocyanurate, alkoxylated pentaerythritol poly(meth)acrylate (e.g., ethoxylated pentaerythritol tri(meth)acrylate), tetrapentaerythritol poly(meth)acrylate (e.g., tetrapentaerythritol tri(meth)acrylate, tetrapentaerythritol nona(meth)acrylate), esters, ethoxylated pentaerythritol tetra(meth)acrylates, propoxylated pentaerythritol tri(meth)acrylates, propoxylated pentaerythritol tetra(meth)acrylates), alkoxylated dipentaerythritol poly(meth)acrylates (e.g. ethoxylated dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol penta(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate), caprolactone-modified pentaerythritol poly(meth)acrylates (e.g. caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate), caprolactone-modified dipentaerythritol poly(meth)acrylates (e.g. caprolactone-modified dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate), and the like.

[0378] Among them, at least one selected from trimethylolpropane tri(meth)acrylate and dipentaerythritol poly(meth)acrylate is preferred.

[0379] The weight average molecular weight of the polymerizable compound (C) is preferably 150 to 2,900, more preferably 250 to 1,500.

[0380] The content of the polymerizable compound (C) is, for example, 5 to 65% by mass, preferably 6 to 50% by mass, and more preferably 8 to 30% by mass relative to the total amount of the solid content of the colored resin composition. If the content of the polymerizable compound (C) is within the above range, the residual film rate when forming a colored pattern and the chemical resistance of the color filter tend to be further improved.

[0381] <Polymerization initiator (D)>

[0382] The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. by the action of light or heat to initiate polymerization, and a known polymerization initiator can be used.

[0383] Examples of the polymerization initiator that generates active radicals include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds.

[0384] The O-acyl oxime compound is a compound having a partial structure represented by formula (d1).

[0385]

[0386] 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-dioxolanylmethyloxy)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-acetoxy-1-[4-(2-hydroxyethyloxy)phenylsulfanylphenyl]propane-1-one-2-imine, N-acetoxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine, 2-[(acetoxy)imino]-3-cyclohexyl-1-[4-(phenylsulfanyl)phenyl]propane-1-one, and the like. Commercially available products such as Irgacure OXE01, OXE02, OXE03 (all manufactured by BASF), N-1919 (manufactured by ADEKA), PBG-314, PBG-317, PBG-326, PBG-327, and PBG-329 (all manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) may also be used. Among them, the O-acyl oxime compound is preferably selected from N-acetoxy-1-[4-(2-hydroxyethyloxy)phenylsulfanylphenyl]propane-1-one-2-imine, N-acetoxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine, 2-[(acetoxy)imino]-3-cyclohexyl-1-[4-(phenylsulfanyl)phenyl]propane-1-one, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, The present invention further comprises at least one selected from the group consisting of 2-[(acetyloxy)imino]-3-cyclohexyl-1-[4-(phenylsulfanyl)phenyl]propane-1-one, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-acetoxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine, and more preferably at least one selected from the group consisting of 2-[(acetyloxy)imino]-3-cyclohexyl-1-[4-(phenylsulfanyl)phenyl]propane-1-one, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-acetoxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine. When these O-acyl oxime compounds are used, a color filter having high brightness tends to be obtained.

[0387] 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.

[0388]

[0389] Examples of the compound having a partial structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane-1-one. Commercially available products such as Irgacure 369, 907, and 379 (all manufactured by BASF) can also be used.

[0390] Examples of compounds having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-〔4-(2-hydroxyethoxy)phenyl〕propane-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, and benzil dimethyl ketal.

[0391] From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (d2).

[0392] 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-methoxyphenyl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine. [2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

[0393] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may also be used.

[0394] 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, Japanese Patent Application Laid-Open No. 6-75372 and Japanese Patent Application Laid-Open No. 6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, (Alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (see, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with alkoxycarbonyl groups (see, for example, Japanese Patent Application Laid-Open No. 7-10913, etc.), and the like.

[0395] 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, benzil, methyl phenylglyoxylate, and titanocene compounds, etc. These are preferably used in combination with the polymerization initiator aid (D1) (particularly amine compounds) described later.

[0396] Examples of the polymerization initiator that generates an acid include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, and diphenyliodonium. p-Toluenesulfonate, diphenyl iodide Hexafluoroantimonate, etc. Salts, nitrobenzyl tosylate, benzoin tosylate, etc.

[0397] The polymerization initiator (D) preferably contains at least one selected from an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound and a biimidazole compound, and more preferably contains an O-acyloxime compound.

[0398] The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and further preferably 2 to 10 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). If the content of the polymerization initiator (D) is within the above range, there is a tendency to increase sensitivity and shorten the exposure time, thereby improving the productivity of the color filter.

[0399] <Polymerization initiator aid (D1)>

[0400] The polymerization initiator aid (D1) is a compound or a sensitizer for accelerating the polymerization of the polymerizable compound to be polymerized by the polymerization initiator. When the polymerization initiator aid (D1) is included, it is usually used in combination with the polymerization initiator (D).

[0401] Examples of the polymerization initiator aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

[0402] Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isopentyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone. Among them, 4,4'-bis(diethylamino)benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may also be used.

[0403] 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, and 2-ethyl-9,10-dibutoxyanthracene.

[0404] Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0405] Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

[0406] When these polymerization initiator aids (D1) are used, their content is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). If the amount of the polymerization initiator aid (D1) is within this range, there is a tendency that a colored pattern can be formed with further high sensitivity, and the productivity of the color filter is improved.

[0407] <Solvent (E)>

[0408] The solvent (E) is not particularly limited, and a solvent commonly used in the field can be used. For example, an ester solvent (a solvent containing -COO- and not containing -O- in the molecule), an ether solvent (a solvent containing -O- and not containing -COO- in the molecule), an ether ester solvent (a solvent containing -COO- and -O- in the molecule), a ketone solvent (a solvent containing -CO- and not containing -COO- in the molecule), an alcohol solvent (a solvent containing OH and not containing -O-, -CO- and -COO- in the molecule), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide, etc. can be mentioned.

[0409] Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0410] Examples of the ether solvent 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, phenethyl ether, and methyl anisole.

[0411] Examples of the ether ester solvent 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.

[0412] Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0413] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0414] Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

[0415] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0416] Among the above solvents, an organic solvent having a boiling point of 120° C. to 180° C. at 1 atm is preferred from the viewpoint of coating properties and drying properties. As the solvent, at least one selected from 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 is preferred, and at least one selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethyl lactate and ethyl 3-ethoxypropionate is more preferred.

[0417] In addition, as the solvent (E), it is also preferable to use an ether ester solvent and a ketone solvent in combination. In this case, as the ether ester solvent, C 2-3 Alkylene glycol mono C 1-4 Alkyl ether acetate, more preferably propylene glycol mono-C 1-4 Alkyl ether acetate. As the ketone solvent, 4-hydroxy-4-methyl-2-pentanone is preferred.

[0418] When the ether ester solvent and the ketone solvent are used in combination, the content of the ketone solvent is preferably 1 to 100 parts by mass, more preferably 3 to 50 parts by mass, and even more preferably 5 to 20 parts by mass based on 100 parts by mass of the total of the ether ester solvent and the ketone solvent.

[0419] The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, relative to the total amount of the colored resin composition. In other words, the solid content of the colored resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness during coating is good, and the color density is not insufficient when forming a color filter, so there is a tendency for display characteristics and sensitivity to become good.

[0420] <Leveling agent (F)>

[0421] Examples of the leveling agent (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms, etc. These may have a polymerizable group in a side chain.

[0422] Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specific examples include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by MOMENTIVE PERFORMANCE MATERIALS JAPAN).

[0423] Examples of the fluorine-based surfactant include surfactants having a fluorine carbon chain in the molecule. Specifically, examples include FLUORAD (registered trademark) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by AGC Corporation (formerly Asahi Glass Co., Ltd.)) and E5844 (manufactured by Daikin Fine Chemicals Laboratories, Ltd.), etc.

[0424] Examples of the above-mentioned organosilicon-based surfactants having fluorine atoms include surfactants having a siloxane bond and a fluorocarbon chain in the molecule, and more specifically, MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, and MEGAFAC F443 (manufactured by DIC Corporation).

[0425] The content of the leveling agent (F) is preferably 0.001 to 0.2 mass %, more preferably 0.002 to 0.1 mass %, and further preferably 0.005 to 0.05 mass % relative to the total amount of the colored resin composition. It should be noted that the content does not include the content of the pigment dispersant described later. If the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

[0426] <Other ingredients>

[0427] The colored resin composition may contain additives known in the technical field, such as a filler, other polymer compounds, an adhesion promoter, an antioxidant, a light stabilizer, and a chain transfer agent, as needed.

[0428] <Method for producing colored resin composition>

[0429] The colored resin composition can be prepared, for example, by mixing a colorant (A) and a resin (B), and, if necessary, a polymerizable compound (C), a polymerization initiator (D), a solvent (E), a leveling agent (F), a polymerization initiation aid (D1), and other components. The mixed colored resin composition can be filtered through a filter having a pore size of about 0.01 to 10 μm.

[0430] The compound (I) as the colorant (A) and the pigment as the colorant (A1) used as needed can be dispersed by containing a pigment dispersant and used as a dispersion in a state uniformly dispersed in a solution. By mixing the remaining components in such a dispersion to a predetermined concentration, the target colored resin composition can be prepared. The compound (I) and the pigment can be dispersed alone or in a mixture of multiples.

[0431] As pigment dispersant, surfactant etc. can be enumerated, and can be any surfactant in cationic, anionic, nonionic and amphoteric. Specifically, surfactant etc. of polyester, polyamine and acrylic acid can be enumerated. These dispersants can be used alone or in combination of 2 or more. As dispersant, when represented by trade name, KP (Shin-Etsu Chemical Co., Ltd.), FLOWLEN (Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (Zeneca Co., Ltd.), EFKA (registered trademark) (BASF Co., Ltd.), AJISPER (registered trademark) (AjinomotoFine-Techno Co., Ltd.), Disperbyk (registered trademark), BYK (registered trademark) (BYK-Chemie Co., Ltd.) etc. can be enumerated.

[0432] When a pigment dispersant is used, the amount used is preferably 5 to 200 parts by mass, more preferably 10 to 150 parts by mass, and even more preferably 20 to 130 parts by mass, based on 100 parts by mass of the colorant (A) (specifically, compound (I) and pigment) in the dispersion. If the amount of the pigment dispersant used is within the above range, there is a tendency to obtain a dispersion in a more uniform dispersed state.

[0433] When the colorant (A) contains a dye, the dye may be dissolved in part or all of the solvent (E) to prepare a solution, and the solution is preferably filtered through a filter having a pore size of about 0.01 to 1 μm.

[0434] [Color Filter]

[0435] As a method for manufacturing a coloring pattern of a color filter by the colored resin composition of the present invention, photolithography, inkjet method, printing method, etc. can be cited. Among them, photolithography is preferred. Photolithography is a method in which the above-mentioned colored resin composition is applied to a substrate and dried to form a composition layer, and the composition layer is exposed through a photomask and developed. In the photolithography, a colored coating film as a cured product of the above-mentioned composition layer can be formed by not using a photomask and / or not developing during exposure.

[0436] The film thickness of the color filter (colored coating or colored pattern) is, for example, 30 μm or less, preferably 20 μm or less, more preferably 6 μm or less, further preferably 3 μm or less, further more preferably 1.5 μm or less, particularly preferably 0.5 μm or less, preferably 0.1 μm or more, more preferably 0.2 μm or more, further preferably 0.3 μm or more.

[0437] As the substrate, a glass plate of quartz glass, borosilicate glass, aluminosilicate glass, soda-lime glass with a silicon dioxide coating on the surface, a resin plate of polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, or a substrate on which aluminum, silver, or a silver / copper / palladium alloy thin film is formed can be used. Other color filter layers, resin layers, transistors, circuits, etc. can be formed on these substrates. In addition, a substrate treated with HMDS on a silicon substrate can also be used.

[0438] The formation of pixels of various colors (color filters of various colors) based on photolithography can be carried out using known or customary devices and conditions. For example, it can be made as follows. First, a colored resin composition is applied to a substrate, and heated and dried (prebaked) and / or dried under reduced pressure to remove volatile components such as solvents and dry them to obtain a smooth composition layer. As coating methods, spin coating, slit coating, slit and spin coating, etc. can be cited. The temperature during heating and drying is preferably 30 to 120°C, more preferably 50 to 110°C. In addition, as a heating time, it is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. When drying under reduced pressure, it is preferably carried out at a temperature range of 20 to 25°C under a pressure of 50 to 150 Pa. The film thickness of the composition layer is not particularly limited, as long as it is appropriately selected according to the film thickness of the target color filter.

[0439] Next, the composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the target application is used. As the light source used in the exposure, a light source that generates light with a wavelength of 250 to 450 nm is preferably used. For example, light less than 250 nm can be cut off using a filter that cuts off the wavelength region, or light near 436 nm, near 408 nm, and near 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength regions. Specifically, mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, etc. can be cited. In order to be able to evenly irradiate parallel light to the entire exposure surface, or to accurately align the photomask with the substrate, it is preferred to use a reduced projection exposure device or a proximity exposure device such as a mask aligner and a stepper.

[0440] The exposed composition layer is brought into contact with a developer and developed to form a colored pattern on the substrate. By developing, the unexposed portion of the composition layer is dissolved in the developer and removed. As the developer, for example, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate and tetramethylammonium hydroxide are preferred. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Furthermore, the developer may also contain a surfactant. The developing method may be any of a paddle method, an immersion method and a spray method. Furthermore, the substrate may be tilted at any angle during development.

[0441] After development, water washing is preferably performed.

[0442] The obtained colored pattern is preferably post-baked. The post-baking temperature is preferably 80 to 250° C., more preferably 100 to 245° C. The post-baking time is preferably 1 to 120 minutes, more preferably 2 to 30 minutes.

[0443] The colored pattern and colored coating film obtained in this manner are useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL display device, etc.), electronic paper, a solid-state imaging element, and the like.

[0444] In particular, the above-mentioned colored pattern and colored coating are useful as green filters in color filters. When the above-mentioned colored pattern or colored coating is made into a film thickness of 2.0 μm, it is preferably satisfied with the following (i) and (ii). The colored resin composition that can form a colored pattern and a colored coating that satisfy the following (i) and (ii) can form a green filter with excellent spectral characteristics. In particular, from the viewpoint of being able to show good spectral characteristics even after long-term use, the above-mentioned colored pattern and colored coating preferably satisfy the following (i) and (ii) even after the light irradiation test described in the Examples column described later.

[0445] (i) Transmittance at 550nm is 35% to 99%

[0446] (ii) Transmittance at 620 nm is 0.1% to 30% (preferably 0.1% to 20%)

[0447] Example

[0448] Hereinafter, the present invention will be described in more detail by giving examples, but the present invention is not limited to the following examples at all, and can certainly be appropriately changed and implemented within the scope of the above and following purports, and they are all included in the technical scope of the present invention. It should be noted that, below, as long as there is no special explanation, "part" means "part by mass", and "%" means "% by mass".

[0449] In the following Examples, the structures of the compounds were confirmed by mass spectrometry (MALDI-TOF MS: JMS-S3000 manufactured by JEOL Ltd.) or mass spectrometry (LC-MS (LC: 1200 model manufactured by Agilent, MS: LC / MSD model manufactured by Agilent)).

[0450] In the following examples, the maximum absorption wavelength was confirmed by ultraviolet-visible-near-infrared absorption spectroscopy (JASCO Corp.: V-770).

[0451] (Synthesis example 1)

[0452] <Preparation of Compound (II-1)>

[0453] Under a nitrogen atmosphere, 23 parts of 4-nitrophthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), 20 parts of 2-(sec-butyl)phenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 20 parts of potassium carbonate (manufactured by Kanto Chemical Co., Ltd.) and 160 parts of dehydrated acetonitrile (manufactured by Kanto Chemical Co., Ltd.) were mixed, heated to 80°C, and stirred at the same temperature for 10 hours. The reaction solution was cooled to room temperature (18 to 24°C) and filtered to obtain filtrate A and residue A. Residue A was washed with 160 parts of acetonitrile, and the obtained acetonitrile solution and filtrate A were combined, and the solvent in the solution was distilled off. The obtained residue was washed with 80 parts of ion-exchanged water and dried to obtain 35 parts of a compound represented by formula (II-1) (hereinafter referred to as compound (II-1)) as a colorless solid (yield 96%).

[0454]

[0455] <Identification of Compound (II-1)>

[0456] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=276

[0457] Exact Mass: 276

[0458] (Example 1)

[0459] <Preparation of Compound (I-e1)>

[0460] Under a nitrogen atmosphere, 10.0 parts of the compound (II-1) prepared in Synthesis Example 1, 1.3 parts of anhydrous aluminum chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 83.0 parts of triethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 8.3 parts of 1,8-diazabicyclo[5,4,0]-7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and heated at 140°C for 10 hours. After the reaction was completed, the reaction solution was cooled to room temperature (18 to 24°C) and poured into 100 parts of ion-exchanged water. The precipitated solid was separated by decantation in the order of 50 parts of ion-exchanged water twice and 50 parts of acetone once. The obtained crude product was purified by silica gel column chromatography (developing solvent: gradient from toluene to tetrahydrofuran) to obtain 2.41 parts of the compound represented by formula (I-e1) (hereinafter referred to as compound (I-e1)) (yield 24%). In addition, the compound represented by formula (IV-e1) (hereinafter referred to as compound (IV-e1)) was not obtained.

[0461]

[0462] <Identification of Compound (I-e1)>

[0463] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=1107

[0464] Exact mass: 1107

[0465] (Synthesis example 2)

[0466] <Preparation of Compound (II-2)>

[0467] Except that 29 parts of 4-bromo-2,6-di(tert-butyl)phenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 20 parts of 2-(sec-butyl)phenol, 35 parts of the compound represented by formula (II-2) (hereinafter referred to as compound (II-2)) were obtained as a colorless solid in the same manner as in Synthesis Example 1 (yield 76%).

[0468]

[0469] <Identification of Compound (II-2)>

[0470] (Mass Spectrometry) Ionization Mode = ESI+: m / z = [M+H] + 411

[0471] Exact mass: 410

[0472] (Example 2)

[0473] <Preparation of Compound (I-e2)>

[0474] Instead of using 10.0 parts of compound (II-1), 14.9 parts of compound (II-2) obtained in Synthesis Example 2 were used. In addition, 5.83 parts (yield 39%) of the compound represented by formula (I-e2) (hereinafter referred to as compound (I-e2)) and 1.09 parts (yield 7%) of the compound represented by formula (IV-e2) (hereinafter referred to as compound (IV-e2)) were obtained in the same manner as in Example 1.

[0475]

[0476] <Identification of Compound (I-e2)>

[0477] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=1642

[0478] Exact mass: 1642

[0479] <Identification of Compound (IV-e2)>

[0480] It was confirmed by silica gel thin layer chromatography (TLC) that there were only two kinds of colored components obtained in the reaction of Example 2. One was confirmed as compound (I-e2) by MALDI-TOF MS as described above. The remaining one showed a unique spectral shape of a metal body by the measurement of an ultraviolet visible near-infrared absorption spectrometer (Japan Spectrophotometer: V-770) (hereinafter referred to as UV-vis measurement), so it was confirmed to be a metal body. In view of the reaction substrate, it was clear that the metal body was an aluminum body. Furthermore, for the Rf value (developing solvent: toluene) in silica gel thin layer chromatography (TLC), the compound represented by the following formula (IV-e16) as a similar compound was 0.30, and the above-mentioned aluminum body was 0.28, so the aluminum body was identified as compound (IV-e2).

[0481]

[0482] (Synthesis example 3)

[0483] <Preparation of Compound (II-3)>

[0484] Except that 18 parts of 2-isopropylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 20 parts of 2-(sec-butyl)phenol, 34 parts of the compound represented by formula (II-3) (hereinafter referred to as compound (II-3)) were obtained as a colorless solid in the same manner as in Synthesis Example 1 (yield 97%).

[0485]

[0486] <Identification of Compound (II-3)>

[0487] (Mass Spectrometry) Ionization Mode = ESI+: m / z = [M+H] + 263

[0488] Exact mass: 262

[0489] (Example 3)

[0490] <Preparation of Compound (I-e3)>

[0491] Instead of using 10.0 parts of compound (II-1) using 9.5 parts of compound (II-3) obtained in Synthesis Example 3, 4.1 parts (yield 43%) of the compound represented by formula (I-e3) (hereinafter referred to as compound (I-e3)) and 0.81 parts (yield 8%) of the compound represented by formula (IV-e3) (hereinafter referred to as compound (IV-e3)) were obtained in the same manner as in Example 1.

[0492]

[0493] <Identification of Compound (I-e3)>

[0494] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=1050

[0495] Exact mass: 1050

[0496] <Identification of Compound (IV-e3)>

[0497] It was confirmed by silica gel thin layer chromatography (TLC) that the coloring components obtained in the reaction of Example 3 were only two. One was confirmed as compound (I-e3) by MALDI-TOF MS as described above. The remaining one showed a unique spectral shape of a metal body by UV-vis measurement, so it was confirmed to be a metal body. In view of the reaction substrate, it was clear that the metal body was an aluminum body. Furthermore, for the Rf value (developing solvent: toluene) in silica gel thin layer chromatography (TLC), the compound represented by formula (IV-e16) as a similar compound was 0.30, and the above-mentioned aluminum body was 0.33, so the aluminum body was identified as compound (IV-e3).

[0498] (Synthesis Example 4)

[0499] <Preparation of Compound (II-4)>

[0500] Except that 25 parts of 2-cyclohexyl-5-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 20 parts of 2-(sec-butyl)phenol, 38 parts of the compound represented by formula (II-4) (hereinafter referred to as compound (II-4)) were obtained as a colorless solid in the same manner as in Synthesis Example 1 (yield 91%).

[0501]

[0502] <Identification of Compound (II-4)>

[0503] (Mass Spectrometry) Ionization Mode = ESI+: m / z = [M+H] + 317

[0504] Exact mass: 316

[0505] (Example 4)

[0506] <Preparation of Compound (I-e4)>

[0507] Instead of using 10.0 parts of compound (II-1), 11.5 parts of compound (II-4) obtained in Synthesis Example 4 were used. In addition, 3.80 parts (yield 33%) of the compound represented by formula (I-e4) (hereinafter referred to as compound (I-e4)) and 0.60 parts (yield 5%) of the compound represented by formula (IV-e4) (hereinafter referred to as compound (IV-e4)) were obtained in the same manner as in Example 1.

[0508]

[0509] <Identification of Compound (I-e4)>

[0510] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=1267

[0511] Exact mass: 1267

[0512] <Identification of Compound (IV-e4)>

[0513] It was confirmed by silica gel thin layer chromatography (TLC) that there were only two kinds of colored components obtained in the reaction of Example 4. One was confirmed as compound (I-e4) by MALDI-TOF MS as described above. The remaining one showed a unique spectral shape of a metal body by UV-vis measurement, so it was confirmed to be a metal body. In view of the reaction substrate, it was clear that the metal body was an aluminum body. Furthermore, for the Rf value (developing solvent: toluene) in silica gel thin layer chromatography (TLC), the compound represented by formula (IV-e16) as a similar compound was 0.30, and the above-mentioned aluminum body was 0.35, so the aluminum body was identified as compound (IV-e4).

[0514] (Synthesis Example 5)

[0515] <Preparation of Compound (II-5)>

[0516] Compound (II-5) was quantitatively obtained as a colorless liquid in the same manner as in Synthesis Example 1 except that 25 parts of 2-tert-butylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 20 parts of 2-(sec-butyl)phenol.

[0517]

[0518] <Identification of Compound (II-5)>

[0519] (Mass Spectrometry) Ionization Mode = ESI+: m / z = [M+H] + 277

[0520] Exact mass: 276

[0521] (Example 5)

[0522] <Preparation of Compound (I-e5)>

[0523] Instead of using 10.0 parts of compound (II-1), 10.0 parts of compound (II-5) obtained in Synthesis Example 5 were used. In addition, 3.01 parts (yield 30%) of the compound represented by formula (I-e5) (hereinafter referred to as compound (I-e5)) and 0.95 parts (yield 9%) of the compound represented by formula (IV-e5) (hereinafter referred to as compound (IV-e5)) were obtained in the same manner as in Example 1.

[0524]

[0525] <Identification of Compound (I-e5)>

[0526] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=1107

[0527] Exact mass: 1107

[0528] <Identification of Compound (IV-e5)>

[0529] It was confirmed by silica gel thin layer chromatography (TLC) that the coloring components obtained in the reaction of Example 5 were only two. One was confirmed as compound (I-e5) by MALDI-TOF MS as described above. The remaining one showed a unique spectral shape of a metal body by UV-vis measurement, so it was confirmed to be a metal body. In view of the reaction substrate, it was clear that the metal body was an aluminum body. Furthermore, for the Rf value (developing solvent: toluene) in silica gel thin layer chromatography (TLC), the compound represented by formula (IV-e16) as a similar compound was 0.30, and the above-mentioned aluminum body was 0.33, so the aluminum body was identified as compound (IV-e5).

[0530] (Synthesis Example 6)

[0531] <Preparation of Compound (II-6)>

[0532] Except that 25 parts of 2-isopropyl-5-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 20 parts of 2-(sec-butyl)phenol, 39 parts of the compound represented by formula (II-6) (hereinafter referred to as compound (II-6)) were obtained as a colorless solid in the same manner as in Synthesis Example 1 (yield 93%).

[0533]

[0534] <Identification of Compound (II-6)>

[0535] (Mass Spectrometry) Ionization Mode = ESI+: m / z = [M+H] + 277

[0536] Exact mass: 276

[0537] (Example 6)

[0538] <Preparation of Compound (I-e6)>

[0539] Instead of using 10.0 parts of compound (II-1), 10.0 parts of compound (II-6) obtained in Synthesis Example 6 were used. In addition, 2.31 parts (yield 23%) of the compound represented by formula (I-e6) (hereinafter referred to as compound (I-e6)) and 1.12 parts (yield 11%) of the compound represented by formula (IV-e6) (hereinafter referred to as compound (IV-e6)) were obtained in the same manner as in Example 1.

[0540]

[0541] <Identification of Compound (I-e6)>

[0542] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=1107

[0543] Exact mass: 1107

[0544] <Identification of Compound (IV-e6)>

[0545] It was confirmed by silica gel thin layer chromatography (TLC) that there were only two kinds of colored components obtained in the reaction of Example 6. One was confirmed as compound (I-e6) by MALDI-TOF MS as described above. The remaining one showed a unique spectral shape of a metal body by UV-vis measurement, so it was confirmed to be a metal body. In view of the reaction substrate, it was clear that the metal body was an aluminum body. Furthermore, for the Rf value (developing solvent: toluene) in silica gel thin layer chromatography (TLC), the compound represented by formula (IV-e16) as a similar compound was 0.30, and the above-mentioned aluminum body was 0.29, so the aluminum body was identified as compound (IV-e6).

[0546] (Synthesis Example 7)

[0547] <Preparation of Compound (II-7)>

[0548] Except that 25 parts of 4-tert-butylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 20 parts of 2-(sec-butyl)phenol, 40 parts of the compound represented by formula (II-7) (hereinafter referred to as compound (II-7)) were obtained as a colorless solid in the same manner as in Synthesis Example 1 (yield 95%).

[0549]

[0550] <Identification of Compound (II-7)>

[0551] (Mass Spectrometry) Ionization Mode = ESI+: m / z = [M+H] + 277

[0552] Exact mass: 276

[0553] (Example 7)

[0554] <Preparation of Compound (I-e7)>

[0555] Instead of using 10.0 parts of compound (II-1), 10.0 parts of compound (II-7) obtained in Synthesis Example 7 were used. In addition, 3.10 parts (yield 31%) of the compound represented by formula (I-e7) (hereinafter referred to as compound (I-e7)) and 1.07 parts (yield 10%) of the compound represented by formula (IV-e7) (hereinafter referred to as compound (IV-e7)) were obtained in the same manner as in Example 1.

[0556]

[0557] <Identification of Compound (I-e7)>

[0558] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=1107

[0559] Exact mass: 1107

[0560] <Identification of Compound (IV-e7)>

[0561] It was confirmed by silica gel thin layer chromatography (TLC) that there were only two kinds of colored components obtained in the reaction of Example 7. One was confirmed as compound (I-e7) by MALDI-TOF MS as described above. The remaining one showed a unique spectral shape of a metal body by UV-vis measurement, so it was confirmed to be a metal body. In view of the reaction substrate, it was clear that the metal body was an aluminum body. Furthermore, for the Rf value (developing solvent: toluene) in silica gel thin layer chromatography (TLC), the compound represented by formula (IV-e16) as a similar compound was 0.30, and the above-mentioned aluminum body was 0.27, so the aluminum body was identified as compound (IV-e7).

[0562] (Synthesis Example 8)

[0563] <Preparation of Compound (II-8)>

[0564] Except that 18 parts of 2,3,6-trimethylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 20 parts of 2-(sec-butyl)phenol, 34 parts of the compound represented by formula (II-8) (hereinafter referred to as compound (II-8)) were obtained as a colorless solid in the same manner as in Synthesis Example 1 (yield 96%).

[0565]

[0566] <Identification of Compound (II-8)>

[0567] (Mass Spectrometry) Ionization Mode = ESI+: m / z = [M+H] + 263

[0568] Exact mass: 262

[0569] (Example 8)

[0570] <Preparation of Compound (I-e8)>

[0571] Except that 9.50 parts of the compound (II-8) obtained in Synthesis Example 8 was used instead of 10.0 parts of the compound (II-1), 2.67 parts of the compound represented by the formula (I-e8) (hereinafter referred to as the compound (I-e8)) were obtained in the same manner as in Example 1 (yield 28%). It should be noted that the compound represented by the formula (IV-e8) (hereinafter referred to as the compound (IV-e8)) was not obtained.

[0572]

[0573] <Identification of Compound (I-e8)>

[0574] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=1050

[0575] Exact mass: 1050

[0576] (Synthesis Example 9)

[0577] <Preparation of Compound (II-9)>

[0578] Except that 24 parts of 2,6-diisopropylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 20 parts of 2-(sec-butyl)phenol, 36 parts of the compound represented by formula (II-9) (hereinafter referred to as compound (II-9)) were obtained as a colorless solid in the same manner as in Synthesis Example 1 (yield 90%).

[0579]

[0580] <Identification of Compound (II-9)>

[0581] (Mass Spectrometry) Ionization Mode = ESI+: m / z = [M+H] + 305

[0582] Exact mass: 304

[0583] (Example 9)

[0584] <Preparation of Compound (I-e9)>

[0585] Except that 11.0 parts of the compound (II-9) obtained in Synthesis Example 9 was used instead of 10.0 parts of the compound (II-1), 5.65 parts of the compound represented by the formula (I-e9) (hereinafter referred to as the compound (I-e9)) were obtained in the same manner as in Example 1 (yield 51%). It should be noted that the compound represented by the formula (IV-e9) (hereinafter referred to as the compound (IV-e9)) was not obtained.

[0586]

[0587] <Identification of Compound (I-e9)>

[0588] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=1219

[0589] Exact mass: 1219

[0590] (Synthesis Example 10)

[0591] <Preparation of Compound (II-10)>

[0592] Except that 18 parts of 2-ethyl-6-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 20 parts of 2-(sec-butyl)phenol, 34 parts of the compound represented by formula (II-10) (hereinafter referred to as compound (II-10)) were obtained as a colorless solid in the same manner as in Synthesis Example 1 (yield 98%).

[0593]

[0594] <Identification of Compound (II-10)>

[0595] (Mass Spectrometry) Ionization Mode = ESI+: m / z = [M+H] + 263

[0596] Exact mass: 262

[0597] (Example 10)

[0598] <Preparation of Compound (I-e10)>

[0599] Except that 9.5 parts of the compound (II-10) obtained in Synthesis Example 10 was used instead of 10.0 parts of the compound (II-1), 1.81 parts of the compound represented by the formula (I-e10) (hereinafter referred to as the compound (I-e10)) were obtained in the same manner as in Example 1 (yield 19%). It should be noted that the compound represented by the formula (IV-e10) (hereinafter referred to as the compound (IV-e10)) was not obtained.

[0600]

[0601] <Identification of Compound (I-10)>

[0602] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=1050

[0603] Exact mass: 1050

[0604] (Synthesis Example 11)

[0605] <Preparation of Compound (II-11)>

[0606] Except that 33 parts of 2,6-diphenylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 20 parts of 2-(sec-butyl)phenol, 44 parts of the compound represented by formula (II-11) (hereinafter referred to as compound (II-11)) were obtained as a colorless solid in the same manner as in Synthesis Example 1 (yield 89%).

[0607]

[0608] <Identification of Compound (II-11)>

[0609] (Mass Spectrometry) Ionization Mode = ESI+: m / z = [M+H] + 373

[0610] Exact mass: 372

[0611] (Example 11)

[0612] <Preparation of Compound (I-e11)>

[0613] 2.44 parts (yield 18%) of a compound represented by formula (I-e11) (hereinafter referred to as compound (I-e11)) were obtained in the same manner as in Example 1, except that 13.5 parts of compound (II-11) obtained in Synthesis Example 11 were used in place of 10.0 parts of compound (II-1). It should be noted that no compound represented by formula (IV-e11) (hereinafter referred to as compound (IV-e11)) was obtained.

[0614]

[0615] <Identification of Compound (I-e11)>

[0616] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=1491

[0617] Exact mass: 1491

[0618] (Synthesis Example 12)

[0619] <Preparation of Compound (II-12)>

[0620] Except that 18 parts of 2,4,6-trimethylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 20 parts of 2-(sec-butyl)phenol, 34 parts of the compound represented by formula (II-12) (hereinafter referred to as compound (II-12)) were obtained as a colorless solid in the same manner as in Synthesis Example 1 (yield 97%).

[0621]

[0622] <Identification of Compound (II-12)>

[0623] (Mass Spectrometry) Ionization Mode = ESI+: m / z = [M+H] + 263

[0624] Exact mass: 262

[0625] (Example 12)

[0626] <Preparation of Compound (I-e12)>

[0627] 9.50 parts of compound (II-12) obtained in Synthesis Example 12 were used instead of 10.0 parts of compound (II-1). In addition, 4.87 parts (yield 51%) of the compound represented by formula (I-e12) (hereinafter referred to as compound (I-e12)) and 1.20 parts (yield 12%) of the compound represented by formula (IV-e12) (hereinafter referred to as compound (IV-e12)) were obtained in the same manner as in Example 1.

[0628]

[0629] <Identification of Compound (I-e12)>

[0630] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=1050

[0631] Exact mass: 1050

[0632] <Identification of Compound (IV-e12)>

[0633] It was confirmed by silica gel thin layer chromatography (TLC) that there were only two kinds of colored components obtained in the reaction of Example 12. One was confirmed as compound (I-e12) by MALDI-TOF MS as described above. The remaining one showed a unique spectral shape of a metal body by UV-vis measurement, so it was confirmed to be a metal body. In view of the reaction substrate, it was clear that the metal body was an aluminum body. Furthermore, for the Rf value (developing solvent: toluene) in silica gel thin layer chromatography (TLC), the compound represented by formula (IV-e16) as a similar compound was 0.30, and the above-mentioned aluminum body was 0.32, so the aluminum body was identified as compound (IV-e12).

[0634] (Synthesis Example 13)

[0635] <Preparation of Compound (II-13)>

[0636] Except that 22 parts of 2-tert-butyl-6-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 20 parts of 2-(sec-butyl)phenol, 38 parts of the compound represented by formula (II-13) (hereinafter referred to as compound (II-13)) were obtained as a colorless solid in the same manner as in Synthesis Example 1 (yield 97%).

[0637]

[0638] <Identification of Compound (II-13)>

[0639] (Mass Spectrometry) Ionization Mode = ESI+: m / z = [M+H] + 291

[0640] Exact mass: 290

[0641] (Example 13)

[0642] <Preparation of Compound (I-e13)>

[0643] Instead of 10.0 parts of compound (II-1), 10.5 parts of compound (II-13) obtained in Synthesis Example 13 were used. In addition, 4.23 parts (yield 40%) of the compound represented by formula (I-e13) (hereinafter referred to as compound (I-e13)) and 1.22 parts (yield 11%) of the compound represented by formula (IV-e13) (hereinafter referred to as compound (IV-e13)) were obtained in the same manner as in Example 1.

[0644]

[0645] <Identification of Compound (I-e13)>

[0646] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=1163

[0647] Exact mass: 1163

[0648] <Identification of Compound (IV-e13)>

[0649] It was confirmed by silica gel thin layer chromatography (TLC) that there were only two kinds of colored components obtained in the reaction of Example 13. One was confirmed as compound (I-e13) by MALDI-TOF MS as described above. The remaining one showed a unique spectral shape of a metal body by UV-vis measurement, so it was confirmed to be a metal body. In view of the reaction substrate, it was clear that the metal body was an aluminum body. Furthermore, for the Rf value (developing solvent: toluene) in silica gel thin layer chromatography (TLC), the compound represented by formula (IV-e16) as a similar compound was 0.30, and the above-mentioned aluminum body was 0.28, so the aluminum body was identified as compound (IV-e13).

[0650] (Synthesis Example 14)

[0651] <Preparation of Compound (II-14)>

[0652] Except that 28 parts of 4-α-cumylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 20 parts of 2-(sec-butyl)phenol, 41 parts of the compound represented by formula (II-14) (hereinafter referred to as compound (II-14)) were obtained as a colorless solid in the same manner as in Synthesis Example 1 (yield 92%).

[0653]

[0654] <Identification of Compound (II-14)>

[0655] (Mass Spectrometry) Ionization Mode = ESI+: m / z = [M+H] + 339

[0656] Exact mass: 338

[0657] (Example 14)

[0658] <Preparation of Compound (I-e14)>

[0659] Instead of 10.0 parts of compound (II-1), 12.3 parts of compound (II-14) obtained in Synthesis Example 14 were used. In addition, 2.95 parts (yield 24%) of the compound represented by formula (I-e14) (hereinafter referred to as compound (I-e14)) and 0.64 parts (yield 5%) of the compound represented by formula (IV-e14) (hereinafter referred to as compound (IV-e14)) were obtained in the same manner as in Example 1.

[0660]

[0661] <Identification of Compound (I-e14)>

[0662] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=1355

[0663] Exact mass: 1355

[0664] <Identification of Compound (IV-e14)>

[0665] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=1416

[0666] Exact mass: 1415

[0667] (Synthesis Example 15)

[0668] <Preparation of Compound (II-15)>

[0669] Except that 25 parts of 3-bromo-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 20 parts of 2-(sec-butyl)phenol, 40 parts of the compound represented by formula (II-15) (hereinafter referred to as compound (II-15)) were obtained as a colorless solid in the same manner as in Synthesis Example 1 (yield 95%).

[0670]

[0671] (Example 15)

[0672] <Preparation of Compound (I-e15)>

[0673] Except that 11.4 parts of the compound (II-15) obtained in Synthesis Example 15 were used instead of 10.0 parts of the compound (II-1), 4.33 parts of the compound represented by the formula (I-e15) (hereinafter referred to as the compound (I-e15)) were obtained in the same manner as in Example 1 (yield 38%). It should be noted that the compound represented by the formula (IV-e15) (hereinafter referred to as the compound (IV-e15)) was not obtained.

[0674]

[0675] <Identification of Compound (I-e15)>

[0676] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=1251

[0677] Exact mass: 1250

[0678] <Identification of Compound (IV-e15)>

[0679] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=1310

[0680] Exact mass: 1310

[0681] (Synthesis Example 16)

[0682] <Preparation of Compound (II-16)>

[0683] Except that 25 parts of 2,6-dimethylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 20 parts of 2-(sec-butyl)phenol, 38 parts of the compound represented by formula (II-16) (hereinafter referred to as compound (II-16)) were obtained as a colorless solid in the same manner as in Synthesis Example 1 (yield 92%).

[0684]

[0685] (Example 16)

[0686] <Preparation of Compound (I-e16)>

[0687] Instead of using 10.0 parts of compound (II-1) using 9.0 parts of compound (II-16) obtained in Synthesis Example 16, the same procedure as in Example 1 was used to obtain 4.43 parts (yield 49%) of a compound represented by formula (I-e16) (hereinafter referred to as compound (I-e16)) and 1.05 parts (yield 11%) of a compound represented by formula (IV-e16) (hereinafter referred to as compound (IV-e16)).

[0688]

[0689] <Identification of Compound (I-e16)>

[0690] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=994

[0691] Exact mass: 994

[0692] <Identification of Compound (IV-e16)>

[0693] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=1054

[0694] Exact mass: 1054

[0695] (Synthesis Example 17)

[0696] <Preparation of Compound (II-17)>

[0697] Except that 39 parts of 4-methoxy-2,5-di(2-methylpentane-2-yl)phenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 20 parts of 2-(sec-butyl)phenol, 50 parts of the compound represented by formula (II-17) (hereinafter referred to as compound (II-17)) were obtained as a colorless solid in the same manner as in Synthesis Example 1 (yield 90%).

[0698]

[0699] (Example 17)

[0700] <Preparation of Compound (I-e17)>

[0701] Instead of using 10.0 parts of compound (II-1) using 15.1 parts of compound (II-17) obtained in Synthesis Example 17, the same procedure as in Example 1 was used to obtain 3.50 parts (yield 23%) of a compound represented by formula (I-e17) (hereinafter referred to as compound (I-e17)) and 0.946 parts (yield 6%) of a compound represented by formula (IV-e17) (hereinafter referred to as compound (IV-e17)).

[0702]

[0703] <Identification of Compound (I-e17)>

[0704] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=1675

[0705] Exact mass: 1675

[0706] <Identification of Compound (IV-e17)>

[0707] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=1735

[0708] Exact mass: 1735

[0709] (Synthesis Example 18)

[0710] <Preparation of Compound (II-18)>

[0711] Except that 16 parts of 2,6-dimethylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) were used instead of 20 parts of 2-(sec-butyl)phenol, and 18.5 parts of 3-nitrophthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were used instead of 23 parts of 4-nitrophthalonitrile, 34 parts of the compound represented by formula (II-18) (hereinafter referred to as compound (II-18)) were obtained as a colorless solid in the same manner as in Synthesis Example 1 (yield 93%).

[0712]

[0713] <Identification of Compound (II-18)>

[0714] (Mass Spectrometry) Ionization Mode = ESI+: m / z = [M+H] + 249

[0715] Exact mass: 248

[0716] (Example 18)

[0717] <Preparation of Compound (I-e18)>

[0718] Instead of using 10.0 parts of compound (II-1) using 9.0 parts of compound (II-18) obtained in Synthesis Example 18, 2.17 parts (yield 24%) of the compound represented by formula (I-e18) (hereinafter referred to as compound (I-e18)) and 0.28 parts (yield 3%) of the compound represented by formula (IV-e18) (hereinafter referred to as compound (IV-e18)) were obtained in the same manner as in Example 1.

[0719]

[0720] <Identification of Compound (I-e18)>

[0721] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=994

[0722] Exact mass: 994

[0723] <Identification of Compound (IV-e18)>

[0724] (Mass Spectrometry) Ionization Mode = MALDI-TOF - :m / z=1054

[0725] Exact mass: 1054

[0726] (Comparative Example 1)

[0727] <Preparation of Compound (I-e16)>

[0728] The reaction was carried out in the same manner as in Example 16 except that anhydrous aluminum chloride was not used. As a result, compound (I-e16) was not obtained.

[0729]

[0730] (Comparative Example 2)

[0731] <Preparation of Compound (I-c1)>

[0732] Under a nitrogen atmosphere, 43 parts of phthalonitrile, 15 parts of anhydrous aluminum chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 105 parts of n-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 51 parts of 1,8-diazabicyclo[5,4,0]-7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and heated at 136°C for 5 hours. After the reaction was completed, the reaction solution was cooled to room temperature (18-24°C) and 630 parts of ethyl acetate were flowed in. The precipitated solid was filtered and further decanted twice with 460 parts of ethyl acetate to separate the crude product. The crude product was purified by reslurry washing using 630 parts of ion exchange water to obtain 32 parts of the compound represented by formula (IV-c1) in the form of a solid (yield 65%), but no compound represented by formula (I-c1) was obtained.

[0733]

[0734] [Table 6]

[0735]

[0736] In Table 6, the molar ratio (Compound (I) / Compound (IV)) indicates the amount of Compound (I) isolated in each Example and Comparative Example relative to 1 mol of Compound (IV).

[0737] From the comparison between Example 16 and Comparative Example 1, it can be seen that compound (I) can be synthesized in a short time and with a higher yield by using the preparation method of the present invention. In addition, for other Examples 1 to 15 and 17 to 18, compound (I) is generated preferentially over compound (IV), and compound (I) is obtained in a short time.

[0738] In Comparative Example 2, only the compound of formula (IV-c1) which is aluminum phthalocyanine was obtained. Therefore, it was found that the effect obtained by the production method of the present invention is specifically obtained in the embodiment having a specific aryloxy group (i).

[0739] (Resin Synthesis Example 1)

[0740] <Preparation of resin B-1>

[0741] An appropriate amount of nitrogen gas was introduced into a flask equipped with a reflux cooler, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen, and 280 parts of propylene glycol monomethyl ether acetate was added and heated to 80°C while stirring. Next, 38 parts of acrylic acid and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decane-8-ester and 3,4-epoxytricyclo[5.2.1.0 2,6 ] A mixed solution of 289 parts of a mixture of decane-9-ester (containing a molar ratio of 1:1) and 125 parts of propylene glycol monomethyl ether acetate. On the other hand, a solution obtained 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 the addition was completed, the mixture was kept at 80°C for 4 hours and then cooled to room temperature to obtain a copolymer (resin B-1) solution having a solid content of 35.1% and a viscosity of 125 mPa·s measured by a B-type viscometer (23°C). The weight average molecular weight Mw of the resulting copolymer was 9.2×10 3 , a dispersion degree of 2.08, and an acid value of 77 mg-KOH / g in terms of solid content. Resin B-1 has the following structural units.

[0742]

[0743] (Resin Synthesis Example 2)

[0744] <Synthesis of Resin B-2>

[0745] An appropriate amount of nitrogen was introduced into a flask equipped with a reflux cooler, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen. 350 parts of propylene glycol monomethyl ether acetate was added and heated to 85°C while stirring. Next, 70 parts of acrylic acid and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decane-8-ester and 3,4-epoxytricyclo[5.2.1.0 2,6 ] A mixed solution of 202 parts of a mixture of a mixture of decane-9-ester (containing a molar ratio of 1:1), 78 parts of vinyltoluene (isomer mixture), and 100 parts of propylene glycol monomethyl ether acetate. On the other hand, a solution obtained by dissolving 33 parts of a polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) in 167 parts of propylene glycol monomethyl ether acetate was added dropwise for 5 hours. After the addition of the initiator solution was completed, it was kept at 85°C for 4 hours and then cooled to room temperature to obtain a copolymer (resin B-2) solution having a viscosity of 431 mPa·s and a solid content of 38.1% as measured by a B-type viscometer (23°C). The weight average molecular weight Mw of the generated copolymer is 1.04×10 4 , a dispersion degree of 2.03, and an acid value of 139 mg-KOH / g in terms of solid content. Resin B-2 has the following structural units.

[0746]

[0747] In addition, the polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.

[0748] Device: HLC-8120GPC (manufactured by TOSOH Co., Ltd.)

[0749] Column: TSK-GELG2000HXL

[0750] Column temperature: 40°C

[0751] Solvent: Tetrahydrofuran

[0752] Flow rate: 1.0mL / min

[0753] Solid content concentration of the analysis sample: 0.001 to 0.01 mass%

[0754] Injection volume: 50μL

[0755] Detector: RI

[0756] Calibration standard substances: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by TOSOH Corporation)

[0757] The ratio of the polystyrene-equivalent weight average molecular weight to the number average molecular weight (Mw / Mn) obtained above was defined as the degree of dispersion.

[0758] <Dispersion Preparation Example 1>

[0759] 5.0 parts of the compound (I-e17) obtained in Example 17, 3.5 parts of a dispersant (BYK LPN-6919 manufactured by BYK) (calculated as solid content), 3.5 parts of a resin B-2 (calculated as solid content), 78 parts of propylene glycol monomethyl ether acetate, and 10 parts of diacetone alcohol are mixed, 300 parts of 0.2 mm zirconium oxide beads are added and shaken, and the zirconium oxide beads are removed by filtration to obtain a dispersion (P-1).

[0760] <Dispersion Preparation Examples 2 to 5>

[0761] Dispersions (P-2) to (P-5) were obtained by the same method as in Dispersion Preparation Example 1 except that the compound (I-e17) in Dispersion Preparation Example 1 was changed to the following compound.

[0762] Dispersion liquid (P-2): Compound (I-e16) obtained in Example 16

[0763] Dispersion liquid (P-3): Compound (I-e18) obtained in Example 17

[0764] Dispersion liquid (P-4): Compound (I-e4) obtained in Example 18

[0765] <Dispersion Preparation Example 6>

[0766]

[0767] The above components were mixed and the pigment was dispersed using a bead mill to obtain a dispersion (P-c1).

[0768] <Dispersion Preparation Example 7>

[0769]

[0770] The above components are mixed, and the pigment is dispersed using a bead mill to obtain a dispersion (A-1).

[0771] <Dispersion Preparation Example 8>

[0772]

[0773] The above components are mixed, and the pigment is dispersed using a bead mill to obtain a dispersion (A-2).

[0774] <Examples A1 to A5 and Comparative Examples A1 to A2>

[0775] (Preparation of Colored Resin Composition)

[0776] The components described in Table 7 were mixed to obtain colored resin compositions E1 to E5 and C1 to C2, respectively. In the preparation of the colored resin composition, the ratio of the colorant in the solid content of the colored resin composition was 40% by mass in Examples A1 to A2 and Comparative Example A1, 35% by mass in Example A3 and Comparative Example A2, 36% by mass in Example A4, and 32% by mass in Example A5.

[0777] [Table 7]

[0778]

[0779] In Table 7, each component represents the following compound.

[0780] Resin (B-1): Resin B-1 (solid content conversion)

[0781] Polymerizable compound (C-1): dipentaerythritol polyacrylate, trade name A-9550, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

[0782] Polymerization initiator (D-1): N-acetoxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine, trade name PBG-327, O-acyl oxime compound, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.

[0783] Leveling agent (F-1): polyether-modified silicone oil, trade name Toray Silicone SH8400, manufactured by DowCorning Toray Co., Ltd.

[0784] Solvent (E-1): Propylene glycol monomethyl ether acetate

[0785] In addition, in Table 7, the amount described in the column of solvent (E-1) shows the total amount including the amount of propylene glycol monomethyl ether acetate contained in resin (B-1).

[0786] <Examples B1 to B9 and Comparative Examples B1 to B4>

[0787] (Creation of coloring patterns)

[0788] Colored resin compositions E1 to E5 and C1 to C2 were applied by spin coating on a 5 cm square glass substrate (EAGLE 2000; manufactured by Corning) and prebaked at 100°C for 3 minutes to form a colored composition layer. After cooling, an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) was used without a photomask in an air atmosphere at 100 mJ / cm2 The coloring composition layer after light irradiation was post-baked in an oven at 230° C. for 20 minutes to obtain a color coating film. After cooling, the film thickness of the obtained color coating film was measured using a film thickness measuring device (DEKTAK3; manufactured by Japan Vacuum Technology Co., Ltd.). The film thickness of the obtained color coating film was the same in all examples and comparative examples, which was 2.0 μm.

[0789] <Evaluation>

[0790] (1) Determination of initial brightness

[0791] The spectrum of the obtained colored coating film was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity coordinates (x, y) and the stimulus value Y in the XYZ colorimetric system of CIE were measured using the characteristic function of the C illuminant. A larger value of Y indicates higher brightness.

[0792] (2) Evaluation of brightness unevenness suppression

[0793] An ultraviolet cut filter (COLORED OPTICAL GLASS L38, manufactured by HOYA Co., Ltd., which cuts off light below 380 nm) was placed on the obtained colored coating film, and a light irradiation test was carried out by irradiating a xenon lamp for 48 or 120 hours (irradiation time is shown in Table 8) using a light resistance tester (SUNTEST CPS+: manufactured by Toyo Seiki Seisaku-sho, Ltd.). When the stimulation value Y before the light irradiation test (the initial brightness obtained in (1) above) was set to 100%, the relative value (%) of the stimulation value Y after the light irradiation test was calculated as the "brightness change rate", and evaluation was performed according to the following evaluation criteria. The results are shown in Table 8. When the brightness change rate is 98.0% or more under the present measurement conditions, it is difficult for the human eye to distinguish the brightness difference between the peripheral part and the central part of the colored filter after long-term use, and it can be said that the performance is sufficient as a color filter.

[0794] Brightness unevenness suppression ◎: Brightness change rate is 99.0% or more

[0795] Brightness unevenness suppression ○: Brightness change rate is 98.0% or more and less than 99.0%

[0796] Brightness unevenness suppression ×: Brightness change rate less than 98.0%

[0797] [Table 8]

[0798]

[0799] (3) Evaluation of green spectrum characteristics

[0800] For the colored coating film after the light irradiation test in the above "(2) Evaluation of brightness unevenness suppression", the spectrum was measured using an ultraviolet visible near-infrared absorption spectrometer (Japan Spectroscope: V-770) to evaluate the transmittance in the green region when the film thickness of the colored coating film was 2.0 μm. The results are shown in Table 9. If the transmittance at 550 nm is 35% to 99% and the transmittance at 620 nm is 0.1% to 30%, it can be said that when the green filter in the color filter is made, it can show better spectral characteristics even after long-term use.

[0801] [Table 9]

[0802]

Claims

1. A colored resin composition comprising a colorant and an alkali-soluble resin, wherein the colorant comprises a compound represented by formula (I), In formula (I), R 1 ~R 16 Each independently represents a hydrogen atom, a bromine atom, an iodine atom, a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, a group represented by formula (ia), a group represented by formula (ib) or a group represented by formula (ic), wherein -CH2- contained in the hydrocarbon group may be substituted by -O- or -CO-, wherein, R 1 ~R 16 At least one of them represents a group represented by formula (ia), a group represented by formula (ib) or a group represented by formula (ic); when there are multiple groups represented by formula (ia), they may be the same or different; when there are multiple groups represented by formula (ib), they may be the same or different; when there are multiple groups represented by formula (ic), they may be the same or different; In formula (ia), R a1 ~R a5 Each independently represents a hydrogen atom, a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, wherein -CH2- contained in the hydrocarbon group may be substituted by -O- or -CO-, wherein R a1 ~R a5 At least one of represents a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, * represents a bonding site, In formula (ib), R b1 ~R b7 Each independently represents a hydrogen atom, a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, wherein -CH2- contained in the hydrocarbon group may be substituted by -O- or -CO-, wherein R b1 ~R b7 At least one of represents a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, * represents a bonding site, In formula (ic), R c1 ~R c7 Each independently represents a hydrogen atom, a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, wherein -CH2- contained in the hydrocarbon group may be substituted by -O- or -CO-, wherein R c1 ~R c7 At least one of them represents a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and * represents a bonding site.

2. The colored resin composition according to claim 1, wherein R 1 ~R 4 At least one of them is a group represented by formula (ia), formula (ib) or formula (ic), R 5 ~R 8 At least one of them is a group represented by formula (ia), formula (ib) or formula (ic), R 9 ~R 12 At least one of them is a group represented by formula (ia), formula (ib) or formula (ic), R 13 ~R 16 At least one of them is a group represented by formula (ia), formula (ib) or formula (ic).

3. The colored resin composition according to claim 2, wherein R 2 and R 3 At least one of them is a group represented by formula (ia), formula (ib) or formula (ic), R 6 and R 7 At least one of them is a group represented by formula (ia), formula (ib) or formula (ic), R 10 and R 11 At least one of them is a group represented by formula (ia), formula (ib) or formula (ic), R 14 and R 15 At least one of them is a group represented by formula (ia), formula (ib) or formula (ic), R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 A hydrogen atom.

4. The colored resin composition according to claim 3, wherein R 2 and R 3 Any one of them is a group represented by formula (ia), formula (ib) or formula (ic), R 6 and R 7 Any one of them is a group represented by formula (ia), formula (ib) or formula (ic), R 10 and R 11 Any one of them is a group represented by formula (ia), formula (ib) or formula (ic), R 14 and R 15 Any one of them is a group represented by formula (ia), formula (ib) or formula (ic), R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 is a hydrogen atom, The four groups represented by the formula (ia), formula (ib) or formula (ic) in the formula (I) are the same groups.

5. The colored resin composition according to claim 2, wherein R 1 , R 5 , R 9 and R 13 are each independently a group represented by formula (ia), formula (ib) or formula (ic), R 2 ~R 4 , R 6 ~R 8 , R 10 ~R 12 and R 14 ~R 16 A hydrogen atom.

6. The colored resin composition according to claim 1 or 2, wherein It further contains a polymerizable compound and a polymerization initiator. 7 . A color filter formed from the colored resin composition according to claim 6 . A display device comprising the color filter according to claim 7. 9 . A solid-state imaging element comprising the color filter according to claim 7 .

10. A method for producing a compound represented by formula (I), comprising reacting a compound represented by formula (II-1) to (II-4) in the presence of a base and a compound represented by formula (III). In formula (I), R 1 ~R 16 Each independently represents a hydrogen atom, a bromine atom, an iodine atom, a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, a group represented by formula (ia), a group represented by formula (ib) or a group represented by formula (ic), wherein -CH2- contained in the hydrocarbon group may be substituted by -O- or -CO-, wherein, R 1 ~R 16 At least one of them represents a group represented by formula (ia), a group represented by formula (ib) or a group represented by formula (ic); when there are multiple groups represented by formula (ia), they may be the same or different; when there are multiple groups represented by formula (ib), they may be the same or different; when there are multiple groups represented by formula (ic), they may be the same or different; In formula (ia), R a1 ~R a5 Each independently represents a hydrogen atom, a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, wherein -CH2- contained in the hydrocarbon group may be substituted by -O- or -CO-, wherein R a1 ~R a5 At least one of represents a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, * represents a bonding site, In formula (ib), R b1 ~R b7 Each independently represents a hydrogen atom, a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, wherein -CH2- contained in the hydrocarbon group may be substituted by -O- or -CO-, wherein R b1 ~R b7 At least one of represents a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, * represents a bonding site, In formula (ic), R c1 ~R c7 Each independently represents a hydrogen atom, a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, wherein -CH2- contained in the hydrocarbon group may be substituted by -O- or -CO-, wherein R c1 ~R c7 At least one of represents a bromine atom, an iodine atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, * represents a bonding site, AIX M 3 (III) In formula (III), X M Represents a halogen atom, a hydroxyl group, or OR M Ji, R M represents a hydrocarbon group having 1 to 6 carbon atoms, In formulas (II-1) to (II-4), R 1 ~R 16 Indicates that the R 1 ~R 16 Same meaning.

11. The manufacturing method according to claim 10, wherein: The amount of the compound represented by the formula (III) used is 0.25 mol to 0.40 mol per 1 mol of the total amount of the compounds represented by the formulae (II-1) to (II-4).

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