CN105408427A

CN105408427A - Compound and colored curable resin composition

Info

Publication number: CN105408427A
Application number: CN201480030604.9A
Authority: CN
Inventors: 铃木智也; 芦田徹; 吴龙虎; 赤坂哲郎
Original assignee: Dongwoo Fine Chem Co Ltd
Current assignee: Dongwoo Fine Chem Co Ltd
Priority date: 2013-05-31
Filing date: 2014-05-29
Publication date: 2016-03-16
Also published as: KR102204232B1; CN106967037B; JPWO2014192973A1; WO2014192973A1; KR102250529B1; TW201823225A; CN107082772A; KR20160015251A; KR20200111285A; JP6370778B2; KR102250530B1; TWI648269B; TWI644905B; KR20200110824A; TW201823226A; TW201502126A; CN106967037A

Abstract

Provided is a compound represented by formula (Ia), as a compound useful as a dye. (Ia) [R1a, R2a, R3a and R4a are each independently an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms, provided that R1a, R2a, R3a and R4a are not all the same group.]

Description

Compound and colored curable resin composition

Technical field

The present invention relates to the compound and colored curable resin composition that can be used as dyestuff.

Background technology

Such as, in order to utilize reflected light or transmitted light and carry out look display in the fields such as filamentary material, liquid crystal indicator, ink-jet, dyestuff is employed.As such dyestuff, known sulfo group xanthene based dye (patent documentation 1) that such as there is xanthene skeleton, that represented by following formula (a).In addition, the also known rhodamine B (non-patent literature 1) represented by following formula (b).

Prior art document

Patent documentation

Patent documentation 1: Unexamined Patent 3-107489 publication

Non-patent literature

Non-patent literature 1: thin Tian Fengzhu " reactive monoazo dyestuffs chemistry ", (strain) skill report hall, 1 edition, in May, 1973,274 pages

Summary of the invention

The problem that invention will solve

Above-mentioned compound known so far solvability in organic solvent may not be satisfied the demand fully.

For solving the means of problem

The present invention comprises following invention.

[1] compound represented by formula (Ia).

[R ^1a, R ^2a, R ^3aand R ^4arepresent the alkyl of carbon number 1 ~ 20 or the cycloalkyl of carbon number 5 ~ 10 independently of one another.In addition, R ^1awith R ^2aring is formed, R together with the nitrogen-atoms can be combined with each other, combined with them ^3awith R ^4aring is formed together with the nitrogen-atoms can be combined with each other, combined with them.But, R ^1a, R ^2a, R ^3aand R ^4anot be all same group.-CH contained in abovementioned alkyl ₂-can by-O-,-NR ^b-or-CO-substitute, hydrogen atom contained in abovementioned alkyl can be replaced by the aromatic hydrocarbyl of halogen atom, carbon number 6 ~ 20 or-OH, and hydrogen atom contained in above-mentioned aromatic hydrocarbyl can be replaced by the alkoxyl group of carbon number 1 ~ 8, R ^brepresent the alkyl of carbon number 1 ~ 3.]

[2] compound Gen Ju [1], wherein, R ^1a, R ^2a, R ^3aand R ^4abe the alkyl of carbon number 1 ~ 20 independently of one another ,-CH contained in abovementioned alkyl ₂-can be substituted by-O-or CO-, hydrogen atom contained in abovementioned alkyl can be replaced by the aromatic hydrocarbyl of halogen atom or carbon number 6 ~ 10.

[3] according to [1] or the compound described in [2], wherein, R ^1a, R ^2a, R ^3aand R ^4ain at least 2 be the alkyl of carbon number 2 ~ 20 ,-CH contained in abovementioned alkyl ₂-can be substituted by-O-or CO-, hydrogen atom contained in abovementioned alkyl can be replaced by the aromatic hydrocarbyl of halogen atom or carbon number 6 ~ 10.

[4] according to the compound described in any one of [1] ~ [3], wherein, R ^1a, R ^2a, R ^3aand R ^4abe the alkyl of carbon number 2 ~ 20 independently of one another ,-CH contained in abovementioned alkyl ₂-can be substituted by-O-.

[5] according to the compound described in any one of [1] ~ [4], wherein, R ^1a, R ^2a, R ^3aand R ^4ain 1 be-CH contained in the alkyl of carbon number 2 ~ 20 ₂-by the alternative group of-O-.

[6] compound Gen Ju [1], wherein, R ^1aand R ^2abe the alkyl of carbon number 2 ~ 6 independently of one another, R ^3aand R ^4abe the alkyl of carbon number 1 ~ 6 independently of one another.

[7] compound Gen Ju [1], wherein, R ^1aand R ^2abe ethyl separately, R ^3aand R ^4abe methyl, propyl group or butyl independently of one another.

[8] compound Gen Ju [1], wherein, R ^1aand R ^2abe ethyl separately, R ^3afor-CH contained in the alkyl of carbon number 4 ~ 15 ₂-by the alternative group of-O-.

[9] compound represented by formula (Ib).

[R ^1b, R ^2band R ^3brepresent the alkyl of carbon number 1 ~ 8 independently of one another, hydrogen atom contained in abovementioned alkyl can be replaced by the aromatic hydrocarbyl of carbon number 6 ~ 10, and hydrogen atom contained in above-mentioned aromatic hydrocarbyl can be replaced by the alkoxyl group of carbon number 1 ~ 3.Ar represents the group represented by formula (i).

(R represents the alkyl of hydrogen atom or carbon number 1 ~ 3, and hydrogen atom contained in abovementioned alkyl can be replaced by halogen atom.M represents the integer of 1 ~ 5.When m is more than 2, multiple R can be mutually the same, also can be different.* the bonding end with nitrogen-atoms is represented.)]

[10] compound Gen Ju [9], wherein, R ^1b, R ^2band R ^3bbe methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or 2-ethylhexyl independently of one another.

[11] according to [9] or the compound described in [10], wherein, R is methyl.

[12] according to the compound described in any one of [9] ~ [11], wherein, m is 1 or 2.

[13] according to the compound described in any one of [9] ~ [12], wherein, Ar is the group represented by formula (C-0), the group represented by formula (C-1) or the group represented by formula (C-2).

(* represents the bonding end with nitrogen-atoms.)

[14] compound represented by formula (Ic).

[X ¹and X ²different from each other, represent the alkyl of carbon number 1 ~ 8 separately, hydrogen atom contained in abovementioned alkyl can be replaced by the aromatic hydrocarbyl of carbon number 6 ~ 10, and hydrogen atom contained in above-mentioned aromatic hydrocarbyl can be replaced by the alkoxyl group of carbon number 1 ~ 3.Ar ¹and Ar ²represent the group represented by formula (i) independently of one another.

[15] compound Gen Ju [14], wherein, X ¹and X ²be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or 2-ethylhexyl separately.

[16] according to [14] or the compound described in [15], wherein, R is methyl.

[17] according to the compound described in any one of [14] ~ [16], wherein, m is 1 or 2.

[18] according to the compound described in any one of [14] ~ [17], wherein, Ar ¹and Ar ²group, the group represented by formula (C-1) or the group represented by formula (C-2) independently of one another for being represented by formula (C-0).

(* represents the bonding end with nitrogen-atoms.)

[19] tinting material, it comprises [1] ~ compound described in any one of [18].

[20] tinting material Gen Ju [19], it also comprises pigment.

[21] colored curable resin composition, it comprises [19] or the tinting material described in [20], resin, polymerizable compound, polymerization starter and solvent.

[22] film, is formed by the colored curable resin composition described in [21].

[23] colour filter, is formed by the colored curable resin composition described in [21].

[24] display unit, the colour filter that it comprises described in [23].

The effect of invention

Compound of the present invention solvability is in organic solvent excellent, for the colour filter formed by the colored curable resin composition comprising compound of the present invention, can expect that lightness is higher.

Embodiment

1st compound of the present invention is that the compound represented by formula (Ia) (is also recited as " compound (Ia) " below sometimes.)。Also its tautomer, steric isomer is comprised in compound of the present invention.

In formula (Ia), R ^1a, R ^2a, R ^3aand R ^4anot be all same group.

As the alkyl of carbon number 1 ~ 20, the straight-chain alkyl of the carbon numbers 1 ~ 20 such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl can be enumerated;

Sec.-propyl, isobutyl-, sec-butyl, isopentyl, 1-methyl amyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 1-ethyl-butyl, 2-ethyl-butyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethyl pentyl group, 2-ethyl pentyl group, 3-ethyl pentyl group, 1-butyl, 1-(1-methylethyl) butyl, 1-(1-methylethyl)-2-methyl-propyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 1-n-propyl amyl group, 2-propylpentyl, 1-(1-methylethyl) amyl group, 1-butyl, the tertiary butyl, 1,1-dimethyl propyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1-Ethyl-2-Methyl propyl group, 1,1-dimethyl amyl group, 1,2-dimethyl amyl group, 1,3-dimethyl amyl group, Isosorbide-5-Nitrae-dimethyl amyl group, 2,2-dimethyl amyl group, 2,3-dimethyl amyl group, 2,4-dimethyl amyl group, 3,3-dimethyl amyl group, 3,4-dimethyl amyl group, 1-ethyl-1-methyl butyl, 1-Ethyl-2-Methyl butyl, 1-ethyl-3-methyl butyl, 2-ethyl-1-methyl butyl, 2-ethyl-3-methyl butyl, 1,1-dimethylhexanyl, 1,2-dimethylhexanyl, 1,3-dimethylhexanyl, Isosorbide-5-Nitrae-dimethylhexanyl, 1,5-dimethylhexanyl, 2,2-dimethylhexanyl, 2,3-dimethylhexanyl, 2,4-dimethylhexanyl, 2,5-dimethylhexanyl, 3,3-dimethylhexanyl, 3,4-dimethylhexanyl, 3,5-dimethylhexanyl, 4,4-dimethylhexanyl, 4,5-dimethylhexanyl, 1-Ethyl-2-Methyl amyl group, 1-ethyl-3-methyl amyl, 1-ethyl-4-methyl amyl, 2-ethyl-1-methyl amyl, 2-Ethyl-2-Methyl amyl group, 2-ethyl-3-methyl amyl, 2-ethyl-4-methyl amyl, 3-ethyl-1-methyl amyl, 3-Ethyl-2-Methyl amyl group, 3-ethyl-3-methyl amyl, 3-ethyl-4-methyl amyl, 1-propyl group-1-methyl butyl, 1-propyl group-2-methyl butyl, 1-propyl group-3-methyl butyl, 1-(1-methylethyl)-1-methyl butyl, 1-(1-methylethyl)-2-methyl butyl, 1-(1-methylethyl)-3-methyl butyl, 1,1-diethyl butyl, branch's chain-like alkyl of the carbon numbers 3 ~ 20 such as 1,2-diethyl butyl.

-CH contained in abovementioned alkyl ₂-can by-O-,-NR ^b-or CO-is alternative, R ^brepresent the alkyl of carbon number 1 ~ 3, as the alkyl of carbon number 1 ~ 3, methyl, ethyl, propyl group, sec.-propyl etc. can be enumerated.As-CH contained in alkyl ₂-by-O-,-NR ^b-or the group that substitutes of-CO-,-CH contained in preferred alkyl ₂-by the alternative group of-O-or-CO-, more preferably contained in alkyl-CH ₂-by the alternative group of-O-.

Hydrogen atom contained in abovementioned alkyl can be replaced by the aromatic hydrocarbyl of halogen atom, carbon number 6 ~ 20 or-OH, and hydrogen atom contained in above-mentioned aromatic hydrocarbyl can be replaced by the alkoxyl group of carbon number 1 ~ 8.As the group that hydrogen atom contained in alkyl is replaced by the aromatic hydrocarbyl of halogen atom, carbon number 6 ~ 20 or-OH, the group that hydrogen atom contained in preferred alkyl is replaced by the aromatic hydrocarbyl of halogen atom or carbon number 6 ~ 20.

As halogen atom, fluorine atom etc. can be enumerated, as the aromatic hydrocarbyl of carbon number 6 ~ 20, phenyl, naphthyl, xenyl, tolyl, ethylphenyl, propyl group phenyl, butyl phenyl, amyl group phenyl, hexyl phenyl, heptyl phenyl, octyl phenyl, nonyl phenyl, decyl phenyl etc. can be enumerated.As the alkoxyl group of carbon number 1 ~ 8, can enumerate methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy, isopentyloxy, hexyloxy, heptan oxygen base, octyloxy etc.

The concrete example of the group that hydrogen atom contained in abovementioned alkyl is replaced by the aromatic hydrocarbyl of carbon number 6 ~ 10 as shown below.Should illustrate, in following formula, * represents the bonding end with nitrogen-atoms.

As-CH contained in alkyl ₂-by-O-,-NR ^b-or the group that replaced by the aromatic hydrocarbyl of halogen atom, carbon number 6 ~ 20 or-OH of the CO-group, the hydrogen atom contained in alkyl that substitute and, contained in alkyl-CH ₂-by-O-,-NR ^b-or-CO-substitute while the group that replaced by the aromatic hydrocarbyl of halogen atom, carbon number 6 ~ 20 or OH of hydrogen atom contained in alkyl, the group represented by following formula (D-1) ~ (D-18), (D-31) ~ (D-45) and (D-50) ~ (D-57) can be enumerated.Should illustrate, in following formula, * represents the bonding end with nitrogen-atoms.

Wherein, more excellent from the view point of the easiness manufactured, solvability in organic solvent, the group preferably represented by formula (D-2), formula (D-8), formula (D-14), formula (D-17), formula (D-42), formula (D-43), formula (D-45) or formula (D-56), the group more preferably represented by formula (D-8), formula (D-14), formula (D-17), formula (D-42) or formula (D-45).

As the cycloalkyl of carbon number 5 ~ 10, cyclopentyl, cyclohexyl, suberyl, ring octyl group, 2-methyl amyl, 2-methylhexyl, 2,5-dimethyl amyl groups, 2,6-dimethylhexanyl etc. can be enumerated.

As R ^1awith R ^2athe ring formed together with the nitrogen-atoms be combined with each other, combined with them, can enumerate pyrrolidine ring, morpholine ring, piperidine ring, piperazine ring etc.

As R ^3awith R ^4athe ring formed together with the nitrogen-atoms be combined with each other, combined with them, can enumerate pyrrolidine ring, morpholine ring, piperidine ring, piperazine ring etc.

Preferred R ^1a, R ^2a, R ^3aand R ^4abe-CH contained in the alkyl of carbon number 1 ~ 20, abovementioned alkyl independently of one another ₂-can be substituted by-O-or CO-, compound (Ia) that hydrogen atom contained in abovementioned alkyl can be replaced by the aromatic hydrocarbyl of halogen atom or carbon number 6 ~ 10.

Preferred R ^1a, R ^2a, R ^3aand R ^4ain at least 2 be-CH contained in the alkyl of carbon number 2 ~ 20, abovementioned alkyl ₂-can be substituted by-O-or CO-, compound (Ia) that hydrogen atom contained in abovementioned alkyl can be replaced by the aromatic hydrocarbyl of halogen atom or carbon number 6 ~ 10.

Preferred R ^1a, R ^2a, R ^3aand R ^4abe-CH contained in the alkyl of carbon number 2 ~ 20, abovementioned alkyl independently of one another ₂-can by-O-substitute compound (Ia).

Preferred R ^1a, R ^2a, R ^3aand R ^4ain 1 be-CH contained in the alkyl of carbon number 2 ~ 20 ₂the compound (Ia) of the group that-quilt-O-substitutes.

Preferred R ^1aand R ^2abe alkyl, the R of carbon number 2 ~ 6 independently of one another ^3aand R ^4abe the compound (Ia) of the alkyl of carbon number 1 ~ 6 independently of one another.

Preferred R ^1aand R ^2abe ethyl, R separately ^3aand R ^4abe the compound (Ia) of methyl, propyl group or butyl independently of one another.

Preferred R ^1aand R ^2abe ethyl, R separately ^3afor-CH contained in the alkyl of carbon number 4 ~ 15 ₂the compound (Ia) of the group that-quilt-O-substitutes.

As the concrete example of compound (Ia), the compound shown in table 1 can be enumerated.In table 1, Me represents-CH ₃, Et represents-CH ₂cH ₃, Pr represents-CH ₂cH ₂cH ₃, i-Pr represents-CH (CH ₃) ₂, Bu represents-CH ₂cH ₂cH ₂cH ₃, i-Bu represents-CH ₂cH (CH ₃) ₂, Pen represents-CH ₂cH ₂cH ₂cH ₂cH ₃, Hex represents-CH ₂cH ₂cH ₂cH ₂cH ₂cH ₃, EtHex represents-CH ₂cH (C ₂h ₅) (CH ₂) ₃cH ₃.

Table 1

Wherein, the easiness manufactured, the aspect that solvability is in organic solvent excellent especially, preferred compound (Ia-2), compound (Ia-3), compound (Ia-4), compound (Ia-5), compound (Ia-6), compound (Ia-7), compound (Ia-8), compound (Ia-9), compound (Ia-13), compound (Ia-14), compound (Ia-15), compound (Ia-16), compound (Ia-51), compound (Ia-55), compound (Ia-59), compound (Ia-63), compound (Ia-66), compound (Ia-67), compound (Ia-68), compound (Ia-69), compound (Ia-70), compound (Ia-71), compound (Ia-73), compound (Ia-75) or compound (Ia-77), more preferably compound (Ia-7), compound (Ia-16), compound (Ia-67), compound (Ia-68) or compound (Ia-69).

Compound (Ia) can by making formula (IIIa)

Shown compound (is recited as " compound (IIIa) " below sometimes.) and formula (IVa)

[in formula (IVa), R ^1aand R ^2athe implication that respective expression is same as described above.]

Shown compound (is recited as " compound (IVa) " below sometimes.) reaction, obtain formula (Va)

Shown compound (is recited as " compound (Va) " below sometimes.), make the compound (Va) that obtains and formula (VIa)

[in formula (VIa), R ^3aand R ^4athe implication that respective expression is same as described above.]

Shown compound (is recited as " compound (VIa) " below sometimes.) react and manufacture.

In addition, also can react by making compound (IIIa) and compound (VIa), obtaining formula (VIIa)

Shown compound (is recited as " compound (VIIa) " below sometimes.), the compound (VIIa) obtained is reacted with compound (IVa), thus also can manufacture compound (Ia).

This reaction can be implemented in the presence of the solvent, as above-mentioned solvent, can enumerate the hydrocarbon solvent such as toluene, dimethylbenzene; The halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, chloroform; The alcoholic solvents such as methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, ethylene glycol; The nitro-hydrocarbon solvents such as oil of mirbane; The ketone solvents such as methyl iso-butyl ketone (MIBK); The amide solvents such as 1-Methyl-2-Pyrrolidone, DMF, N,N-dimethylacetamide; Water; Deng.

Temperature of reaction preferably-10 DEG C ~ 180 DEG C, more preferably 0 DEG C ~ 100 DEG C.Preferably 1 hour ~ 12 hours reaction times, more preferably 1 hour ~ 8 hours.

The usage quantity of compound (IVa) or compound (VIa), relative to 1 mole compound (IIIa), is preferably more than 1 mole less than 30 moles, is more preferably more than 2 moles less than 4 moles.

The method obtained by reaction mixture as the compound (Ia) of target compound is not particularly limited, known various gimmick can be adopted.Such as, reaction mixture and acid (such as acetic acid, hydrochloric acid etc.) can be mixed together, the crystallization that leaching is separated out.For above-mentioned acid, preferably after modulating aqueous acid in advance, reaction mixture is added in the above-mentioned aqueous solution.Temperature when adding reaction mixture is preferably more than 0 DEG C less than 50 DEG C, is more preferably more than 10 DEG C less than 40 DEG C.In addition, reaction mixture is added to after in aqueous acid, preferably stir 0.5 ~ 2 hours at such a temperature.For the crystallization of leaching, preferably clean with water etc., next dry.In addition, as required, the known gimmicks such as recrystallization can be adopted to refine further.

2nd compound of the present invention is that the compound represented by formula (Ib) (is also recited as " compound (Ib) " below sometimes.)。Also its tautomer is comprised in compound of the present invention.

(R represents the alkyl of hydrogen atom or carbon number 1 ~ 3, and hydrogen atom contained in abovementioned alkyl can be replaced by halogen atom.M represents the integer of 1 ~ 5.When m is more than 2, multiple R can mutually the same also can be different.* the bonding end with nitrogen-atoms is represented.)]

As by R ^1b, R ^b2and R ^3bthe alkyl of the carbon number 1 ~ 8 represented, can enumerate the straight-chain alkyl such as such as methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl;

Sec.-propyl, isobutyl-, sec-butyl, isopentyl, 1-methyl amyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 1-ethyl-butyl, 2-ethyl-butyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethyl pentyl group, 2-ethyl pentyl group, 3-ethyl pentyl group, 1-butyl, 1-(1-methylethyl) butyl, 1-(1-methylethyl)-2-methyl-propyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, the n-propylpentyl of 1-, 2-propylpentyl, 1-(1-methylethyl) amyl group, 1-butyl, the tertiary butyl, 1,1-dimethyl propyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1-Ethyl-2-Methyl propyl group, 1,1-dimethyl amyl group, 1,2-dimethyl amyl group, 1,3-dimethyl amyl group, Isosorbide-5-Nitrae-dimethyl amyl group, 2,2-dimethyl amyl group, 2,3-dimethyl amyl group, 2,4-dimethyl amyl group, 3,3-dimethyl amyl group, 3,4-dimethyl amyl group, 1-ethyl-1-methyl butyl, 1-Ethyl-2-Methyl butyl, 1-ethyl-3-methyl butyl, 2-ethyl-1-methyl butyl, 2-ethyl-3-methyl butyl, 1,1-dimethylhexanyl, 1,2-dimethylhexanyl, 1,3-dimethylhexanyl, Isosorbide-5-Nitrae-dimethylhexanyl, 1,5-dimethylhexanyl, 2,2-dimethylhexanyl, 2,3-dimethylhexanyl, 2,4-dimethylhexanyl, 2,5-dimethylhexanyl, 3,3-dimethylhexanyl, 3,4-dimethylhexanyl, 3,5-dimethylhexanyl, 4,4-dimethylhexanyl, 4,5-dimethylhexanyl, 1-Ethyl-2-Methyl amyl group, 1-ethyl-3-methyl amyl, 1-ethyl-4-methyl amyl, 2-ethyl-1-methyl amyl, 2-Ethyl-2-Methyl amyl group, 2-ethyl-3-methyl amyl, 2-ethyl-4-methyl amyl, 3-ethyl-1-methyl amyl, 3-Ethyl-2-Methyl amyl group, 3-ethyl-3-methyl amyl, 3-ethyl-4-methyl amyl, 1-propyl group-1-methyl butyl, 1-propyl group-2-methyl butyl, 1-propyl group-3-methyl butyl, 1-(1-methylethyl)-1-methyl butyl, 1-(1-methylethyl)-2-methyl butyl, 1-(1-methylethyl)-3-methyl butyl, 1,1-diethyl butyl, point branched-chain alkyl such as 1,2-diethyl butyl, Deng.

Hydrogen atom contained in the alkyl of these carbon numbers 1 ~ 8 can be replaced by the aromatic hydrocarbyl of carbon number 6 ~ 10, as the aromatic hydrocarbyl of carbon number 6 ~ 10, can enumerate phenyl, naphthyl, tolyl, ethylphenyl, n-propyl phenyl, isopropyl phenyl etc.Hydrogen atom contained in the aromatic hydrocarbyl of these carbon numbers 6 ~ 10 can be replaced by the alkoxyl group of carbon number 1 ~ 3, as the alkoxyl group of carbon number 1 ~ 3, can enumerate methoxyl group, oxyethyl group, positive propoxy, isopropoxy.

As the group that hydrogen atom contained in abovementioned alkyl is replaced by the aromatic hydrocarbyl of carbon number 6 ~ 10, example group described as follows can be enumerated.

(* represents the bonding end with nitrogen-atoms.)

As the alkyl of the carbon number 1 ~ 3 represented by R, methyl, ethyl, n-propyl, sec.-propyl etc. can be enumerated, as the group that hydrogen atom contained in the alkyl of carbon number 1 ~ 3 is replaced by halogen atom, following group etc. can be enumerated.

M represents the integer of 1 ~ 5, obtains from the view point of raw material, is preferably 1 or 2.

As the group represented by formula (i), example group described as follows can be enumerated.Wherein, the group preferably represented by formula (C-0), the group represented by formula (C-1) or the group represented by formula (C-2).

(* represents the bonding end with nitrogen-atoms.)

As compound (Ib), the compound such as shown in table 2 can be enumerated.In table 2, Me represents-CH ₃, Et represents-CH ₂cH ₃, Pr represents-CH ₂cH ₂cH ₃, i-Pr represents-CH (CH ₃) ₂, Bu represents-CH ₂cH ₂cH ₂cH ₃, t-Bu represents-C (CH ₃) ₃, EtHex represents-CH ₂cH (C ₂h ₅) (CH ₂) ₃cH ₃.The sequence number as the illustrative above-mentioned formula of the group represented by formula (i) is represented by the sequence number that C starts in the Ar hurdle of table 2.

Table 2

Compound	R ^1b	R ^2b	R ^3b	Ar
					Ib-1	Me	Me	Me	C-0
Ib-2	Me	Me	Me	C-1
					Ib-3	Me	Me	Me	C-2
Ib-4	Me	Me	Me	C-3
					Ib-5	Me	Me	Me	C-4
Ib-6	Me	Me	Me	C-5
					Ib-7	Me	Me	Me	C-6
Ib-8	Et	Et	Me	C-0
					Ib-9	Et	Et	Me	C-1
Ib-10	Et	Et	Me	C-2
					Ib-11	Et	Et	Me	C-3
Ib-12	Et	Et	Me	C-4
					Ib-13	Et	Et	Me	C-5
Ib-14	Et	Et	Me	C-6

Ib-15	Pr	Pr	Me	C-0
					Ib-16	Pr	Pr	Me	C-1
Ib-17	Pr	Pr	Me	C-2
					Ib-18	Pr	Pr	Me	C-3
Ib-19	Pr	Pr	Me	C-4
					Ib-20	Pr	Pr	Me	C-5
Ib-21	Pr	Pr	Me	C-6
					Ib-22	Bu	Bu	Me	C-0
Ib-23	Bu	Bu	Me	C-1
					Ib-24	Bu	Bu	Me	C-2
Ib-25	Bu	Bu	Me	C-3
					Ib-26	Bu	Bu	Me	C-4
Ib-27	Bu	Bu	Me	C-5
					Ib-28	Bu	Bu	Me	C-6
Ib-29	Me	Me	Et	C-0
					Ib-30	Me	Me	Et	C-1
Ib-31	Me	Me	Et	C-2
					Ib-32	Me	Me	Et	C-3
Ib-33	Me	Me	Et	C-4
					Ib-34	Me	Me	Et	C-5
Ib-35	Me	Me	Et	C-6
					Ib-36	Et	Et	Et	C-0
Ib-37	Et	Et	Et	C-1
					Ib-38	Et	Et	Et	C-2
Ib-39	Et	Et	Et	C-3
					Ib-40	Et	Et	Et	C-4
Ib-41	Et	Et	Et	C-5
					Ib-42	Et	Et	Et	C-6
Ib-43	Pr	Pr	Et	C-0

Ib-44	Pr	Pr	Et	C-1
					Ib-45	Pr	Pr	Et	C-2
Ib-46	Pr	Pr	Et	C-3
					Ib-47	Pr	Pr	Et	C-4
Ib-48	Pr	Pr	Et	C-5
					Ib-49	Pr	Pr	Et	C-6
Ib-50	Bu	Bu	Et	C-0
					Ib-51	Bu	Bu	Et	C-1
Ib-52	Bu	Bu	Et	C-2
					Ib-53	Bu	Bu	Et	C-3
Ib-54	Bu	Bu	Et	C-4
					Ib-55	Bu	Bu	Et	C-5
Ib-56	Bu	Bu	Et	C-6
					Ib-57	Me	Me	Pr	C-0
Ib-58	Me	Me	i-Pr	C-0
					Ib-59	Me	Me	Bu	C-0
Ib-60	Me	Me	t-Bu	C-0
					Ib-61	Me	Me	EtHex	C-0
Ib-62	Me	Me	Pr	C-1
					Ib-63	Me	Me	i-Pr	C-1
Ib-64	Me	Me	Bu	C-1
					Ib-65	Me	Me	t-Bu	C-1
Ib-66	Me	Me	EtHex	C-1
					Ib-67	Me	Me	Pr	C-2
Ib-68	Me	Me	i-Pr	C-2
					Ib-69	Me	Me	Bu	C-2
Ib-70	Me	Me	t-Bu	C-2
					Ib-71	Me	Me	EtHex	C-2
Ib-72	Et	Et	Pr	C-0

Ib-73	Et	Et	i-Pr	C-0
					Ib-74	Et	Et	Bu	C-0
Ib-75	Et	Et	t-Bu	C-0
					Ib-76	Et	Et	EtHex	C-0
Ib-77	Et	Et	Pr	C-1
					Ib-78	Et	Et	i-Pr	C-1
Ib-79	Et	Et	Bu	C-1
					Ib-80	Et	Et	t-Bu	C-1
Ib-81	Et	Et	EtHex	C-1
					Ib-82	Et	Et	Pr	C-2
Ib-83	Et	Et	i-Pr	C-2
					Ib-82	Et	Et	Bu	C-2
Ib-84	Et	Et	t-Bu	C-2
					Ib-85	Et	Et	EtHex	C-2
Ib-86	Pr	Pr	Pr	C-0
					Ib-87	Pr	Pr	i-Pr	C-0
Ib-88	Pr	Pr	Bu	C-0
					Ib-89	Pr	Pr	t-Bu	C-0
Ib-90	Pr	Pr	EtHex	C-0
					Ib-91	Pr	Pr	Pr	C-1
Ib-92	Pr	Pr	i-Pr	C-1
					Ib-93	Pr	Pr	Bu	C-1
Ib-94	Pr	Pr	t-Bu	C-1
					Ib-95	Pr	Pr	EtHex	C-1
Ib-96	Pr	Pr	Pr	C-2
					Ib-97	Pr	Pr	i-Pr	C-2
Ib-98	Pr	Pr	Bu	C-2
					Ib-99	Pr	Pr	t-Bu	C-2
Ib-100	Pr	Pr	EtHex	C-2

Ib-101	Bu	Bu	Pr	C-0
					Ib-102	Bu	Bu	i-Pr	C-0
Ib-103	Bu	Bu	Bu	C-0
					Ib-104	Bu	Bu	t-Bu	C-0
Ib-105	Bu	Bu	EtHex	C-0
					Ib-106	Bu	Bu	Pr	C-1
Ib-107	Bu	Bu	i-Pr	C-1
					Ib-108	Bu	Bu	Bu	C-1
Ib-109	Bu	Bu	t-Bu	C-1
					Ib-110	Bu	Bu	EtHex	C-1
Ib-111	Bu	Bu	Pr	C-2
					Ib-112	Bu	Bu	i-Pr	C-2
Ib-113	Bu	Bu	Bu	C-2
					Ib-114	Bu	Bu	t-Bu	C-2
Ib-115	Bu	Bu	EtHex	C-2

Wherein, the aspect that solvability is in organic solvent excellent especially, preferred compound (Ib-8), compound (Ib-36), compound (Ib-37), compound (Ib-38) and compound (Ib-101).

Next, the manufacture method of compound (Ib) is described.

As the manufacture method of compound (Ib), can enumerate and make formula (IIb)

Shown compound (is recited as " compound (IIb) " below sometimes.) and formula (IIIb)

[in formula (IIIb), R ^1band R ^2bthe implication that respective expression is same as described above.]

Shown compound (is recited as " compound (IIIb) " below sometimes.) react in organic solvent, obtain formula (IVb)

[in formula (IVb), R ^1band R ^2bthe implication that respective expression is same as described above.]

Shown compound (is recited as " compound (IVb) " below sometimes.) after, with formula (V)

[in formula (Vb), R ^3b, R and m represent implication same as described above separately.]

Shown compound (is recited as " compound (Vb) " below sometimes.) manufacture method of reacting in organic solvent.

As compound (IIb) and the organic solvent in the reaction of compound (IIIb), the hydrocarbon solvent such as toluene, dimethylbenzene can be enumerated; The halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, chloroform; The alcoholic solvents such as methyl alcohol, ethanol, butanols; The nitration hydrocarbon solvents such as oil of mirbane; The ketone solvents such as methyl iso-butyl ketone (MIBK); The amide solvents such as 1-Methyl-2-Pyrrolidone; Deng.

Compound (IIb) and the temperature of reaction preferably 0 DEG C ~ 100 DEG C in the reaction of compound (IIIb), more preferably 20 DEG C ~ 80 DEG C.Preferably 1 hour ~ 12 hours reaction times, more preferably 1 hour ~ 8 hours.

The usage quantity of compound (IIIb), relative to 1 mole compound (IIb), is preferably more than 1 mole less than 30 moles, is more preferably more than 2 moles less than 20 moles.

As compound (IVb) and the organic solvent in the reaction of compound (Vb), the hydrocarbon solvent such as toluene, dimethylbenzene can be enumerated; The halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, chloroform; The alcoholic solvents such as methyl alcohol, ethanol, butanols; The nitration hydrocarbon solvents such as oil of mirbane; The ketone solvents such as methyl iso-butyl ketone (MIBK); The amide solvents such as 1-Methyl-2-Pyrrolidone; Deng.

Compound (IVb) and the temperature of reaction preferably 30 DEG C ~ 180 DEG C in the reaction of compound (Vb), more preferably 20 DEG C ~ 130 DEG C.Preferably 1 hour ~ 24 hours reaction times, more preferably 1 hour ~ 8 hours.

The usage quantity of compound (Vb), relative to 1 mole compound (IIIb), is preferably more than 1 mole less than 30 moles, is more preferably more than 2 moles less than 20 moles.

The method obtained by reaction mixture as the compound (Ib) of target compound is not particularly limited, known various gimmick can be adopted.Such as, reaction mixture and acid (such as acetic acid etc.) can be mixed together, the crystallization that leaching is separated out.For above-mentioned acid, after preferably modulating aqueous acid in advance, reaction mixture is added in the above-mentioned aqueous solution.Temperature when adding reaction mixture is preferably more than 10 DEG C less than 50 DEG C, is more preferably more than 20 DEG C less than 50 DEG C, more preferably more than 20 DEG C less than 30 DEG C.In addition, after adding reaction mixture to aqueous acid, preferably 0.5 ~ 2 hours is stirred at such a temperature.For the crystallization of leaching, preferably clean with water etc., next dry.In addition, as required, the known gimmicks such as recrystallization can be adopted to refine further.

3rd compound of the present invention is that the compound represented by formula (Ic) (is also recited as " compound (Ic) " below sometimes.)。Also its tautomer is comprised in compound of the present invention.

X ¹and X ²different from each other.

As by X ¹and X ²the alkyl of the carbon number 1 ~ 8 represented, can enumerate the straight-chain alkyl such as such as methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl;

(* represents the bonding end with nitrogen-atoms.)

X ¹and X ²different from each other, be more preferably methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or 2-ethylhexyl.

As the group represented by formula (i), example group described as follows can be enumerated.Wherein, the group preferably represented by formula (C-0), the group represented by formula (C-1) or the group represented by formula (C-2).In addition, preferred Ar ¹and Ar ²for same group.

(* represents the bonding end with nitrogen-atoms.)

As compound (Ic), the compound such as shown in table 3 can be enumerated.In table 2, Me represents-CH ₃, Et represents-CH ₂cH ₃, Pr represents-CH ₂cH ₂cH ₃, i-Pr represents-CH (CH ₃) ₂, Bu represents-CH ₂cH ₂cH ₂cH ₃, t-Bu represents-C (CH ₃) ₃, EtHex represents-CH ₂cH (C ₂h ₅) (CH ₂) ₃cH ₃.The X of table 3 ¹hurdle represents as with X by the sequence number that A starts in recording ¹the group represented and the sequence number of illustrative above-mentioned formula.Ar ¹and Ar ²represent as with Ar by the sequence number that C starts in hurdle ¹and Ar ²the group represented and the sequence number of illustrative above-mentioned formula.

Table 3

Compound	X ¹	X ²	Ar ¹	Ar ²
					Ic-1	Me	Et	C-0	C-0
Ic-2	Me	Et	C-1	C-1
					Ic-3	Me	Et	C-2	C-2
Ic-4	Me	Et	C-3	C-3
					Ic-5	Me	Et	C-4	C-4
Ic-6	Me	Et	C-5	C-5
					Ic-7	Me	Et	C-6	C-6
Ic-8	Me	Pr	C-0	C-0
					Ic-9	Me	i-Pr	C-0	C-0
Ic-10	Me	Bu	C-0	C-0
					Ic-11	Me	t-Bu	C-0	C-0
Ic-12	Me	EtHex	C-0	C-0

Ic-13	Me	Et	C-1	C-1
					Ic-14	Me	Pr	C-1	C-1
Ic-15	Me	i-Pr	C-1	C-1
					Ic-16	Me	Bu	C-1	C-1
Ic-17	Me	t-Bu	C-1	C-1
					Ic-18	Me	EtHex	C-1	C-1
Ic-19	Me	Et	C-2	C-2
					Ic-20	Me	Pr	C-2	C-2
Ic-21	Me	i-Pr	C-2	C-2
					Ic-22	Me	Bu	C-2	C-2
Ic-23	Me	t-Bu	C-2	C-2
					Ic-24	Me	EtHex	C-2	C-2
Ic-25	A-1	Me	C-0	C-0
					Ic-26	A-1	Et	C-0	C-0
Ic-27	A-1	Pr	C-0	C-0
					Ic-28	A-1	i-Pr	C-0	C-0
Ic-29	A-1	Bu	C-0	C-0
					Ic-30	A-1	t-Bu	C-0	C-0
Ic-31	A-1	EtHex	C-0	C-0
					Ic-32	A-2	Me	C-0	C-0
Ic-33	A-2	Et	C-0	C-0
					Ic-34	A-2	Pr	C-0	C-0
Ic-35	A-2	i-Pr	C-0	C-0
					Ic-36	A-2	Bu	C-0	C-0
Ic-37	A-2	t-Bu	C-0	C-0
					Ic-38	A-2	EtHex	C-0	C-0
Ic-39	A-10	Me	C-0	C-0
					Ic-40	A-10	Et	C-0	C-0
Ic-41	A-10	Pr	C-0	C-0

Ic-42	A-10	i-Pr	C-0	C-0
					Ic-43	A-10	Bu	C-0	C-0
Ic-44	A-10	t-Bu	C-0	C-0
					Ic-45	A-10	EtHex	C-0	C-0
Ic-46	A-11	Me	C-0	C-0
					Ic-47	A-11	Et	C-0	C-0
Ic-48	A-11	Pr	C-0	C-0
					Ic-49	A-11	i-Pr	C-0	C-0
Ic-50	A-11	Bu	C-0	C-0
					Ic-51	A-11	t-Bu	C-0	C-0
Ic-52	A-11	EtHex	C-0	C-0
					Ic-53	A-1	Me	C-1	C-1
Ic-54	A-1	Et	C-1	C-1
					Ic-55	A-1	Pr	C-1	C-1
Ic-56	A-1	i-Pr	C-1	C-1
					Ic-57	A-1	Bu	C-1	C-1
Ic-58	A-1	t-Bu	C-1	C-1
					Ic-59	A-1	EtHex	C-1	C-1
Ic-60	A-2	Me	C-1	C-1
					Ic-61	A-2	Et	C-1	C-1
Ic-62	A-2	Pr	C-1	C-1
					Ic-63	A-2	i-Pr	C-1	C-1
Ic-64	A-2	Bu	C-1	C-1
					Ic-65	A-2	t-Bu	C-1	C-1
Ic-66	A-2	EtHex	C-1	C-1
					Ic-67	A-10	Me	C-1	C-1
Ic-68	A-10	Et	C-1	C-1
					Ic-69	A-10	Pr	C-1	C-1
Ic-70	A-10	i-Pr	C-1	C-1

Ic-71	A-10	Bu	C-1	C-1
					Ic-72	A-10	t-Bu	C-1	C-1
Ic-73	A-10	EtHex	C-1	C-1
					Ic-74	A-11	Me	C-1	C-1
Ic-75	A-11	Et	C-1	C-1
					Ic-76	A-11	Pr	C-1	C-1
Ic-77	A-11	i-Pr	C-1	C-1
					Ic-78	A-11	Bu	C-1	C-1
Ic-79	A-11	t-Bu	C-1	C-1
					Ic-80	A-11	EtHex	C-1	C-1
Ic-81	A-11	Me	C-2	C-2
					Ic-82	A-11	Et	C-2	C-2
Ic-83	A-11	Pr	C-2	C-2
					Ic-82	A-11	i-Pr	C-2	C-2
Ic-84	A-11	Bu	C-2	C-2
					Ic-85	A-11	t-Bu	C-2	C-2
Ic-86	A-11	EtHex	C-2	C-2
					Ic-87	A-1	Me	C-2	C-2
Ic-88	A-1	Et	C-2	C-2
					Ic-89	A-1	Pr	C-2	C-2
Ic-90	A-1	i-Pr	C-2	C-2
					Ic-91	A-1	Bu	C-2	C-2
Ic-92	A-1	t-Bu	C-2	C-2
					Ic-93	A-1	EtHex	C-2	C-2
Ic-94	A-2	Me	C-2	C-2
					Ic-95	A-2	Et	C-2	C-2
Ic-96	A-2	Pr	C-2	C-2
					Ic-97	A-2	i-Pr	C-2	C-2
Ic-98	A-2	Bu	C-2	C-2

Ic-99	A-2	t-Bu	C-2	C-2
					Ic-100	A-2	EtHex	C-2	C-2
Ic-101	A-10	Me	C-2	C-2
					Ic-102	A-10	Et	C-2	C-2
Ic-103	A-10	Pr	C-2	C-2
					Ic-104	A-10	i-Pr	C-2	C-2
Ic-105	A-10	Bu	C-2	C-2
					Ic-106	A-10	t-Bu	C-2	C-2
Ic-107	A-10	EtHex	C-2	C-2
					Ic-108	A-11	Me	C-2	C-2
Ic-109	A-11	Et	C-2	C-2
					Ic-110	A-11	Pr	C-2	C-2
Ic-111	A-11	i-Pr	C-2	C-2
					Ic-112	A-11	Bu	C-2	C-2
Ic-113	A-11	t-Bu	C-2	C-2
					Ic-114	A-11	EtHex	C-2	C-2
Ic-115	Et	Pr	C-0	C-0
					Ic-116	Et	i-Pr	C-0	C-0
Ic-117	Et	Bu	C-0	C-0
					Ic-118	Et	t-Bu	C-0	C-0
Ic-119	Et	EtHex	C-0	C-0
					Ic-120	Et	Et	C-1	C-1
Ic-121	Et	Pr	C-1	C-1
					Ic-122	Et	i-Pr	C-1	C-1
Ic-123	Et	Bu	C-1	C-1
					Ic-124	Et	t-Bu	C-1	C-1
Ic-125	Et	EtHex	C-1	C-1
					Ic-126	Et	Et	C-2	C-2
Ic-127	Et	Pr	C-2	C-2

Ic-128	Et	i-Pr	C-2	C-2
					Ic-129	Et	Bu	C-2	C-2
Ic-130	Et	t-Bu	C-2	C-2
					Ic-131	Et	EtHex	C-2	C-2
Ic-132	Me	Et	C-0	C-1
					Ic-133	Me	Et	C-1	C-2
Ic-134	Me	Et	C-0	C-2
					Ic-135	Et	Pr	C-0	C-1
Ic-136	Et	Pr	C-1	C-2
					Ic-137	Et	Pr	C-0	C-2
Ic-138	Me	Et	C-1	C-0
					Ic-139	Me	Et	C-2	C-1
Ic-140	Me	Et	C-2	C-0
					Ic-141	Et	Pr	C-1	C-0
Ic-142	Et	Pr	C-2	C-1
					Ic-143	Et	Pr	C-2	C-0
Ic-144	Me	Pr	C-0	C-1
					Ic-145	Me	Pr	C-1	C-2
Ic-146	Me	Pr	C-0	C-2
					Ic-147	Me	Pr	C-1	C-0
Ic-148	Me	Pr	C-2	C-1
					Ic-149	Me	Pr	C-2	C-0

Wherein, the aspect that solvability is in organic solvent excellent especially, preferred compound (Ic-1), compound (Ic-7), compound (Ic-132), compound (Ic-134), compound (Ic-138) and compound (Ic-140).

Next, the manufacture method of compound (Ic) is described.

As the manufacture method of compound (Ic), can enumerate and make formula (IIc)

Shown compound (is recited as " compound (IIc) " below sometimes.) and formula (IIIc)

[in formula (IIIc), X ¹, R and m represent implication same as described above separately.]

Shown compound (is recited as " compound (IIIc) " below sometimes.) react in organic solvent, obtain by formula (IVc)

[in formula (IVc), X ¹, R and m represent implication same as described above separately.]

The compound represented (is recited as " compound (IVc) " below sometimes.) after, with formula (Vc)

[in formula (Vc), X ², R and m represent implication same as described above separately.]

Shown compound (is recited as " compound (Vc) " below sometimes.) manufacture method of reacting in organic solvent.

As compound (IIc) and the organic solvent in the reaction of compound (IIIc), the hydrocarbon solvent such as toluene, dimethylbenzene can be enumerated; The halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, chloroform; The alcoholic solvents such as methyl alcohol, ethanol, butanols; The nitration hydrocarbon solvents such as oil of mirbane; The ketone solvents such as methyl iso-butyl ketone (MIBK); The amide solvents such as 1-Methyl-2-Pyrrolidone; Deng.

Compound (IIc) and the temperature of reaction preferably 0 DEG C ~ 100 DEG C in the reaction of compound (IIIc), more preferably 20 DEG C ~ 80 DEG C.Preferably 1 hour ~ 12 hours reaction times, 1 hour ~ 8 hours.

The usage quantity of compound (IIIc), relative to 1 mole compound (IIc), is preferably more than 1 mole less than 30 moles, is more preferably more than 2 moles less than 20 moles.

As compound (IVc) and the organic solvent in the reaction of compound (Vc), the hydrocarbon solvent such as toluene, dimethylbenzene can be enumerated; The halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, chloroform; The alcoholic solvents such as methyl alcohol, ethanol, butanols; The nitration hydrocarbon solvents such as oil of mirbane; The ketone solvents such as methyl iso-butyl ketone (MIBK); The amide solvents such as 1-Methyl-2-Pyrrolidone; Deng.

Compound (IVc) and the temperature of reaction preferably 30 DEG C ~ 180 DEG C in the reaction of compound (Vc), more preferably 20 DEG C ~ 130 DEG C.Preferably 1 hour ~ 24 hours reaction times, more preferably 1 hour ~ 8 hours.

The usage quantity of compound (Vc), relative to 1 mole compound (IIIc), is preferably more than 1 mole less than 30 moles, is more preferably more than 2 moles less than 20 moles.

The method obtained by reaction mixture as the compound (Ic) of target compound is not particularly limited, known various gimmick can be adopted.Such as, reaction mixture and acid (such as, acetic acid etc.) can be mixed together, the crystallization that leaching is separated out.For above-mentioned acid, after preferably modulating aqueous acid in advance, reaction mixture is added in the above-mentioned aqueous solution.Temperature when adding reaction mixture is preferably more than 10 DEG C less than 50 DEG C, is more preferably more than 20 DEG C less than 50 DEG C, more preferably more than 20 DEG C less than 30 DEG C.In addition, after adding reaction mixture to aqueous acid, preferably 0.5 ~ 2 hours is stirred at the same temperature.For the crystallization of leaching, preferably clean with water etc., next dry.In addition, as required, the known gimmicks such as recrystallization can be adopted to refine further.

Compound (Ia), compound (Ib) and compound (Ic) (are recited as " compound (I) " below sometimes in the lump.) can be used as dyestuff, due to display high resolution in organic solvent, therefore can be used as the dyestuff used in the colour filter of the display unit such as liquid crystal indicator especially.

Form the content of compound (I) contained in the colored curable resin composition of colour filter, relative to the total amount that solid is divided, preferably below more than 0.025 quality % 48 quality %, more preferably below more than 0.08 quality % 42 quality %, further preferred below more than 0.1 quality % 30 quality %.At this, " total amount that solid is divided " in this specification sheets refers to the amount of the content eliminating solvent from the total amount of colored curable resin composition.The total amount that solid is divided and can being measured by the known analysis means of such as liquid chromatography or gas-chromatography etc. relative to the content of its each composition.

Colored curable resin composition of the present invention contains toner (A), resin (B), polymerizable compound (C), polymerization starter (D), solvent (E).And then, flow agent (F) can be comprised.

Tinting material (A) inclusion compound (I), preferably also comprises pigment (A1), and then, the dyestuff (A2) different from compound (I) can be comprised.

When tinting material (A) also comprises pigment (A1) and/or dyestuff (A2) while inclusion compound (I), the content of compound (I), relative to the total amount of tinting material (A), preferably below more than 0.5 quality % 80 quality %, more preferably below more than 1 quality % 70 quality %, further preferred below more than 1 quality % 50 quality %.

< pigment (A1) >

As pigment (A1), known pigment can be used without particular limitation, the compound being such as categorized as pigment in colour index (TheSocietyofDyersandColourists publication) can be enumerated.

As pigment, (following record of omitting C.I. Pigment Yellow 73 becomes a sequenced and records can to enumerate such as C.I. Pigment Yellow 73 1.), 3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,137,138,139,147,148,150,153,154,166,173,194, the yellow ultramarines such as 214;

C.I. pigment Orange 13,31,36,38,40,42,43,51,55,59,61,64,65,71, the orange pigmentss such as 73;

C.I. Pigment Red 9,97,105,122,123,144,149,166,168,175,176,177,180,192,209,215,216,224,242,254,255,264, the red pigments such as 265;

C.I. pigment Blue 15,15:3,15:4,15:6,60, the green pigments such as 80;

C.I. pigment violet 1,19,23,29,32,36, the violet pigments such as 38;

C.I. pigment Green 7,36, the veridians such as 58;

C.I. the brown such as pigment brown 23,25;

C.I. Pigment black 1,7 Deng ?look pigment etc.

These pigment can be used alone, also can be used in combination by two or more.

As pigment, the red pigments such as the yellow ultramarines such as preferred C.I. pigment yellow 13 8,139,150, C.I. Pigment red 177,242,254, C.I. pigment Blue 15,15:3,15:4,15:6, the green pigments such as 60 and C.I. pigment violet 1,19,23,29,32,36, the violet pigments such as 38.By comprising above-mentioned pigment, the optimization employing the transmitted spectrum of the colour filter of colored curable resin composition of the present invention is easy, and the photostabilization of colour filter and chemicals-resistant become good.

For pigment (A1); as required, rosin process can be implemented, employ the surface treatment of the pigment derivative that imported acidic-group or basic group etc., adopt the grafting process to surface of pigments of macromolecular compound etc., adopt the micronize process of sulfuric acid particles method etc. or adopt the removing process etc. for the clean process of organic solvent, water etc., the employing ion exchange method of ionic impurity etc. removed by impurity.

Pigment (A1) preferable particle size is homogeneous.By carrying out dispersion treatment containing pigment dispersing agent, the dispersible pigment dispersion of the state that pigment disperses in the solution equably can be obtained.

As above-mentioned pigment dispersing agent, the tensio-active agent etc. of such as positively charged ion system, negatively charged ion system, nonionic system, both sexes, Polyester, polyamines system, acrylic acid series etc. can be enumerated.These pigment dispersing agents can be used alone, and also two or more can be combinationally used.As pigment dispersing agent, represent by trade(brand)name, KP (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacture), フローレ Application (common prosperity society chemistry (strain) manufacture), ソ Le スパース (ゼネカ (strain) manufacture), EFKA (manufacture of BASF society), アジスパー (aginomoto Off ァイ Application テ Network ノ (strain) manufacture), Disperbyk (manufacture of PVC ッ Network ケミー society) etc. can be enumerated.

When using pigment dispersing agent, its usage quantity, relative to pigment (A1), is preferably below more than 1 quality % 100 quality %, is more preferably below more than 5 quality % 50 quality %.If the usage quantity of pigment dispersing agent is in above-mentioned scope, there is the tendency obtaining the dispersible pigment dispersion of homogeneous dispersion state.

When tinting material (A) comprises pigment (A1), the content of pigment (A1), relative to the total amount of tinting material (A), preferably below more than 20 quality % 99.5 quality %, more preferably below more than 30 quality % 99 quality %.

< dyestuff (A2) >

As dyestuff (A2), the dyestuffs such as oil-soluble colourant, matching stain, basic dyestuff, substantive dyestuff, mordanting dye, the amine salt of matching stain, the sulfone amide derivative of matching stain can be enumerated, in colour index (TheSocietyofDyersandColourists publication), be such as categorized as dyestuff compound, the middle known dyestuff recorded of dyeing ノート (Se Ran society) can be enumerated.In addition, according to chemical structure, azoic dyestuff, cyanine dyes, triphenhlmethane dye, xanthene dye, phthalocyanine pigment, naphthoquinone dyestuff, quinonimine dye, methine dyes, azomethine dyes, side's acid (ス Network ワリリウ system) dyestuff, acridine dye, styryl dye, coumarine dye, quinoline dye and nitro-dye etc. can be enumerated.In these, preferred organic solvent-soluble dye.

Particularly, C.I. solvent yellow 4,14,15,23,24,38,62,63,68,82,94,98,99,162 can be enumerated;

C.I. solvent red 45,49,125,130,218;

C.I. solvent orange 2,7,11,15,26,56;

C.I. solvent blue 4,5,37,67,70,90;

C.I. solvent green 1, 4, 5, 7, 34, 35 solvent dyes such as C.I. such as grade, C.I. turmeric yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251,

C.I. azogeramine, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 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,

C.I. von Muller's indicator 6,7,8,10,12,26,50,51,52,56,62,63,64,74,75,94,95,107,108,169,173;

C.I. acid violet 6B, 7,9,17,19,30,102;

C.I. Blue VRS, 7,9,15,18,22,29,42,59,60,62,70,72,74,82,83,86,87,90,92,93,100,102,103,104,113,117,120,126,130,131,142,147,151,154,158,161,166,167,168,170,171,184,187,192,199,210,229,234,236,242,243,256,259,267,285,296,315,335;

C.I. the C.I. matching stain such as acid green 1,3,5,9,16,50,58,63,65,80,104,105,106,109,

C.I. direct Huang 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129,136,138,141;

C.I. directly red 79,82,83,84,91,92,96,97,98,99,105,106,107,172,173,176,177,179,181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246,250;

C.I. direct orange 26,34,39,41,46,50,52,56,57,61,64,65,68,70,96,97,106,107;

C.I. direct purple 47,52,54,59,60,65,66,79,80,81,82,84,89,90,93,95,96,103,104;

C.I. direct indigo plant 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 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, 167, 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, C.I. the C.I. substantive dyestuff such as sun green 25,27,31,32,34,37,63,65,66,67,68,69,72,77,79,82,

C.I. DISPERSE YELLOW 54,76 dispersed dye such as C.I. such as grade,

C.I. alkali red 1:1,10;

C.I. alkali blue 1,3,5,7,9,19,24,25,26,28,29,40,41,54,58,59,64,65,66,67,68;

C.I. alkali green 1; Deng C.I. basic dyestuff,

C.I. reactive yellow 2,76,116;

C.I. reactive orange 16;

C.I. reactive red 36; Deng C.I. reactive dyestuffs,

C.I. mordant yellow 5,8,10,16,20,26,30,31,33,42,43,45,56,61,62,65;

C.I. mordant rouge 1,2,4,9,12,14,17,18,19,22,23,24,25,26,27,30,32,33,36,37,38,39,41,43,45,46,48,53,56,63,71,74,85,86,88,90,94,95;

C.I. mordant dyeing orange 3,4,5,8,12,13,14,20,21,23,24,28,29,32,34,35,36,37,42,43,47,48;

C.I. mordant dyeing purple 1,2,4,5,7,14,22,24,30,31,32,37,40,41,44,45,47,48,53,58;

C.I. mordant dyeing indigo plant 1,2,3,7,9,12,13,15,16,19,20,21,22,26,30,31,39,40,41,43,44,49,53,61,74,77,83,84;

C.I. the C.I. mordanting dye such as viridon FF 1,3,4,5,10,15,26,29,33,34,35,41,43,53,

C.I. vat dyes such as C.I. such as Vat green 1 grade, etc.

Wherein, preferred cyan dye, purple dye and orchil.

These dyestuffs suitably can be selected according to the spectrophotometric spectra of required colour filter.These dyestuffs can be used alone, and also two or more may be used.

When comprising dyestuff (A2), its containing ratio, relative to the total amount of tinting material (A), is preferably below more than 0.5 quality % 80 quality %, is more preferably below more than 40 quality % 90 quality %.

The containing ratio of tinting material (A), relative to the total amount that solid is divided, is preferably below more than 5 quality % 70 quality %, is more preferably below more than 5 quality % 60 quality %, more preferably below more than 5 quality % 50 quality %.If the containing ratio of tinting material (A) is in above-mentioned scope, then can obtain required light splitting, depth of shade.

< resin (B) >

Resin (B) is preferably alkali soluble resin (B).Alkali soluble resin (B) (hereinafter sometimes referred to " resin (B) ") is the multipolymer of the structural unit of the monomer (a) comprised from least one selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides.

As such resin (B), following resin [K1] ~ [K6] etc. can be enumerated.

Resin [K1] is selected from the monomer (a) (hereinafter sometimes referred to " (a) ") of at least one in unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides and has the multipolymer of the cyclic ether structure of carbon number 2 ~ 4 and the monomer (b) (hereinafter sometimes referred to " (b) ") of ethylenic unsaturated bond;

Resin [K2] (a) and (b) and can be (but, different with (b) from (a) with the monomer (c) of (a) copolymerization.) multipolymer of (hereinafter sometimes referred to " (c) ");

The multipolymer of resin [K3] (a) and (c);

Resin [K4] makes (b) and (a) resin with the copolymer reaction of (c);

Resin [K5] makes (a) and (b) resin with the copolymer reaction of (c);

The copolymer reaction that resin [K6] makes (a) and (b) and (c) and then the resin that carboxylic acid anhydride is reacted.

As (a), particularly, the such as unsaturated monocarboxylic class such as vinylformic acid, methacrylic acid, β-crotonic acid, o-, m-, p-vinyl benzoic acid can be enumerated;

Toxilic acid, fumaric acid, citraconic acid, methylfumaric acid, methylene-succinic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid, 1, the unsaturated dicarboxylic acid class such as 4-tetrahydrobenzene dicarboxylic acid;

Methyl-5-norbornylene-2, the dicyclo unsaturated compound class containing carboxyl such as 3-dicarboxylic acid, 5-carboxyl dicyclo [2.2.1] hept-2-ene", 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene"s, 5-carboxyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-6-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-6-ethyl dicyclo [2.2.1] hept-2-ene";

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic acid acid anhydride, 4-vinylphthalic acid acid anhydride, 3,4,5,6-Tetra Hydro Phthalic Anhydride, 1,2, the unsaturated dicarboxylic acid class acid anhydrides such as 3,6-Tetra Hydro Phthalic Anhydride, dimethyl tetrahydro Tetra hydro Phthalic anhydride, 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene" acid anhydrides;

Unsaturated list [(methyl) acryloxyalkyl] the ester class of the polycarboxylic acid of mono succinate [2-(methyl) acryloyl-oxyethyl] ester, phthalic acid list [2-(methyl) acryloyl-oxyethyl] ester etc. more than 2 yuan;

The unsaturated esters of acrylic acid etc. containing hydroxyl and carboxyl in same a part that α-(hydroxymethyl) vinylformic acid is such.

In these, from the aspect of copolyreaction, the deliquescent aspect of resin in alkali aqueous solution that obtain, preferred vinylformic acid, methacrylic acid, maleic anhydride etc.

B () refers to the polymerizable compound of cyclic ether structure (such as, being selected from least a kind in oxyethane ring, trimethylene oxide ring and tetrahydrofuran (THF) ring) and the ethylenic unsaturated bond such as with carbon number 2 ~ 4.

B () preferably has the cyclic ether of carbon number 2 ~ 4 and the monomer of (methyl) acryloxy.

Should illustrate, in this specification sheets, " (methyl) vinylformic acid " represents at least a kind that is selected from vinylformic acid and methacrylic acid.The statement of " (methyl) acryl " and " (methyl) acrylate " etc. also has the same meaning.

As (b), the monomer (b1) (hereinafter sometimes referred to " (b1) ") such as with epoxy ethyl and ethylenic unsaturated bond, the monomer (b2) (hereinafter sometimes referred to " (b2) ") with oxetanylmethoxy and ethylenic unsaturated bond, the monomer (b3) (hereinafter sometimes referred to " (b3) ") etc. with tetrahydrofuran base and ethylenic unsaturated bond can be enumerated.

As (b1), the monomer (b1-1) (hereinafter sometimes referred to " (b1-1) ") of the structure that the unsaturated aliphatic hydrocarbon such as with straight-chain or branch's chain is at least partially epoxidized can be enumerated, there is the monomer (b1-2) (hereinafter sometimes referred to " (b1-2) ") of the structure that ester ring type unsaturated hydrocarbons is at least partially epoxidized.

As (b1-1), (methyl) glycidyl acrylate can be enumerated, Beta-methyl glycidyl (methyl) acrylate, β-ethyl glycidyl base (methyl) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl base ether, m-vinylbenzyl glycidyl base ether, p-vinylbenzyl glycidyl base ether, Alpha-Methyl-o-vinylbenzyl glycidyl base ether, Alpha-Methyl-m-vinylbenzyl glycidyl base ether, Alpha-Methyl-p-vinylbenzyl glycidyl base ether, two (glycidoxypropyl methyl) vinylbenzene of 2,3-, two (glycidoxypropyl methyl) vinylbenzene of 2,4-, two (glycidoxypropyl methyl) vinylbenzene of 2,5-, two (glycidoxypropyl methyl) vinylbenzene of 2,6-, 2,3,4-tri-(glycidoxypropyl methyl) vinylbenzene, 2,3,5-tri-(glycidoxypropyl methyl) vinylbenzene, 2,3,6-tri-(glycidoxypropyl methyl) vinylbenzene, 3,4,5-tri-(glycidoxypropyl methyl) vinylbenzene, 2,4,6-tri-(glycidoxypropyl methyl) vinylbenzene etc.

As (b1-2), vinylcyclohexene monoxide, 1,2-epoxy-4-vinyl cyclohexane (such as, セロキサイ De 2000 can be enumerated; (strain) ダイセ Le manufacture), (methyl) vinylformic acid 3,4-epoxycyclohexanecarboxylate (such as, サイ Network ロマー A400; (strain) ダイセ Le manufacture), (methyl) vinylformic acid 3,4-epoxycyclohexanecarboxylate (such as, サイ Network ロマー M100; (strain) ダイセ Le manufactures), the compound that represented by formula (VI) and the compound etc. represented by formula (VII).

[in formula (VI) and formula (VII), R ^aand R ^brepresent the alkyl of hydrogen atom or carbon number 1 ~ 4, hydrogen atom contained in abovementioned alkyl can be optionally substituted by a hydroxyl group.

X ^aand X ^brepresent singly-bound ,-R ^c-, *-R ^c-O-, *-R ^c-S-or *-R ^c-NH-.

R ^crepresent the alkylidene group of carbon number 1 ~ 6.

* the bonding end with O is represented.]

As the alkyl of carbon number 1 ~ 4, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl etc. can be enumerated.

As the alkyl that hydrogen atom is optionally substituted by a hydroxyl group, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyl-1-methylethyl, 2-hydroxyl-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl etc. can be enumerated.

As R ^aand R ^b, preferably, hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl can be enumerated, more preferably, hydrogen atom, methyl can be enumerated.

As the alkylidene group of carbon number 1 ~ 6, methylene radical, ethylidene, propane-1,2-bis-base, propane-1,3-bis-base, butane-Isosorbide-5-Nitrae-two base, pentane-1,5-bis-base, hexane-1,6-bis-base etc. can be enumerated.

As X ^aand X ^b, preferably, singly-bound, methylene radical, ethylidene, *-CH can be enumerated ₂-O-and *-CH ₂cH ₂-O-, more preferably, can enumerate singly-bound, *-CH ₂cH ₂-O-(* represents the bonding end with O).

As the compound represented by formula (VI), can enumerate by any one compound etc. represented of formula (VI-1) ~ formula (VI-15).Wherein, the compound preferably represented by formula (VI-1), formula (VI-3), formula (VI-5), formula (VI-7), formula (VI-9) or formula (VI-11) ~ formula (VI-15), the compound more preferably represented by formula (VI-1), formula (VI-7), formula (VI-9) or formula (VI-15).

As the compound represented by formula (VII), can enumerate by any one compound etc. represented of formula (VII-1) ~ formula (VII-15).Wherein, the compound preferably represented by formula (VII-1), formula (VII-3), formula (VII-5), formula (VII-7), formula (VII-9) or formula (VII-11) ~ formula (VII-15), the compound more preferably represented by formula (VII-1), formula (VII-7), formula (VII-9) or formula (VII-15).

The compound represented by formula (VI) and the compound represented by formula (VII) can use separately individually, also the compound represented by formula (VI) and the compound represented by formula (VII) can be used.When by them also, the compound represented by formula (VI) and the compound that represented by formula (VII) containing ratio with molar basis, be preferably 5:95 ~ 95:5, be more preferably 10:90 ~ 90:10, more preferably 20:80 ~ 80:20.

As (b2), more preferably there is the monomer of oxetanylmethoxy and (methyl) acryloxy.As (b2), 3-methyl-3-methacryloxymethyl trimethylene oxide, 3-methyl-3-acryloyloxymethyl trimethylene oxide, 3-ethyl-3-methacryloxymethyl trimethylene oxide, 3-ethyl-3-acryloyloxymethyl trimethylene oxide, 3-methyl-3-methacryloxyethyl trimethylene oxide, 3-methyl-3-acryloyl-oxyethyl trimethylene oxide, 3-ethyl-3-methacryloxyethyl trimethylene oxide, 3-ethyl-3-acryloyl-oxyethyl trimethylene oxide etc. can be enumerated.

As (b3), more preferably there is the monomer of tetrahydrofuran base and (methyl) acryloxy.As (b3), particularly, tetrahydrofurfuryl acrylate (such as, PVC スコート V#150, Osaka Organic Chemical Industry (strain) manufacture), tetrahydrofurfuryl methacrylate etc. can be enumerated.

As (b), can improve further the colour filter obtained thermotolerance, chemicals-resistant etc. reliability in, be preferably (b1).And then, colored curable resin composition excellent storage stability in, more preferably (b1-2).

As (c), such as (methyl) methyl acrylate can be enumerated, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) dodecylacrylate, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) vinylformic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid 2-methyl cyclohexyl, (methyl) vinylformic acid three ring [5.2.1.0 ^2,6] decane-8-base ester (in this technical field, as trivial name, is called " (methyl) vinylformic acid dicyclo pentyl ester ".In addition, be sometimes referred to as " (methyl) vinylformic acid three ring ester in the last of the ten Heavenly stems ".), (methyl) vinylformic acid three ring [5.2.1.0 ^2,6] decene-8-base ester (in this technical field, as trivial name, is called " (methyl) vinylformic acid dicyclopentenyloxyethyl methacrylate ".), (methyl) esters of acrylic acid such as (methyl) vinylformic acid dicyclo pentyloxy ethyl ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid diamantane ester, (methyl) allyl acrylate, (methyl) propargylacrylate, (methyl) phenyl acrylate, (methyl) vinylformic acid naphthalene ester, (methyl) benzyl acrylate;

(methyl) esters of acrylic acid containing hydroxyl such as (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester;

The dicarboxylic diesters such as ethyl maleate, DEF, diethyl itaconate;

Dicyclo [2.2.1] hept-2-ene", 5-methyl bicycle [2.2.1] hept-2-ene", 5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxyl dicyclo [2.2.1] hept-2-ene", 5-hydroxymethyl dicyclo [2.2.1] hept-2-ene", 5-(2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5-methoxyl group dicyclo [2.2.1] hept-2-ene", 5-oxyethyl group dicyclo [2.2.1] hept-2-ene", 5,6-dihydroxyl dicyclo [2.2.1] hept-2-ene", 5,6-bis-(hydroxymethyl) dicyclo [2.2.1] hept-2-ene", 5,6-bis-(2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5,6-dimethoxy dicyclo [2.2.1] hept-2-ene", 5,6-diethoxy dicyclo [2.2.1] hept-2-ene", 5-hydroxy-5-methyl base dicyclo [2.2.1] hept-2-ene", 5-hydroxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxymethyl-5-methyl bicycle [2.2.1] hept-2-ene", uncle 5--butoxy carbonyl dicyclo [2.2.1] hept-2-ene", 5-cyclohexyloxy carbonyl dicyclo [2.2.1] hept-2-ene", 5-phenyloxycarbonyl dicyclo [2.2.1] hept-2-ene", two (uncle-butoxy carbonyl) dicyclo [2.2.1] hept-2-ene" of 5,6-, the dicyclo unsaturated compound classes such as two (cyclohexyloxy carbonyl) dicyclo [2.2.1] hept-2-ene"s of 5,6-,

The di carbonyl imide derivatives class such as N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, N-succinimido-3-maleimidobenzoyl salt, N-succinimido-4-maleimidobutyrate salt, N-succinimido-6-maleimidohexanoic acid salt, N-succinimido-3-maleimidopropionic acid salt, N-(9-acridyl) maleimide;

Vinylbenzene, alpha-methyl styrene, m-vinyl toluene, p-methylstyrene, Vinyl toluene, p-methoxystyrene, vinyl cyanide, methacrylonitrile, vinylchlorid, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1,3-divinyl, isoprene, 2,3-dimethyl-1,3-butadiene etc.

In these, from the aspect of copolyreaction and thermotolerance, optimization styrene, Vinyl toluene, (methyl) benzyl acrylate, (methyl) vinylformic acid three ring [5.2.1.0 ^2,6] decane-8-base ester, N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, dicyclo [2.2.1] hept-2-ene".

In resin [K1], from the ratio of the structural unit of each monomer, in the entire infrastructure unit forming resin [K1], be preferably:

Structural unit from (a): 2 ~ 60 % by mole

Structural unit from (b): 40 ~ 98 % by mole,

Be more preferably:

Structural unit from (a): 10 ~ 50 % by mole

Structural unit from (b): 50 ~ 90 % by mole.

If the ratio of the structural unit of resin [K1] is in above-mentioned scope, there is the storage stability of colored curable resin composition, resulting visualization when forming colored pattern and the tendency of the excellent solvent resistance of colour filter that obtains.

The citing document recorded in the method that resin [K1] can be recorded in such as reference " laboratory method of Polymer Synthesizing " (large Jin Longhangzhu press (strain) chemistry is with people's the 1st edition the 1st printing distribution on March 1st, 1972) and the document manufactures.

Particularly, can enumerate by the specified amount of (a) and (b), polymerization starter and solvent etc. are loaded in reaction vessel, such as, with nitrogen, oxygen be replaced, thus form deoxidizing atmosphere, the method heating while stirring and be incubated.Should illustrate, polymerization starter and solvent etc. are as used herein not particularly limited, normally used material in this field can be used.As polymerization starter, such as azo-compound (2 can be enumerated, 2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2,4-methyl pentane nitrile) etc.), organo-peroxide (benzoyl peroxide etc.), as solvent, as long as each monomer is dissolved, as the solvent (E) of colored curable resin composition of the present invention, solvent described later etc. can be enumerated.

Should illustrate, for the multipolymer obtained, reacted solution can be used as former state, also can use solution that is concentrated or dilution, also can use the product that methods such as adopting redeposition is taken out as solid (powder).Especially, during this polymerization, as solvent, solvent contained in the colored curable resin composition of the application of the invention, as former state reacted solution can be used in the modulation of colored curable resin composition of the present invention, therefore, it is possible to make the manufacturing process of colored curable resin composition of the present invention simplify.

In resin [K2], from the ratio of the structural unit of each monomer, in the entire infrastructure unit forming resin [K2], be preferably:

Structural unit from (a): 2 ~ 45 % by mole

Structural unit from (b): 2 ~ 95 % by mole

Structural unit from (c): 1 ~ 65 % by mole,

Be more preferably:

Structural unit from (a): 5 ~ 40 % by mole

Structural unit from (b): 5 ~ 80 % by mole

Structural unit from (c): 5 ~ 60 % by mole.

If the ratio of the structural unit of resin [K2] is in above-mentioned scope, there is the storage stability of colored curable resin composition, the tendency of the solvent resistance of the resulting visualization and colour filter that obtains when forming colored pattern, thermotolerance and mechanical strength.

Manufacture in the same manner as the method that resin [K2] can such as be recorded with the manufacture method as resin [K1].

In resin [K3], from the ratio of the structural unit of each monomer, in the entire infrastructure unit forming resin [K3], be preferably:

Structural unit from (a): 2 ~ 60 % by mole

Structural unit from (c): 40 ~ 98 % by mole,

Be more preferably:

Structural unit from (a): 10 ~ 50 % by mole

Structural unit from (c): 50 ~ 90 % by mole.

Manufacture in the same manner as the method that resin [K3] can such as be recorded with the manufacture method as resin [K1].

Resin [K4] can by obtaining the multipolymer of (a) and (c), the carboxylic acid that cyclic ether and (a) of the carbon number 2 ~ 4 that (b) is had have and/or carboxylic acid anhydride addition and manufacture.

First, the multipolymer of (a) and (c) is manufactured in the same manner as the method can recorded with the manufacture method as resin [K1].Under this situation, the ratio from the structural unit of each monomer is preferably the ratio identical with the ratio enumerated in resin [K3].

Next, the carboxylic acid from (a) in the cyclic ether of the carbon number 2 ~ 4 (b) being had and above-mentioned multipolymer and/or a part for carboxylic acid anhydride are reacted.

Then the manufacture of the multipolymer of (a) and (c), atmosphere in flask is replaced into air by nitrogen, the catalysts (such as three (dimethylaminomethyl) phenol etc.) and stopper (such as quinhydrones etc.) etc. of (b), carboxylic acid or carboxylic acid anhydride and cyclic ether are loaded in flask, such as, react 1 ~ 10 hour at 60 ~ 130 DEG C, thus resin [K4] can be manufactured.

B the usage quantity of (), relative to (a) 100 moles, preferably 5 ~ 80 moles, is more preferably 10 ~ 75 moles.By becoming this scope, there is the storage stability of colored curable resin composition, the balance of the solvent resistance of the resulting visualization and pattern that obtains when forming pattern, thermotolerance, physical strength and light sensitivity becomes good tendency.Because the reactivity of cyclic ether is high, unreacted (b) is not easily remaining, therefore as (b) that be used for resin [K4], and preferably (b1), more preferably (b1-1).

The usage quantity of above-mentioned catalysts, relative to total amount 100 mass parts of (a), (b) and (c), preferably 0.001 ~ 5 mass parts.The usage quantity of above-mentioned stopper, relative to the total amount of 100 mass parts (a), (b) and (c), preferably 0.001 ~ 5 mass parts.

For reaction conditionss such as feed process, temperature of reaction and times, can consider producing apparatus, polymerization produce thermal discharge etc. suitably adjust.Further, in the same manner as polymerizing condition, the thermal discharge etc. of producing apparatus, polymerization generation can be considered, suitably adjust feed process, temperature of reaction.

For resin [K5], as the first stage, in the same manner as the manufacture method of above-mentioned resin [K1], obtain the multipolymer of (b) and (c).As described above, the multipolymer obtained can use reacted solution as former state, also can use solution that is concentrated or dilution, also can use the product that methods such as adopting redeposition is taken out as solid (powder).

From the ratio of the structural unit of (b) and (c), the total mole number of the entire infrastructure unit of the multipolymer above-mentioned relative to formation, is separately preferably

Structural unit from (b): 5 ~ 95 % by mole

Structural unit from (c): 5 ~ 95 % by mole,

Be more preferably

Structural unit from (b): 10 ~ 90 % by mole

Structural unit from (c): 10 ~ 90 % by mole.

And then, under the condition same with the manufacture method of resin [K4], the cyclic ether from (b) that the multipolymer of the carboxylic acid had by making (a) or carboxylic acid anhydride and (b) and (c) has reacts, thus can obtain resin [K5].

With the usage quantity of (a) of above-mentioned copolymer reaction, relative to (b) 100 moles, preferably 5 ~ 80 moles.Because the reactivity of cyclic ether is high, unreacted (b) is not easily remaining, therefore as (b) that be used for resin [K5], and preferably (b1), more preferably (b1-1).

Resin [K6] is the resin making carboxylic acid anhydride and resin [K5] react further.

Make the hydroxyl reaction that carboxylic acid anhydride produces with the reaction by cyclic ether and carboxylic acid or carboxylic acid anhydride.

As carboxylic acid anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic acid acid anhydride, 4-vinylphthalic acid acid anhydride, 3 can be enumerated, 4,5,6-Tetra Hydro Phthalic Anhydride, 1,2,3,6-Tetra Hydro Phthalic Anhydride, dimethyl tetrahydro Tetra hydro Phthalic anhydride, 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene" acid anhydrides etc.The usage quantity of carboxylic acid anhydride, relative to the usage quantity of 1 mole (a), preferably 0.5 ~ 1 mole.

As resin (B), particularly, (methyl) vinylformic acid 3,4-epoxycyclohexanecarboxylate/(methyl) acrylic copolymer, (methyl) vinylformic acid 3,4-epoxy three ring [5.2.1.0 can be enumerated ^2.6] last of the ten Heavenly stems resin [K1] such as ester/(methyl) acrylic copolymer, (methyl) glycidyl acrylate/(methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) glycidyl acrylate/vinylbenzene/(methyl) acrylic copolymer, (methyl) vinylformic acid 3,4-epoxy three ring [5.2.1.0 ^2.6] last of the ten Heavenly stems ester/(methyl) vinylformic acid/N-N-cyclohexylmaleimide multipolymer, (methyl) vinylformic acid 3,4-epoxy three ring [5.2.1.0 ^2.6] last of the ten Heavenly stems ester/(methyl) vinylformic acid/vinyl toluene copolymer, the resin [K2] such as 3-methyl-3-(methyl) acryloyloxymethyl trimethylene oxide/(methyl) vinylformic acid/styrol copolymer, the resins [K3] such as (methyl) benzyl acrylate/(methyl) acrylic copolymer, vinylbenzene/(methyl) acrylic copolymer, (methyl) benzyl acrylate/(methyl) vinylformic acid three ring ester in the last of the ten Heavenly stems/(methyl) acrylic copolymer, make the resin of (methyl) glycidyl acrylate and (methyl) benzyl acrylate/(methyl) acrylic copolymer addition, make the resin of (methyl) glycidyl acrylate and (methyl) vinylformic acid three ring ester/vinylbenzene in the last of the ten Heavenly stems/(methyl) acrylic copolymer addition, make the resins [K4] such as the resin of (methyl) glycidyl acrylate and (methyl) vinylformic acid three ring ester in the last of the ten Heavenly stems/(methyl) benzyl acrylate/(methyl) acrylic copolymer addition, make the resin of the copolymer reaction of (methyl) vinylformic acid and (methyl) vinylformic acid three ring ester in the last of the ten Heavenly stems/(methyl) glycidyl acrylate, make the resins [K5] such as the resin of the copolymer reaction of (methyl) vinylformic acid and (methyl) vinylformic acid three ring ester/vinylbenzene in the last of the ten Heavenly stems/(methyl) glycidyl acrylate, the resins [K6] etc. such as the resin that (methyl) vinylformic acid is reacted with Tetra Hydro Phthalic Anhydride further with the resin of the copolymer reaction of (methyl) vinylformic acid three ring ester in the last of the ten Heavenly stems/(methyl) glycidyl acrylate.

Resin (B) is preferably selected from the one in resin [K1], resin [K2] and resin [K3], is more preferably the one be selected from resin [K2] and resin [K3].If be these resins, then the resulting visualization excellence of colored curable resin composition.

From the view point of the adaptation of colored pattern and substrate, more preferably resin [K2].

The weight-average molecular weight of the polystyrene conversion of resin (B) is preferably 3,000 ~ 100,000, is more preferably 5,000 ~ 50,000, and more preferably 5,000 ~ 30,000.If molecular weight is in above-mentioned scope, then have that hardness of film improves, residual film ratio also high, a unexposed portion tendency that the resolution of the favorable solubility of image-developing liquor, colored pattern is improved.

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

The acid number of resin (B) is preferably 50 ~ 170mg-KOH/g, is more preferably 60 ~ 150mg-KOH/g, more preferably 70 ~ 135mg-KOH/g.At this, acid number is the value as measuring with the amount (mg) of the potassium hydroxide needed for resin (B) in 1g, such as, can obtain by using potassium hydroxide aqueous solution carry out titration.

The content of resin (B), relative to the total amount that solid is divided, is preferably 7 ~ 65 quality %, is more preferably 13 ~ 60 quality %, more preferably 17 ~ 55 quality %.If the content of resin (B), in above-mentioned scope, can form colored pattern, and there is the resolution of colored pattern and the tendency of residual film ratio raising.

< polymerizable compound (C) >

Polymerizable compound (C) is the compound that can utilize living radical and/or the acid polymerization produced by polymerization starter (D), the compound etc. of the ethylenic unsaturated bond such as with polymerizability can be enumerated, be preferably (methyl) acrylic compound.

As the polymerizable compound with 1 ethylenic unsaturated bond, such as nonylphenol acrylate phenyl carbitol ester, vinylformic acid 2-hydroxyl-3-phenoxy propyl ester, vinylformic acid 2-ethylhexyl carbitol ester, vinylformic acid 2-hydroxy methacrylate, NVP etc. and above-mentioned (a), (b) and (c) can be enumerated.

As the polymerizable compound with 2 ethylenic unsaturated bonds, two (acryloyl-oxyethyl) ether, 3-methyl pentanediol two (methyl) acrylate etc. of such as 1,6-hexylene glycol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triglycol two (methyl) acrylate, dihydroxyphenyl propane can be enumerated.

Wherein, polymerizable compound (C) preferably has the polymerizable compound of the ethylenic unsaturated bond of more than 3.As such polymerizable compound, such as trimethylolpropane tris (methyl) acrylate can be enumerated, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, tripentaerythritol eight (methyl) acrylate, tripentaerythritol seven (methyl) acrylate, tetrapentaerythritol ten (methyl) acrylate, tetrapentaerythritol nine (methyl) acrylate, three (2-(methyl) acryloyl-oxyethyl) isocyanuric acid ester, glycol-modified tetramethylolmethane four (methyl) acrylate, glycol-modified Dipentaerythritol six (methyl) acrylate, propylene glycol modified tetramethylolmethane four (methyl) acrylate, propylene glycol modified Dipentaerythritol six (methyl) acrylate, caprolactone modification tetramethylolmethane four (methyl) acrylate, caprolactone modification Dipentaerythritol six (methyl) acrylate etc., wherein, preferred Dipentaerythritol five (methyl) acrylate and Dipentaerythritol six (methyl) acrylate.

The weight-average molecular weight of polymerizable compound (C) is preferably more than 150 2, less than 900, is more preferably 250 ~ 1, less than 500.

The content of polymerizable compound (C), relative to the total amount that solid is divided, is preferably 7 ~ 65 quality %, is more preferably 13 ~ 60 quality %, more preferably 17 ~ 55 quality %.

In addition, the content ratio [resin (B): polymerizable compound (C)] of resin (B) and polymerizable compound (C) is in quality criteria, be preferably 20:80 ~ 80:20, be more preferably 35:65 ~ 80:20.

If the content of polymerizable compound (C) is in above-mentioned scope, also exist colored pattern formed time residual film ratio and colour filter chemicals-resistant improve tendency.

< polymerization starter (D) >

Polymerization starter (D) as long as can utilize the effect of light, heat and produce living radical, acid etc., the compound of initiated polymerization, is then not particularly limited, can uses known polymerization starter.

As polymerization starter (D), O-acyl group oxime compound, alkyl phenyl ketone compound, united imidazole, triaizine compounds and acylphosphine oxide compound etc. can be enumerated.

Above-mentioned O-acyl group oxime compound is the compound with the part-structure represented by formula (d1).Below, * represents bonding end.

As above-mentioned O-acyl group oxime compound, such as N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) butane-1-ketone-2-imines can be enumerated, N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) octane-1-ketone-2-imines, N-benzoyloxy-1-(4-Phenylsulfanyl phenyl)-3-cyclopentyl propane-1-ketone-2-imines, N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-{2-methyl-4-(3, 3-dimethyl-2, 4-dioxolyl methoxyl group) benzoyl }-9H-carbazole-3-base] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-3-cyclopentyl propane-1-imines, N-benzoyloxy-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-3-cyclopentyl propane-1-ketone-2-imines etc.The commercially available product such as IrgacureOXE01, OXE02 (above for BASF society manufactures), N-1919 (manufacture of ADEKA society) can be used.Wherein, O-acyl group oxime compound is preferably selected from least a kind in N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) butane-1-ketone-2-imines, N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) octane-1-ketone-2-imines and N-benzoyloxy-1-(4-Phenylsulfanyl phenyl)-3-cyclopentyl propane-1-ketone-2-imines, more preferably N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) octane-1-ketone-2-imines.

Abovementioned alkyl phenyl ketone compound is the compound such as with the part-structure represented by formula (d2) or the part-structure represented by formula (d3).In these part-structures, phenyl ring can have substituting group.

As the compound with the part-structure represented by formula (d2), such as 2-methyl-2-morpholino-1-(4-methylsulfanyl phenyl) propane-1-ketone, 2-dimethylamino-1-(4-morphlinophenyl)-2-benzyl butane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl] butane-1-ketone etc. can be enumerated.Can use Irgacure369,907, the commercially available product of 379 (above for BASF society manufacture) etc.

As the compound with the part-structure represented by formula (d3), oligopolymer, α, α-diethoxy acetophenone, the benzil dimethyl ketal etc. of such as 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl] propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-pseudoallyl phenyl) propane-1-ketone can be enumerated.

In light sensitivity, as alkyl phenyl ketone compound, preferably there is the compound of the part-structure represented by formula (d2).

The compound of above-mentioned united imidazole such as being represented by formula (d5).

[in formula (d5), R ¹³~ R ¹⁸expression can have the aryl of substituent carbon number 6 ~ 10.]

As the aryl of carbon number 6 ~ 10, such as phenyl, tolyl, xylyl, ethylphenyl and naphthyl etc. can be enumerated, be preferably phenyl.

Alternatively base, can enumerate the alkoxyl group etc. of such as halogen atom, carbon number 1 ~ 4.As halogen atom, such as fluorine atom, chlorine atom, bromine atoms, atomic iodine etc. can be enumerated, be preferably chlorine atom.As the alkoxyl group of carbon number 1 ~ 4, such as methoxyl group, oxyethyl group, propoxy-, butoxy etc. can be enumerated, be preferably methoxyl group.

As united imidazole, such as 2 can be enumerated, 2 '-bis-(2-chloro-phenyl-)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2,3-dichlorophenyl)-4,4 ' 5,5 '-tetraphenyl bisglyoxaline is (for example, referring to Unexamined Patent 6-75372 publication, Unexamined Patent 6-75373 publication etc.), 2,2 '-bis-(2-chloro-phenyl-)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2-chloro-phenyl-)-4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxaline, 2,2 '-bis-(2-chloro-phenyl-)-4,4 ', 5,5 '-four (dialkoxy phenyl) bisglyoxaline, 2,2 '-bis-(2-chloro-phenyl-)-4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxaline is (for example, referring to examined patent publication 48-38403 publication, JP 62-174204 publication etc.), 4,4 ', 5, the imidazolium compounds that the phenyl of 5 '-position is replaced by carbalkoxy is (for example, referring to Unexamined Patent 7-10913 publication etc.) etc.Wherein, the compound preferably represented by following formula and their mixture.

As above-mentioned triaizine compounds, such as 2 can be enumerated, two (the trichloromethyl)-6-(4-p-methoxy-phenyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl group naphthyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-piperonyl-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(5-methyl furan-2-base) vinyl]-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(furans-2-base) vinyl]-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-1 of 4-, 3, 5-triazine, 2, two (trichloromethyl)-6-[2-(3 of 4-, 4-Dimethoxyphenyl) vinyl]-1, 3, 5-triazine etc.

As above-mentioned acylphosphine oxide compound, TMDPO etc. can be enumerated.

And then, as polymerization starter (D), the bitter almond oil camphor compounds such as bitter almond oil camphor, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether can be enumerated; Benzophenone, o-benzoyl methyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 3,3 ', 4,4 '-four (tert-butyl peroxide carbonyl) benzophenone, 2, the benzophenone cpds such as 4,6-tri-methyl benzophenone; The naphtoquinone compounds such as 9,10-phenanthrenequione, 2-ethyl-anthraquinone, camphorquinone; 10-butyl-2-chloro-acridine ketone, benzil, phenylglyoxalates methyl esters, two cyclopentadiene titanium compounds etc.

These preferably cause auxiliary agent (D1) (particularly amine) combinationally use with described later polymerizations.

Polymerization starter (D) preferably comprises the polymerization starter of at least one be selected from alkyl phenyl ketone compound, triaizine compounds, acylphosphine oxide compound, O-acyl group oxime compound and united imidazole; more preferably, be the polymerization starter comprising O-acyl group oxime compound.

The content of polymerization starter (D), relative to total amount 100 mass parts of resin (B) and polymerizable compound (C), is preferably 0.1 ~ 40 mass parts, is more preferably 1 ~ 30 mass parts.

< polymerization causes auxiliary agent (D1) >

It is the compound or the sensitizing agent that have caused the polymerization of the polymerizable compound of polymerization for promotion polymerization starter that polymerization causes auxiliary agent (D1).When comprising polymerization initiation auxiliary agent (D1), usual and polymerization starter (D) combinationally uses.

Cause auxiliary agent (D1) as polymerization, amine compound, alkoxy anthracene compound, thioxanthone compounds and carboxylic acid cpd etc. can be enumerated.

As above-mentioned amine compound, trolamine can be enumerated, methyldiethanolamine, tri-isopropanolamine, 4-dimethylaminobenzoic acid methyl esters, EDMAB, 4-dimethylaminobenzoic acid isopentyl ester, phenylformic acid 2-dimethylamino ethyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethyl-p-toluidine, 4, 4 '-bis-(dimethylamino) benzophenone (common name Michler's keton), 4, 4 '-bis-(diethylamino) benzophenone, 4, 4 '-bis-(ethylmethylamino) benzophenone etc., wherein, preferably 4, 4 '-bis-(diethylamino) benzophenone.The commercially available product of EAB-F (hodogaya chemical industry (strain) manufacture) etc. can be used.

As above-mentioned alkoxy anthracene compound, 9,10-dimethoxy anthracene, EDMO, 9,10-diethoxy anthracenes, 2-ethyl-9,10-diethoxy anthracene, 9,10-dibutoxy anthracenes, 2-ethyl-9,10-dibutoxy anthracene etc. can be enumerated.

As above-mentioned thioxanthone compounds, ITX, ITX, 2,4-diethyl thioxanthones, 2,4-bis-clopenthixal ketones, the chloro-4-propoxythioxanthone of 1-etc. can be enumerated.

As above-mentioned carboxylic acid cpd, Phenylsulfanyl acetic acid, methyl phefzylsulfanyl acetic acid, ethylphenyl sulfanyl acetic acid, methylethyl phenyl sulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, p-methoxy-phenyl sulfanyl acetic acid, Dimethoxyphenyl sulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenyl sulfanyl acetic acid, N-phenylglycine, phenoxyethanoic acid, naphthalene sulfenyl acetic acid, N-naphthyl glycine, naphthyloxy acetic acid etc. can be enumerated.

When using these polymerizations to cause auxiliary agent (D1), its content, relative to total amount 100 mass parts of resin (B) and polymerizable compound (C), preferably 0.1 ~ 30 mass parts, is more preferably 1 ~ 20 mass parts.If polymerization causes the amount of auxiliary agent (D1) within the scope of this, then can form colored pattern with ISO further, the productivity of colour filter is tended to improve.

< solvent (E) >

Solvent (E) is not particularly limited, normally used solvent in this field can be used.Such as, ester solvent (comprising-COO-in molecule, not containing the solvent of-O-), ether solvents (comprising-O-in molecule, not containing the solvent of-COO-), ether-ether solvent (comprising the solvent of-COO-and-O-in molecule), ketone solvent (comprising-CO-in molecule, not containing the solvent of-COO-), alcoholic solvent (comprising OH in molecule, not containing the solvent of-O-,-CO-and-COO-), aromatic hydrocarbon solvents, amide solvent, dimethyl sulfoxide (DMSO) etc. can be enumerated.

As ester solvent, methyl lactate, ethyl lactate, n-Butyl lactate, 2-hydroxy-methyl isobutyl acid, vinyl acetic monomer, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, Propyl pyruvate, methyl acetoacetate, methyl aceto acetate, adnoral acetate, gamma-butyrolactone etc. can be enumerated.

As ether solvents, ethylene glycol monomethyl ether can be enumerated, ethylene glycol monomethyl ether, ethylene glycol list propyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, carbiphene, diethylene glycol monobutyl ehter, propylene glycol monomethyl ether, propylene glycol monoethyl, propylene glycol monopropyl ether, glycol monobutyl ether, 3-methoxyl group-n-butyl alcohol, 3-methoxyl group-3-methyl butanol, tetrahydrofuran (THF), tetrahydropyrans, 1, 4-diox, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, glycol ether methyl ethyl ether, glycol ether dipropyl ether, diethylene glycol dibutyl ether, phenylmethylether, phenyl ethyl ether, methyl anisole etc.

As ether-ether solvent, Methoxy Methyl Acetate can be enumerated, Methoxy acetic acid ethyl ester, Methoxy acetic acid butyl ester, oxyethyl group ritalin, oxyethyl group vinyl acetic monomer, 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, 2-methoxy methyl propionate, 2-methoxypropionate, 2-methoxy propyl propyl propionate, 2-ethoxypropanoate, 2-ethoxyl ethyl propionate, 2-methoxyl group-2 Methylpropionic acid methyl esters, 2-oxyethyl group-2 Methylpropionic acid ethyl ester, 3-methoxybutyl acetic ester, 3-methyl-3-methoxybutyl acetic ester, propylene glycol monomethyl ether, propylene glycol monoethyl acetic ester, propylene glycol monopropyl ether acetic ester, ethylene glycol monomethyl ether acetic acid ester, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ehter acetic ester, dipropylene glycol methyl ether acetic ester etc.

As ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, dipropyl ketone, 4-methyl-2 pentanone, cyclopentanone, pimelinketone, isophorone etc. can be enumerated.

As alcoholic solvent, methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, hexalin, ethylene glycol, propylene glycol, glycerine etc. can be enumerated.

As aromatic hydrocarbon solvents, benzene,toluene,xylene, 1，3，5-trimethyl-benzene etc. can be enumerated.

As amide solvent, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone etc. can be enumerated.

These solvents can be used alone, and also two or more may be used.

Wherein, preferred propylene glycol monomethyl ether, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxyl ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, carbiphene, 3-methoxybutyl acetic ester, 3-methoxyl group-n-butyl alcohol, 4-hydroxy-4-methyl-2-pentanone, N, dinethylformamide, N-Methyl pyrrolidone etc., more preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetic ester, ethyl lactate, 3-methoxybutyl acetic ester, 3-methoxyl group-n-butyl alcohol, 3-ethoxyl ethyl propionate, N-Methyl pyrrolidone.

The content of solvent (E), relative to the total amount of colored curable resin composition, is preferably 70 ~ 95 quality %, is more preferably 75 ~ 92 quality %.In other words, the solid of colored curable resin composition divides preferably 5 ~ 30 quality %, is more preferably 8 ~ 25 quality %.

If the content of solvent (E) is in above-mentioned scope, flatness during coating becomes good, and when defining colour filter because depth of shade does not have deficiency, therefore there is the tendency that display characteristic becomes good.

< flow agent (F) >

As flow agent (F), silicone based surfactants, fluorine system tensio-active agent can be enumerated and there is the silicone based surfactants etc. of fluorine atom.These can have polymerizable group at side chain.

As silicone based surfactants, the tensio-active agent etc. with siloxane bond can be set forth in molecule.Particularly, トーレシリコー Application DC3PA can be enumerated, トーレシリコー Application SH7PA, トーレシリコー Application DC11PA, トーレシリコー Application SH21PA, トーレシリコー Application SH28PA, トーレシリコー Application SH29PA, トーレシリコー Application SH30PA, トーレシリコー Application SH8400 (trade(brand)name: eastern レダウコーニ Application グ (strain) manufactures), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacture), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufacture of モメ Application ティ Block パフォーマ Application スマテリア Le ズジャパ Application contract commercial firm) etc.

As above-mentioned fluorine system tensio-active agent, the tensio-active agent etc. with fluorocarbon chain can be set forth in molecule.Particularly, Off ロラー De (registered trademark) FC430 can be enumerated, Off ロラー De FC431 (Sumitomo スリーエ system (strain) manufacture), メガ Off ァッ Network (registered trademark) F142D, メガ Off ァッ Network F171, メガ Off ァッ Network F172, メガ Off ァッ Network F173, メガ Off ァッ Network F177, メガ Off ァッ Network F183, メガ Off ァッ Network F554, メガ Off ァッ Network R30, メガ Off ァッ Network RS-718-K (DIC (strain) manufacture), エ Off トップ (registered trademark) EF301, エ Off トップ EF303, エ Off トップ EF351, エ Off トップ EF352 (Mitsubishi マテリア Le electronics changes into (strain) and manufactures), サー Off ロ Application (registered trademark) S381, サー Off ロ Application S382, サー Off ロ Application SC101, サー Off ロ Application SC105 (Asahi Glass (strain) manufacture) and E5844 (manufacture of (strain) ダイキ Application Off ァイ Application ケミカ Le institute) etc.

As the above-mentioned silicone based surfactants with fluorine atom, the tensio-active agent etc. with siloxane bond and fluorocarbon chain can be set forth in molecule.Particularly, メガ Off ァッ Network (registered trademark) R08, メガ Off ァッ Network BL20, メガ Off ァッ Network F475, メガ Off ァッ Network F477 and メガ Off ァッ Network F443 (DIC (strain) manufacture) etc. can be enumerated.

When containing flow agent (F), its content, relative to the total amount of colored curable resin composition, be preferably below more than 0.001 quality % 0.2 quality %, be more preferably below more than 0.002 quality % 0.1 quality %, more preferably below more than 0.005 quality % 0.07 quality %.If the content of flow agent (F) is in above-mentioned scope, then the flatness of colour filter can be made to become good.

Other compositions of < >

Colored curable resin composition of the present invention, as required, can comprise known additive in these technical fields such as weighting agent, other macromolecular compound, closely sealed promotor, antioxidant, photostabilizer, chain-transfer agent.

The manufacture method > of < colored curable resin composition

Colored curable resin composition of the present invention, can by will such as tinting material (A), resin (B), polymerizable compound (C), polymerization starter (D) and solvent (E), use as required, flow agent (F), polymerization cause auxiliary agent (D1) and other compositions mix and modulate.

For the pigment of situation comprising pigment (A1), preferably mix with part or all of solvent (E) in advance, use ball mill etc. to make it disperse until the median size of pigment becomes about less than 0.2 μm.Now, part or all of above-mentioned pigment dispersing agent, resin (B) can be coordinated as required.By mixing remaining composition to become the concentration of regulation in the dispersible pigment dispersion obtained like this, the colored curable resin composition of target can be modulated.

For compound (I), be preferably dissolved in advance in part or all of solvent (E) and modulate solution.Preferably with the strainer in about 0.01 ~ 1 μm, aperture, above-mentioned solution is filtered.

Preferably with the strainer in about 0.01 ~ 10 μm, aperture, mixed colored curable resin composition is filtered.

The manufacture method > of < colour filter

As the method being manufactured colored pattern by colored curable resin composition of the present invention, photolithography, ink jet method, print process etc. can be enumerated.Wherein, preferred light lithography.Photolithography is that above-mentioned colored curable resin composition is coated substrate, dry and form coloring compositions nitride layer, via photomask by above-mentioned coloring compositions nitride layer exposure the method for video picture.In photolithography, by inapplicable photomask and/or not video picture when exposing, thus the painted film of the cured article as above-mentioned coloring compositions nitride layer can be formed.The colored pattern of such formation, painted film are colour filter of the present invention.

The thickness of the colour filter made is not particularly limited, according to the suitably adjustment such as object, purposes, such as, can be 0.1 ~ 30 μm, be preferably 0.1 ~ 20 μm, be more preferably 0.5 ~ 6 μm.

As substrate, silica glass, pyrex, alumina silicate glass, effects on surface can be used to have carried out the resin board of the sheet glass, polycarbonate, polymethylmethacrylate, polyethylene terephthalate etc. of the soda-lime glass of silica-coating etc., silicon, on aforesaid substrate, define the product of aluminium, silver, silver/copper/palldium alloy film etc.These substrates can form other color-filter layer, resin layer, transistor, circuit etc.

Adopt the formation of photolithographic each color pixel can carry out under known or usual device, condition.Such as, can as described belowly make.

First, colored curable resin composition is coated on substrate, by heat drying (prebake) and/or drying under reduced pressure, thus the volatile component removings such as solvent is dry, obtain level and smooth coloring compositions nitride layer.

As coating process, spin-coating method, slot coated method, slit and method of spin coating etc. can be enumerated.

Carry out the temperature preferably 30 ~ 120 DEG C during heat drying, more preferably 50 ~ 110 DEG C.In addition, as heat-up time, be preferably 10 seconds ~ 60 minutes, be more preferably 30 seconds ~ 30 minutes.

When carrying out drying under reduced pressure, preferably carry out under the pressure of 50 ~ 150Pa, under the temperature range of 20 ~ 25 DEG C.

Thickness facing to colour cell compound layer is not particularly limited, and suitably can select according to the thickness of the colour filter of target.

Next, for coloring compositions nitride layer, expose via the photomask of the colored pattern for the formation of target.Pattern on above-mentioned photomask is not particularly limited, the pattern conformed to the purposes of target can be used.

As the light source for exposing, preferably produce the light source of the light of the wavelength of 250 ~ 450nm.Such as, the wave filter that blocked by the light less than 350nm can be used and this wavelength region is blocked, or using the bandpass filter by the light near 436nm, near 408nm, near 365nm takes out these wavelength regions optionally to be taken out.Particularly, as light source, mercuryvapour lamp, photodiode, metal halide lamp, halogen lamp etc. can be enumerated.

Due to parallel rays can be irradiated equably to plane of exposure entirety, carry out photomask and define the correct contraposition of substrate of coloring compositions nitride layer, therefore preferably use the exposure apparatus such as mask aligner and step unit.

By making the coloring compositions nitride layer after exposure contact and video picture with image-developing liquor, thus form colored pattern on substrate.By video picture, the unexposed portion of coloring compositions nitride layer dissolves and is removed in image-developing liquor.

As image-developing liquor, preference is as the aqueous solution of the basic cpds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethyl ammonium hydroxide.Concentration in the aqueous solution of these basic cpds is preferably 0.01 ~ 10 quality %, is more preferably 0.03 ~ 5 quality %.And then image-developing liquor can comprise tensio-active agent.

Developing method can be any one of paddle (パ De Le) method, pickling process and spray method etc.And then, substrate can be made to tilt arbitrary angle when video picture.Preferably wash after video picture.

And then, cure after preferably the colored pattern obtained being carried out.Rear stoving temperature preferably 150 ~ 250 DEG C, more preferably 160 ~ 235 DEG C.After cure preferably 1 ~ 120 minute time, more preferably 10 ~ 60 minutes.

The colored curable resin composition of the application of the invention, can manufacture the colour filter of extra high lightness.Above-mentioned colour filter can be used as the colour filter for display unit (such as, liquid crystal indicator, organic El device, Electronic Paper etc.) and solid-state imager.

Embodiment

Next, enumerate embodiment, the present invention is specifically described further.In example, representing % and part of content and even usage quantity, as long as no special instructions, is then quality criteria.

In following embodiment, the structure of compound is by mass analysis (LC; Agilent system 1200 type, MASS; Agilent LC/MSD type) confirm.

[embodiment 1a]

The compound 50.0 parts represented by formula (IIIa), Virahol (manufacturing with the pure pharmaceutical worker's industry (strain) of light) 350 parts are at room temperature mixed, to instill diethylamide (Tokyo changes into industry (strain) manufacture) 18.1 parts at the temperature of 20 DEG C being no more than in the mixture, stir 3 hours at 20 DEG C.Reaction solution is dropped into 10% hydrochloric acid 2100 parts.Residue as suction strainer obtains the precipitate obtained, dry after cleaning with ion exchanged water 373 parts, obtains the compound 23.6 parts represented by formula (Cl-22).Yield is 43%.

The qualification of the compound represented by formula (Cl-22)

(mass analysis) ionization mode=ESI ⁺: m/z=[M+H] ⁺442.1

ExactMass：441.1

The compound 5.0 parts represented by formula (Cl-22), N-Methyl pyrrolidone (manufacturing with the pure pharmaceutical worker's industry (strain) of light) 35 parts are at room temperature mixed, in mixture, dipropylamine (Tokyo changes into industry (strain) manufacture) 3.4 parts is instilled being no more than at the temperature of 20 DEG C, be warmed up to 80 DEG C, stir 3 hours.After reaction solution cool to room temperature, add concentrated hydrochloric acid 3.4 parts, the mixture obtained is dropped in saturated aqueous common salt 315 parts.Residue as suction strainer obtains the precipitate obtained, dry after cleaning with ion exchanged water 630 parts, obtains the compound 3.9 parts represented by formula (Ia-7).Yield is 69%.

The qualification of the compound represented by formula (I-7a)

(mass analysis) ionization mode=ESI ⁺: m/z=[M+H] ⁺507.7

ExactMass：506.7

[embodiment 2a]

The compound 2.0 parts represented by formula (Cl-22), chloroform (manufacturing with the pure pharmaceutical worker's industry (strain) of light) 14 parts are at room temperature mixed, be no more than the formula (VIa-O4) 2.3 parts that at the temperature of 20 DEG C, instillation adopts the manufacture method recorded in special table 2011-513193 paragraph sequence number [0149] ~ [0154] to obtain in mixture, be warmed up to 80 DEG C, stir 22 hours.After reaction solution cool to room temperature, with 10% hydrochloric acid 98 parts carry out 2 times, to carry out with 10% salt solution 98 parts 2 times, to carry out after 2 separatory clean with ion exchanged water 98 parts, by chloroform distillation removing, dry, obtain the compound 1.2 parts represented by formula (Ia-69).Yield is 41%.

(mass analysis) ionization mode=ESI+:m/z=[M+H] ⁺641.3

ExactMass：640.3

[embodiment 3a]

The compound 7.5 parts represented by formula (Cl-22), N-Methyl pyrrolidone (manufacturing with the pure pharmaceutical worker's industry (strain) of light) 52.5 parts are at room temperature mixed, in mixture, to instill 2-(ethylamino) ethanol (Tokyo changes into industry (strain) manufacture) 4.5 parts at the temperature of 20 DEG C being no more than, stir 8 hours at 60 DEG C.After reaction solution cool to room temperature, drop into 10% salt solution 263 parts.Residue as suction strainer obtains the precipitate obtained, dry after cleaning with ion exchanged water 263 parts, obtains the compound 23.6 parts represented by formula (Ia-78).Yield is 43%.

The qualification of the compound represented by formula (Ia-78)

(mass analysis) ionization mode=ESI ⁺: m/z=[M+H] ⁺494.3

ExactMass：494.2

[embodiment 4a]

The compound 10.0 parts represented by formula (Cl-22), ion exchanged water 90 parts, 4-piperidine carboxylic acid (Tokyo changes into industry (strain) manufacture) 7.3 parts, 7.8 parts, salt of wormwood are at room temperature mixed, stirs 6 hours at 80 DEG C.After reaction solution cool to room temperature, put in 10% hydrochloric acid 115 parts.Residue as suction strainer obtains the precipitate obtained, dry after cleaning with ion exchanged water 345 parts, obtains the compound 10.9 parts represented by formula (Ia-90).Yield is 95%.

The qualification of the compound represented by formula (Ia-90)

(mass analysis) ionization mode=ESI ⁺: m/z=[M+H] ⁺535.2

ExactMass：534.2

[embodiment 5a]

The compound 25.0 parts represented by formula (IIIa), Virahol (manufacturing with the pure pharmaceutical worker's industry (strain) of light) 100 parts, 2-(methylamino) ethanol (Tokyo changes into industry (strain) manufacture) 27.8 parts are at room temperature mixed, stirs 2.5 hours at 80 DEG C.After reaction solution cool to room temperature, drop in saturated aqueous common salt 1225 parts, the residue as suction strainer obtains the precipitate obtained.In residue, add 10% hydrochloric acid 625 parts, stir after 1 hour, suction strainer is carried out to slurry, obtains residue, dry after cleaning with ion exchanged water 625 parts, obtain the compound 12.4 parts represented by formula (Ia-42).Yield is 42%.

The qualification of the compound represented by formula (Ia-42)

(mass analysis) ionization mode=ESI ⁺: m/z=[M+H] ⁺483.2

ExactMass：482.2

[embodiment 6a]

The compound 10.0 parts represented by formula (Cl-22), DMF 70.0 parts, diethanolamine (Tokyo changes into industry (strain) manufacture) 4.8 parts are at room temperature mixed, stirs 6 hours at 60 DEG C.After reaction solution cool to room temperature, drop in ion exchanged water 840 parts.Residue as suction strainer obtains the precipitate obtained, dry after cleaning with ion exchanged water 219 parts, obtains the compound 8.2 parts represented by formula (Ia-43).Yield is 71%.

The qualification of the compound represented by formula (Ia-43)

(mass analysis) ionization mode=ESI ⁺: m/z=[M+H] ⁺511.2

ExactMass：510.2

[embodiment 7a]

The compound 8.0 parts represented by formula (Cl-22), ion exchanged water 56.0 parts, N-methyl-D-glucarnine (Tokyo changes into industry (strain) manufacture) 8.8 parts are at room temperature mixed, stirs 4 hours at 80 DEG C.After reaction solution cool to room temperature, drop in saturated aqueous common salt 73 parts.Residue as suction strainer obtains the precipitate obtained, and carries out 3 times, the then clean rear drying of use ion exchanged water 20 parts, obtain the compound 6.4 parts represented by formula (Ia-100) with 10% salt solution 20 parts.Yield is 59%.

The qualification of the compound represented by formula (Ia-100)

(mass analysis) ionization mode=ESI ⁺: m/z=[M+H] ⁺601.2

ExactMass：600.2

[embodiment 8a]

The compound 16.0 parts represented by formula (Cl-22), ion exchanged water 112.0 parts, Virahol (manufacturing with the pure pharmaceutical worker's industry (strain) of light) 48 parts, N-ethyl-D-Glucose amine (Tokyo changes into industry (strain) manufacture) 18.9 parts are at room temperature mixed, stirs 13 hours at 80 DEG C.After reaction solution cool to room temperature, drop in saturated aqueous common salt 112 parts.Residue as suction strainer obtains the precipitate obtained, and carries out 3 times, the then clean rear drying of use ion exchanged water 30 parts, obtain the compound 6.4 parts represented by formula (Ia-101) with 10% salt solution 30 parts.Yield is 59%.

The qualification of the compound represented by formula (Ia-101)

(mass analysis) ionization mode=ESI ⁺: m/z=[M+H] ⁺615.2

ExactMass：614.2

[embodiment 9a]

The compound 4.0 parts represented by formula (IIIa), Virahol (manufacturing with the pure pharmaceutical worker's industry (strain) of light) 40 parts, ion exchanged water 20 parts, N-methyl-D-glucarnine (Tokyo changes into industry (strain) manufacture) 8.8 parts are at room temperature mixed, stirs 6 hours at 75 DEG C.After reaction solution cool to room temperature, the residue as suction strainer obtains the precipitate obtained.In residue, add Virahol 57 parts, stir after 1 hour, suction strainer is carried out to slurry, obtains residue, dry after cleaning with Virahol 57 parts and ion exchanged water 57 parts, obtain the compound 4.7 parts represented by formula (Ia-104).Yield is 66%.

The qualification of the compound represented by formula (Ia-104)

(mass analysis) ionization mode=ESI ⁺: m/z=[M+H] ⁺723.2

ExactMass：722.2

[embodiment 10a]

The compound 3.0 parts represented by formula (Cl-22), ion exchanged water 9 parts, sarkosine (Tokyo changes into industry (strain) manufacture) 1.5 parts, 2.4 parts, salt of wormwood (manufacturing with the pure pharmaceutical worker's industry (strain) of light) are at room temperature mixed, stirs 7 hours at 75 DEG C.After reaction solution cool to room temperature, put in 5% hydrochloric acid 135 parts.Residue as suction strainer obtains the precipitate obtained, dry after cleaning with ion exchanged water 47 parts, obtains the compound 1.6 parts represented by formula (Ia-110).Yield is 48%.

The qualification of the compound represented by formula (Ia-110)

(mass analysis) ionization mode=ESI ⁺: m/z=[M+H] ⁺494.3

ExactMass：494.2

[embodiment 11a]

The compound 3.0 parts represented by formula (Cl-22), ion exchanged water 9 parts, imino-diacetic acetic acid (Tokyo changes into industry (strain) manufacture) 2.3 parts, 2.4 parts, salt of wormwood (manufacturing with the pure pharmaceutical worker's industry (strain) of light) are at room temperature mixed, stirs 7 hours at 75 DEG C.After reaction solution cool to room temperature, put in 5% hydrochloric acid 135 parts.Residue as suction strainer obtains the precipitate obtained, dry after cleaning with ion exchanged water 47 parts, obtains the compound 1.5 parts represented by formula (Ia-112).Yield is 42%.

The qualification of the compound represented by formula (Ia-112)

(mass analysis) ionization mode=ESI ⁺: m/z=[M+H] ⁺538.2

ExactMass：538.1

[embodiment 12a]

The compound 8.0 parts represented by formula (IIIa), ion exchanged water 72 parts, 2-(ethylamino) ethanol (Tokyo changes into industry (strain) manufacture) 8.1 parts are at room temperature mixed, stirs 6 hours at 80 DEG C.After reaction solution cool to room temperature, put in saturated aqueous common salt 120 parts, the residue as suction strainer obtains the precipitate obtained.In residue, add 10% hydrochloric acid 60 parts, stir after 1 hour, suction strainer is carried out to slurry, obtains residue, dry after cleaning with ion exchanged water 60 parts, obtain the compound 4.2 parts represented by formula (I-44).Yield is 42%.

The qualification of the compound represented by formula (Ia-44)

(mass analysis) ionization mode=ESI ⁺: m/z=[M+H] ⁺510.3

ExactMass：510.2

[comparative example 1a]

The compound 10.0 parts represented by formula (IIIa), Virahol (manufacturing with the pure pharmaceutical worker's industry (strain) of light) 40 parts are at room temperature mixed, instill diethylamine (Tokyo changes into industry (strain) manufacture) 7.2 parts in the mixture, be warmed up to 65 DEG C, stir 3 hours.After reaction solution cool to room temperature, drop in 0.5% salt solution 280 parts.Residue as suction strainer obtains the precipitate obtained, dry after cleaning with ion exchanged water 200 parts, obtains the compound 8.0 parts represented by formula (a).Yield is 68%.

The qualification of the compound represented by formula (a)

(mass analysis) ionization mode=ESI ⁺: m/z=[M+H] ⁺479.3

ExactMass：478.2

The mensuration > of < solubleness

As described belowly obtain the solubleness of compound in propylene glycol monomethyl ether (hereinafter referred to as PGME) obtained in the compound and comparative example 1a obtained separately in embodiment 1a ~ 12a.

In 10mL sample hose with following ratio by compound and above-mentioned solvent, then, sample hose embolism is sealed, with ultrasonic vibration machine vibration 3 minutes at 30 DEG C.Then, at room temperature place after 30 minutes, carry out suction strainer, by its residue of visual observation.When failing to confirm insolubles, solvability is judged as that well, when can confirm insolubles, solvability is judged as bad.Describe solvability in table 4 and be judged as good peak concentration.× mean to be 1%, bad.

Table 4

	Compound	Peak concentration
			Embodiment 1a	Ia-7	7％
Embodiment 2a	Ia-69	10％
			Embodiment 3a	Ia-78	1％
Embodiment 4a	Ia-90	1％

Embodiment 5a	Ia-42	1％
			Embodiment 6a	Ia-43	1％
Embodiment 7a	Ia-100	1％
			Embodiment 8a	Ia-101	1％
Embodiment 9a	Ia-104	1％
			Embodiment 10a	Ia-110	1％
Embodiment 11a	Ia-112	1％
			Embodiment 12a	Ia-44	1％
Comparative example 1a	a	×

The mensuration > of < absorbancy

The compound 0.35g obtained separately in embodiment 1a ~ 12a is dissolved in chloroform or DMF (hereinafter referred to as DMF), makes volume be 250cm ³, by 2cm wherein ³100cm is become with chloroform or ethyl lactate (hereinafter referred to as EL) dilution ³, the solution of modulation concentration 0.028g/L.For above-mentioned solution, use ultraviolet-visible pectrophotometer (V-650DS; Japan's light splitting (strain) manufactures) (quartz cell, optical path length: 1cm) determine maximum absorption wavelength (λ _max) and maximum absorption wavelength (λ _max) under absorbancy.Show the result in table 5.

Table 5

[embodiment 1b]

Using compound (IIb) 40 parts, as the diethylamine (Tokyo change into industry (strain) manufacture) 146 parts of compound (IIIb) under the existence of 1-Methyl-2-Pyrrolidone 100 parts, mix under dark conditions, the solution obtained is stirred 3 hours at 30 DEG C.By after the reaction solution cool to room temperature that obtains, add in the mixed solution of 400 parts, water, 35% hydrochloric acid 20 parts, at room temperature stir 1 hour, result crystallization.Dry after obtaining the crystallization of precipitation as the residue of suction strainer, obtain the compound 40 parts represented by formula (Ib-37A).

Next, by the compound 44.1 parts represented by formula (Ib-37A) and N-methyl-o-Tolylamine (Tokyo changes into industry (strain) manufacture) 27.1 parts under the existence of 1-Methyl-2-Pyrrolidone 50 parts, heating 5 hours at 130 DEG C.By after the reaction solution cool to room temperature that obtains, filter, clean with 100 parts, water, by the crystallizing and drying obtained, obtain the compound 48.6 parts represented by formula (Ib-37).

The qualification of the compound represented by formula (Ib-37)

(mass analysis) ionization mode=ESI+:m/z=[M+H] ⁺541.2

ExactMass：540.2

[embodiment 2b ~ 5b]

In the same manner as embodiment 1b, obtain the compound (embodiment 2b) represented by formula (Ib-8), the compound (embodiment 3b) represented by formula (Ib-36), the compound (embodiment 4b) represented by formula (Ib-38), the compound (embodiment 5b) that represented by formula (Ib-101) respectively.

The qualification of the compound represented by formula (Ib-8)

(mass analysis) ionization mode=ESI+:m/z=[M+H] ⁺512.3

ExactMass：512.2

The qualification of the compound represented by formula (Ib-36)

(mass analysis) ionization mode=ESI+:m/z=[M+H] ⁺526.3

ExactMass：526.2

The qualification of the compound represented by formula (Ib-38)

(mass analysis) ionization mode=ESI+:m/z=[M+H] ⁺555.2

ExactMass：554.2

The qualification of the compound represented by formula (Ib-101)

(mass analysis) ionization mode=ESI+:m/z=[M+H] ⁺597.3

ExactMass：596.3

The mensuration > of < solubleness

As described belowly obtain the compound that obtains separately in embodiment 1b ~ 5b and rhodamine B (Tokyo changes into industry (strain) manufacture) solubleness in propylene glycol monomethyl ether (hereinafter referred to as PGME), ethyl lactate (hereinafter referred to as EL), propylene glycol monomethyl ether (hereinafter referred to as PGMEA).

In 50mL sample hose, with following ratio by compound and above-mentioned solvent, then, sample hose embolism is sealed, at 30 DEG C, use ultrasonic vibration machine vibration 3 minutes.Then, at room temperature place after 30 minutes, carry out suction strainer, by its residue of visual observation.When failing to confirm insolubles, solvability is judged as well, being designated as zero at table 6, and when can confirm insolubles, solvability is judged as bad, be designated as in table 6 ×.

10% compound 0.1g, solvent 1g

15% compound 0.15g, solvent 1g

1% compound 0.01g, solvent 1g

Table 6

Compound (b) is rhodamine B (Tokyo changes into industry (strain) manufacture).

[embodiment 1c]

Using compound (IIc) 20 parts and as the N-ethyl-o-Tolylamine (manufacturing with the pure pharmaceutical worker's industry (strain) of light) 14 parts of compound (IIIc) under the existence of 1-Methyl-2-Pyrrolidone 50 parts, mix under dark conditions, the solution obtained is stirred 3 hours at 30 DEG C.By after the reaction solution cool to room temperature that obtains, add in the mixed solution of 400 parts, water, 35% hydrochloric acid 20 parts, at room temperature stir 1 hour, result crystallization.Dry after obtaining the crystallization of precipitation as the residue of suction strainer, obtain the compound 25 parts represented by formula (Ic-132A).

Next, the compound 50 parts that will be represented by formula (Ic-132A) and N-metlyl-phenylamine (manufacturing with the pure pharmaceutical worker's industry (strain) of light) 10.7 parts heating 5 hours under the existence of 1-Methyl-2-Pyrrolidone 50 parts, at 100 DEG C.By after the reaction solution cool to room temperature that obtains, filter, clean with 100 parts, water, by the crystallizing and drying obtained, obtain the compound 50 parts represented by formula (Ic-132).

The qualification of the compound represented by formula (Ic-132)

(mass analysis) ionization mode=ESI+:m/z=[M+H] ⁺575.2

ExactMass：574.1

[embodiment 2c ~ 6c]

In the same manner as embodiment 1c, obtain the compound (embodiment 2c) represented by formula (Ic-1), the compound (embodiment 3c) represented by formula (Ic-7), the compound (embodiment 4c) represented by formula (Ic-134), the compound (embodiment 5c) represented by formula (Ic-138), the compound (embodiment 6c) that represented by formula (Ic-140) respectively.

The qualification of the compound represented by formula (Ic-1)

(mass analysis) ionization mode=ESI+:m/z=[M+H] ⁺561.3

ExactMass：560.2

The qualification of the compound represented by formula (Ic-7)

(mass analysis) ionization mode=ESI+:m/z=[M+H] ⁺561.3

ExactMass：560.2

The qualification of the compound represented by formula (Ic-134)

(mass analysis) ionization mode=ESI+:m/z=[M+H] ⁺589.2

ExactMass：588.2

The qualification of the compound represented by formula (Ic-138)

(mass analysis) ionization mode=ESI+:m/z=[M+H] ⁺575.3

ExactMass：574.2

The qualification of the compound represented by formula (Ic-140)

(mass analysis) ionization mode=ESI+:m/z=[M+H] ⁺589.2

ExactMass：588.2

The mensuration > of < solubleness

As described belowly obtain the compound that obtains separately in embodiment 1c ~ 6c and rhodamine B (Tokyo changes into industry (strain) manufacture) solubleness in propylene glycol monomethyl ether (hereinafter referred to as PGME), ethyl lactate (hereinafter referred to as EL), propylene glycol monomethyl ether (hereinafter referred to as PGMEA).

In 50mL sample hose, with following ratio by compound and above-mentioned solvent, then, sample hose embolism is sealed, at 30 DEG C, use ultrasonic vibration machine vibration 3 minutes.Then, at room temperature place after 30 minutes, carry out suction strainer, by its residue of visual observation.When failing to confirm insolubles, solvability is judged as well, being designated as zero in table 7, and when can confirm insolubles, solvability is judged as bad, be designated as in table 7 ×.

10% compound 0.1g, solvent 1g

15% compound 0.15g, solvent 1g

1% compound 0.01g, solvent 1g

Table 7

Compound (b) is rhodamine B (Tokyo changes into industry (strain) manufacture).

[synthesis of resin (B-1)]

In the flask possessing reflux cooler, dropping funnel and agitator, flow into appropriate nitrogen and become nitrogen atmosphere, loading propylene glycol monomethyl ether 100 parts, be heated to 85 DEG C while stirring.Next, instillation makes methacrylic acid 19 parts, 3,4-epoxy three ring [5.2.1.0 to use dropping liquid pump to last about 5 hours in above-mentioned flask ^2,6] decane-8-base acrylate and 3,4-epoxy three ring [5.2.1.0 ^2,6] mixture (containing than with molar ratio computing, being 50:50) (trade(brand)name " E-DCPA ", Co., Ltd. ダイセ Le manufacture) 171 parts of solution be dissolved in propylene glycol monomethyl ether 40 parts of decane-9-base acrylate.On the other hand, instillation makes polymerization starter 2 to use other dropping liquid pump to last about 5 hours in flask, two (2,4-methyl pentane nitrile) the 26 parts of solution be dissolved in propylene glycol monomethyl ether 120 parts of 2 '-azo.After the instillation of polymerization starter terminates, remain on this temperature about 3 hours, then cool to room temperature, obtain the solution that solid divides the multipolymer (resin (B-1)) of 43.5%.The weight-average molecular weight of the resin (B-1) obtained is 8000, and molecular weight distribution is 1.98, and solid divides the acid number of conversion to be 53mg-KOH/g.

GPC method is adopted to carry out the weight-average molecular weight (Mw) of the polystyrene conversion of resin and the mensuration of number-average molecular weight (Mn) under the following conditions.

Device: HLC-8120GPC (Dong ソー (strain) manufactures)

Post: TSK-GELG2000HXL

Column temperature: 40 DEG C

Solvent: THF

Flow velocity: 1.0mL/min

Detected liquid-solid shape divides concentration: 0.001 ~ 0.01 quality %

Injection rate: 50 μ L

Detector: RI

Correction reference material: TSKSTANDARDPOLYSTYRENE

F-40、F-4、F-288、

A-2500、A-500

(Dong ソー (strain) manufactures)

Using the ratio (Mw/Mn) of the weight-average molecular weight of polystyrene conversion obtained above and number-average molecular weight as molecular weight distribution.

[modulation of colored curable resin composition (a)]

By tinting material (A): the compound 2.6 parts represented by formula (Ia-7), formula (Ia-69), formula (Ia-78), formula (Ia-90), formula (Ia-42), formula (Ia-43), formula (Ia-100), formula (Ia-101), formula (Ia-104), formula (Ia-110), formula (Ia-112) or formula (Ia-44);

C.I. pigment Blue 15: 630.1 parts;

Acrylic acid series pigment dispersing agent 13 parts;

Alkali soluble resin (B): resin (B-1) (solid divides conversion) 53 parts;

Polymerizable compound (C): dipentaerythritol acrylate (KAYARAD (registered trademark) DPHA; Japan's chemical drug (strain) manufactures) 50 parts;

Polymerization starter (D): N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) octane-1-ketone-2-imines (Irgacure (registered trademark) OXE-01; BASF society manufactures; O-acyl group oxime compound) 10 parts;

Solvent (E): propylene glycol monomethyl ether 700 parts;

Solvent (E): propylene glycol monomethyl ether 80 parts;

And

Flow agent (F): メガ Off ァッ Network (registered trademark) F554 (DIC (strain) manufacture) 0.1 part

Be obtained by mixing colored curable resin composition (a).

[modulation of colored curable resin composition (b)]

By tinting material (A): the compound 2.5 parts represented by formula (Ib-37), formula (Ib-8), formula (Ib-36), formula (Ib-38) or formula (Ib-101);

C.I. pigment Blue 15: 630.1 parts;

Acrylic acid series pigment dispersing agent 13 parts;

Alkali soluble resin (B): resin (B-1) (solid divides conversion) 50 parts;

Solvent (E): propylene glycol monomethyl ether 720 parts;

Solvent (E): propylene glycol monomethyl ether 80 parts;

And

Be obtained by mixing colored curable resin composition (b).

[modulation of colored curable resin composition (c)]

By tinting material (A): the compound 2.6 parts represented by formula (Ic-132), formula (Ic-1), formula (Ic-7), formula (Ic-134), formula (Ic-138) or formula (Ic-140);

C.I. pigment Blue 15: 630.1 parts;

Acrylic acid series pigment dispersing agent 13 parts;

Alkali soluble resin (B): resin (B-1) (solid divides conversion) 53 parts;

Solvent (E): propylene glycol monomethyl ether 700 parts;

Solvent (E): propylene glycol monomethyl ether 80 parts;

And

Be obtained by mixing colored curable resin composition (c).

[formation of pattern]

At the glass substrate (イーグ Le XG of 2 inch square; コーニ Application グ society manufacture) on be coated with cured composition for color (a), (b) or (c) with spin-coating method after, at 100 DEG C, prebake 3 minutes, obtains composition layer.After cooling, what make to define the glass substrate of composition layer and silica glass photomask is spaced apart 100 μm, uses exposure machine (TME-150RSK; トプコ Application (strain) manufactures), under air atmosphere, with the exposure of 150mJ/cm2 (365nm benchmark), carry out rayed.As photomask, use the photomask defining 100 μm of lines and space pattern.After rayed, above-mentioned film is flooded 80 seconds and video picture in the water system image-developing liquor comprising nonionic system tensio-active agent 0.12% and potassium hydroxide 0.04% at 23 DEG C, after washing, in an oven, carry out 20 minutes at 220 DEG C after cure, obtain pattern.

Industry utilizes possibility

Compound of the present invention solvability is in organic solvent excellent.The colour filter formed by the colored curable resin composition comprising compound of the present invention can expect that lightness is higher.

Claims

1. the compound represented by formula (Ia):

R ^1a, R ^2a, R ^3aand R ^4arepresent the alkyl of carbon number 1 ~ 20 or the cycloalkyl of carbon number 5 ~ 10 independently of one another, in addition, R ^1awith R ^2aring is formed, R together with the nitrogen-atoms can be combined with each other, combined with them ^3awith R ^4aring is formed together with the nitrogen-atoms can be combined with each other, combined with them, but, R ^1a, R ^2a, R ^3aand R ^4anot be all same group ,-CH contained in abovementioned alkyl ₂-can by-O-,-NR ^b-or-CO-substitute, hydrogen atom contained in abovementioned alkyl can be replaced by the aromatic hydrocarbyl of halogen atom, carbon number 6 ~ 20 or-OH, and hydrogen atom contained in above-mentioned aromatic hydrocarbyl can be replaced by the alkoxyl group of carbon number 1 ~ 8, R ^brepresent the alkyl of carbon number 1 ~ 3.

2. compound according to claim 1, wherein, R ^1a, R ^2a, R ^3aand R ^4abe the alkyl of carbon number 1 ~ 20 independently of one another ,-CH contained in abovementioned alkyl ₂-can be substituted by-O-or CO-, hydrogen atom contained in abovementioned alkyl can be replaced by the aromatic hydrocarbyl of halogen atom or carbon number 6 ~ 10.

3. compound according to claim 1 and 2, wherein, R ^1a, R ^2a, R ^3aand R ^4ain at least 2 be the alkyl of carbon number 2 ~ 20 ,-CH contained in abovementioned alkyl ₂-can be replaced by-O-or CO-, hydrogen atom contained in abovementioned alkyl can be replaced by the aromatic hydrocarbyl of halogen atom or carbon number 6 ~ 10.

4. the compound according to any one of claims 1 to 3, wherein, R ^1a, R ^2a, R ^3aand R ^4abe the alkyl of carbon number 2 ~ 20 independently of one another ,-CH contained in abovementioned alkyl ₂-can be substituted by-O-.

5. the compound according to any one of Claims 1 to 4, wherein, R ^1a, R ^2a, R ^3aand R ^4ain 1 be-CH contained in the alkyl of carbon number 2 ~ 20 ₂-by the alternative group of-O-.

6. compound according to claim 1, wherein, R ^1aand R ^2abe the alkyl of carbon number 2 ~ 6 independently of one another, R ^3aand R ^4abe the alkyl of carbon number 1 ~ 6 independently of one another.

7. compound according to claim 1, wherein, R ^1aand R ^2abe ethyl separately, R ^3aand R ^4abe methyl, propyl group or butyl independently of one another.

8. compound according to claim 1, wherein, R ^1aand R ^2abe ethyl separately, R ^3afor-CH contained in the alkyl of carbon number 4 ~ 15 ₂-by the alternative group of-O-.

9. the compound represented by formula (Ib):

R ^1b, R ^2band R ^3brepresent the alkyl of carbon number 1 ~ 8 independently of one another, hydrogen atom contained in abovementioned alkyl can be replaced by the aromatic hydrocarbyl of carbon number 6 ~ 10, hydrogen atom contained in above-mentioned aromatic hydrocarbyl can be replaced by the alkoxyl group of carbon number 1 ~ 3, the group shown in Ar expression (i)

R represents the alkyl of hydrogen atom or carbon number 1 ~ 3, and hydrogen atom contained in abovementioned alkyl can be replaced by halogen atom, and m represents the integer of 1 ~ 5, and when m is more than 2, multiple R can be mutually the same, also can be different, and * represents the bonding end with nitrogen-atoms.

10. compound according to claim 9, wherein, R ^1b, R ^2band R ^3bbe methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or 2-ethylhexyl independently of one another.

11. compounds according to claim 9 or 10, wherein, R is methyl.

12. compounds according to any one of claim 9 ~ 11, wherein, m is 1 or 2.

13. compounds according to any one of claim 9 ~ 12, wherein, Ar is the group represented by formula (C-0), the group represented by formula (C-1) or the group represented by formula (C-2),

* the bonding end with nitrogen-atoms is represented.

14. compounds represented by formula (Ic):

X ¹and X ²different from each other, represent the alkyl of carbon number 1 ~ 8 separately, hydrogen atom contained in abovementioned alkyl can be replaced by the aromatic hydrocarbyl of carbon number 6 ~ 10, and hydrogen atom contained in above-mentioned aromatic hydrocarbyl can be replaced by the alkoxyl group of carbon number 1 ~ 3, Ar ¹and Ar ²represent the group represented by formula (i) independently of one another,

15. compounds according to claim 14, wherein, X ¹and X ²be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or 2-ethylhexyl separately.

16. compounds according to claims 14 or 15, wherein, R is methyl.

17. compounds according to claims 14 or 15, wherein, m is 1 or 2.

18. compounds according to claims 14 or 15, wherein, Ar ¹and Ar ²group, the group represented by formula (C-1) or the group represented by formula (C-2) independently of one another for being represented by formula (C-0),

* the bonding end with nitrogen-atoms is represented.

19. tinting materials, it comprises the compound described in any one of claim 1 ~ 18.

20. tinting materials according to claim 19, it also comprises pigment.

21. colored curable resin compositions, it comprises tinting material, resin, polymerizable compound, polymerization starter and solvent described in claim 19 or 20.

22. films, are formed by colored curable resin composition according to claim 21.

23. colour filters, are formed by colored curable resin composition according to claim 21.

24. display unit, it comprises colour filter according to claim 23.