CN102618085B

CN102618085B - Salt and dyestuff

Info

Publication number: CN102618085B
Application number: CN201210025673.3A
Authority: CN
Inventors: 赤坂哲郎; 吴龙虎; 金象同
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2011-01-19
Filing date: 2012-01-17
Publication date: 2015-11-25
Anticipated expiration: 2032-01-17
Also published as: JP2012233151A; JP6019580B2; KR101940107B1; TW201237117A; CN102618085A; KR20120084262A; TWI516550B

Abstract

A kind of salt is the n valency organometallic anions M of the atoms metal containing the metal ion that can form more than divalent ^n-, and derive from and can form the cationic salt of the dyestuff of salt with this organometallic anions, and this organometallic anions meets specific prerequisite for during compound shown in formula (1), and this salt solvent borne is in organic solvent excellent.M ^n-nZ ⁺？(1)。

Description

Salt and dyestuff

Technical field

The present invention relates to as the useful salt of dyestuff.

Background technology

Dyestuff uses in the field of such as filamentary material, liquid crystal indicator, ink-jet and recording materials etc.

As such dyestuff, there will be a known such as Japanese Laid-Open Patent Publication 2008-106111 publication and Japanese Laid-Open Patent Publication 2011-100114 publication and Wuhan University Journal, the compound that Edition, the 51st volume the 6th phase, 699-703 page, the compound represented as following formula (d-1) for 2005, formula (d-2) represent and the compound that formula (h-1) represents.

Summary of the invention

From in the past just known above-claimed cpd sometimes to differ the solvability met surely in organic solvent.

The invention provides following [1] ~ [6].

[1] salt, is characterized in that, is the n valency organometallic anions M of the atoms metal containing the metal ion that can form more than divalent ^n-, and derive from the salt that can form the positively charged ion (oniumcation) of the dyestuff of salt with this organometallic anions, and this organometallic anions meets following prerequisite A for during compound shown in formula (1).

M ^n-nZ ⁺(1)

[in formula (1), M ^n-represent above-mentioned organometallic anions.Z ⁺represent hydrogen ion (hydron) or alkali metal cation.N represents the integer of 1 ~ 3.When n is the integer of more than 2, multiple Z ⁺can identical mutually also can be different.]

Prerequisite A: the concentration of the compound represented by formula (1) is the absorbancy of the measured in solution of 0.028g/L is less than 0.05 in 400 ~ 900nm district.

[2] [1] salt of recording, described positively charged ion be derive from cyanin (cyanine) dyestuff positively charged ion, derive from triarylmethane (triarymethane) dyestuff positively charged ion, derive from the positively charged ion of xanthene (xanthene) dyestuff or derive from the positively charged ion of anthraquinone (anthraquinone) dyestuff.

[3] [1] or [2] salt of recording, described n valency organometallic anions M ^n-be the organometallic anions with the structure deriving from following compound, described compound has multiplely can have substituent Whitfield's ointment (salicylicAcid) or the carboxymethyl (carboxymethyl) with amino bonded.

[4] salt of any one record of [1] ~ [3], described n valency organometallic anions M ^n-in the contained atoms metal that can form the metal ion of more than divalent be Al, Cr or Co.

[5] dyestuff, the salt that in using [1] ~ [4], any one is recorded is as effective constituent.

[6] coloured composition, containing the dyestuff that [5] are recorded.

Salt of the present invention is excellent in the solvability of organic solvent.

Salt of the present invention, is characterized in that, is the n valency organometallic anions M of the atoms metal containing the metal ion that can form more than divalent ^n--and derive from and can form the cationic salt of the dyestuff of salt with this organometallic anions, and this organometallic anions, when meeting compound (sometimes claiming " compound (1) " below) that formula (1) represents, meets following prerequisite A.

M ^n-nZ ⁺(1)

[in formula (1), M ^n-represent above-mentioned organometallic anions.Z ⁺represent hydrogen ion or alkali metal cation.N represents the integer of 1 ~ 3.When n is the integer of more than 2, multiple Z ⁺can be the same or different.]

Salt of the present invention-electric charge with+electric charge is identical.

As the dyestuff of salt can be formed with this organometallic anions, for example there are anthocyanin dye, anthraquinone dye, triarylmethane dye, xanthene dye, phthalocyanine pigment, triarylmethane colouring matters, acridine dye, azines, thiazine dyes, oxazine dyestuff, azomethine dyes and azoic dyestuff etc.Wherein, preferred anthocyanin dye, triarylmethane dye, xanthene dye and anthraquinone dye.The positively charged ion that salt of the present invention like this comes from dyestuff by origin is formed, and shows as the useful color characteristics of dyestuff.

As positively charged ion, for example there are the ammonium cation, oxo positively charged ion, sulfo group positively charged ion, phosphonium cation etc. that such as derive from above-mentioned dyestuff respectively.

Below, just form the positively charged ion of salt of the present invention, enumerate the dyestuff particular instantiation becoming its source.

As the positively charged ion deriving from anthocyanin dye, for example there are the positively charged ion etc. such as with the skeleton represented with formula (1-1) ~ formula (1-42) respectively.Further, in formula, " n-Pr " represents n-propyl, and " n-Bu " represents normal-butyl, and " s-Bu " represents sec-butyl.

As anthocyanin dye, for example there are the salt that the positively charged ion that represents with formula (1-1) ~ formula (1-42) respectively and above-mentioned counter anion are formed.As counter anion, for example there are halide ions (such as Cl-, Br-, I-), cross chloric acid negatively charged ion, salt acid anion, sulfocyanic acid negatively charged ion, phosphorus hexafluoride negatively charged ion, antimony hexafluoride negatively charged ion, tetrafluoride boron anion, C ₆h ₅sO ₃ ^-, CH ₃-C ₆h ₄sO ₃ ^-, CF ₃sO ₃ ^-deng.

The cationic dyestuff of triarylmethane dye is derived from as guiding, such as example there are respectively with C.I. alkalescence red 9, C.I. alkaline purple 1, C.I. alkalescence purple 2, C.I. alkaline purple 3, C.I. alkalescence purple 4, C.I. alkaline purple 13, C.I. basic violet 14, C.I. alkalescence purple 23, C.I. alkali blue 1, C.I. alkali blue 5, C.I. Blue 7, C.I. alkali blue 8, C.I. alkali blue 11, C.I. alkali blue 15, C.I. alkali blue 18, C.I. alkali blue 20, C.I. alkali blue 21, C.I. alkali blue 24, C.I. alkali blue 26, C.I. alkali green 1, C.I. the pigment that represents of alkali green 4 and following formula (g-1) ~ (g-7).In addition, also there can be exemplified the dyestuff of the presoma that can become them, as C.I. solvent blue 5 (presoma of C.I. Blue 7 can be become) etc.

Cationic dyestuff, i.e. xanthene dye that so-called guiding derives from xanthene dye are the general names of the dyestuff in molecule with xanthene skeleton.Preferably on this xanthene skeleton, at least there is the amino that can be substituted, more preferably there are two amino that can be substituted.The nitrogen-atoms of the amino that the positively charged ion contained by salt of the present invention preferably can be substituted is the positively charged ion with the structure of carrying positive charge, more preferably iminium cations.

As involved xanthene dye, for example there are eosin (Eosin) based dye, fluorescein (Fluorescein) based dye, rhodamine (Rhodamine) based dye, pyronine (Pyronine) based dye, red alkalescence (Rosamine) based dye etc.Again, for example there are as at Synlett, 2010, No., rhodamine (Rhodamine) based dye that the Sauerstoffatom of p.89-92 described xanthene skeleton is replaced by sulphur atom, selenium atom or tellurium atom or red alkaline (Rosamine) based dye etc.

Xanthene dye has Cl-or PF usually ₆ ^-deng inorganic anion, or there is in molecule carboxylic acid ion (-COO ^-) or sulfonate ion (-SO ₃ ^-) etc. acidic-group.The former situation, xanthene dye is so-called basic dyestuff, and the positively charged ion deriving from xanthene dye normally eliminates the positively charged ion of part or all (preferably whole) inorganic anion from xanthene dye.The situation of the latter, xanthene dye is so-called inner salt, the positively charged ion of the structure that the acidic groups that the inside salt that the positively charged ion deriving from xanthene dye normally relates to has part or all (preferably whole) are neutralized.Here, acidic groups is such as carboxylic acid ion (-COO ^-) group that is neutralized is carboxyl (-COOH) or its salt (-COONa etc.), sulfonate ion (-SO ₃ ^-) group that is neutralized is sulfo group (-SO ₃or its salt (-SO H) ₃na etc.).

The dyestuff etc. that in xanthene dye, C.I. alkalescence red 2 with C.I. alkali red 1:1, C.I. alkalescence as specifically exemplifying of basic dyestuff is red 3, C.I. alkalescence is red 4, alkalescence is red 8, alkali red 1:1 1, C.I. alkaline purple 10, C.I. alkali violet 11:1, C.I. alkalescence purple 25 and following formula (h-1) ~ (h-82) represent.

In xanthene dye, the concrete example as inner salt for example there are respectively with the dyestuff etc. that C.I. medium red 27 and following formula (h-100) ~ (h-118) represent.

As guiding the cationic dyestuff deriving from anthraquinone dye, for example there are C.I. alkali blue 22, C.I. Basic Blue 35, C.I. alkali blue 45, C.I. alkali blue 47 etc.

The compound (1) of the negatively charged ion of guiding salt of the present invention meets following prerequisite A.

Prerequisite A: be the absorbancy of the measured in solution of 0.028g/L by the concentration of compound (1) be less than 0.05 in 400 ~ 900nm district.

Compound (1) being dissolved in any one in ethyl lactate, chloroform, DMF, ion exchanged water, methyl alcohol, ethanol and toluene, making the solution for measuring absorbancy.

For the absorbancy of this measured in solution 400 ~ 900nm.This absorbancy below 0.05, is preferably less than 0.035 in the whole region of 400 ~ 900nm, and further preferably less than 0.005.

Meet prerequisite A by compound (1), salt of the present invention has and keeps as the color characteristics of cationic dyestuff and the tendency of the solvability excellence at organic solvent.

Basic metal in the compound represented with formula (1) for example there are sodium and potassium etc.

M ^n-nZ ⁺(1)

[in formula (1), M ^n-represent the n valency organometallic anions containing atoms metal more than divalent.Z ⁺represent hydrogen ion or alkali metal cation.N represents the integer of 1 ~ 3.When n is the integer of more than 2, multiple Z ⁺can be the same or different each other.]

Above-mentioned organometallic anions has the structure by ionic linkage or coordinate bond combination between the atoms metal of the metal ion that can form more than divalent and organic compound.

As above-mentioned organic compound, for example there are and can have substituent Whitfield's ointment, there is multiple compound with the carboxymethyl of amino bonded, substituent benzilic acid can be had, substituent amygdalic acid can be had and can substituent pyridine carboxylic acid etc. be had.As organometallic anions M ^n-, preferably have the organometallic anions of the structure deriving from compound, described compound has multiple compound can with substituent Whitfield's ointment or the carboxymethyl with amino bonded.

As having above-mentioned substituent Whitfield's ointment, for example there are Whitfield's ointment, 3-cresotinic acid, 3-tert-butyl salicylic acid, 3-aminosallcylic acid, 3-chloro-salicylic acid, 4-bromo ortho-oxybenzoic acid, 3-methoxysalicylic acid, 2-hydroxyl bigcatkin willow, 3-Nitrosalicylic Acid, 4-trifluoromethyl Whitfield's ointment, 3,5-di-tert-butyl salicylic acid, 3,5-dibromosalicylic acid, 3,5-dichlorosalicylic acid, 3,5,6-tri-chloro-salicylic acid, 4-hydroxyl Whitfield's ointment, 5-hydroxyl Whitfield's ointment etc.

As the compound of carboxymethyl with multiple and above-mentioned amino bonded, such as, for example there are

Deng.

As described substituent benzilic acid can be had, for example there are such as

deng.

As above-mentioned substituent amygdalic acid can be had, for example there are such as

Deng.

As above-mentioned substituent pyridine carboxylic acid can be had, for example there are such as

Deng.

As the atoms metal of metal ion that can form more than divalent, for example there are Al, Cr, Co, Fe, Cu, Ni, Co, Zn, Mg, Ca and Ba etc.

Especially, preferred Al, Cr and Co.

As the negatively charged ion M forming compound (1) ^n-, for example there are such as negatively charged ion (c-1) ~ negatively charged ion (c-72) etc.

[table 1]

Negatively charged ion M ^n-	M ¹	R ¹¹	R ¹²	R ¹³	R ¹⁴
						Negatively charged ion (c-1)	Cr ³⁺	H	H	H	H
Negatively charged ion (c-2)	Cr ³⁺	H	tBu	H	tBu
						Negatively charged ion (c-3)	Cr ³⁺	H	NH ₂	H	H
Negatively charged ion (c-4)	Cr ³⁺	H	H	NH ₂	H
						Negatively charged ion (c-5)	Cr ³⁺	H	H	H	NH ₂
Negatively charged ion (c-6)	Cr ³⁺	H	Cl	H	H
						Negatively charged ion (c-7)	Cr ³⁺	H	H	Cl	H
Negatively charged ion (c-8)	Cr ³⁺	H	Br	H	H
						Negatively charged ion (c-9)	Cr ³⁺	H	H	Br	H
Negatively charged ion (c-10)	Cr ³⁺	H	I	H	H
						Negatively charged ion (c-11)	Cr ³⁺	H	H	I	H
Negatively charged ion (c-12)	Cr ³⁺	H	CH ₃	H	H
						Negatively charged ion (c-13)	Cr ³⁺	H	OCH ₃	H	H
Negatively charged ion (c-14)	Cr ³⁺	OH	H	H	H
						Negatively charged ion (c-15)	Cr ³⁺	H	OH	H	H
Negatively charged ion (c-16)	Cr ³⁺	H	H	OH	H
						Negatively charged ion (c-17)	Cr ³⁺	H	H	H	OH
Negatively charged ion (c-18)	Cr ³⁺	H	F	H	H
						Negatively charged ion (c-19)	Cr ³⁺	H	NO ₂	H	H
Negatively charged ion (c-20)	Cr ³⁺	H	H	CF ₃	H
						Negatively charged ion (c-21)	Cr ³⁺	H	Cl	H	Cl
Negatively charged ion (c-22)	Cr ³⁺	H	Br	H	Br
						Negatively charged ion (c-23)	Cr ³⁺	H	I	H	I
Negatively charged ion (c-24)	Cr ³⁺	H	OH	OH	H

Connect [table 1]

Negatively charged ion M ^n-	M ¹	R ¹¹	R ¹²	R ¹³	R ¹⁴
						Negatively charged ion (c-25)	Cr ³⁺	OH	H	OH	H
Negatively charged ion (c-26)	Cr ³⁺	Cl	Cl	H	Cl
						Negatively charged ion (c-27)	Al ³⁺	H	H	H	H
Negatively charged ion (c-28)	Al ³⁺	H	tBu	H	tBu
						Negatively charged ion (c-29)	Al ³⁺	H	NH ₂	H	H
Negatively charged ion (c-30)	Al ³⁺	H	H	NH ₂	H
						Negatively charged ion (c-31)	Al ³⁺	H	H	H	NH ₂
Negatively charged ion (c-32)	Al ³⁺	H	Cl	H	H
						Negatively charged ion (c-33)	Al ³⁺	H	H	Cl	H

[table 2]

Negatively charged ion (c-34)	Al ³⁺	H	Br	H	H
						Negatively charged ion (c-35)	Al ³⁺	H	H	Br	H
Negatively charged ion (c-36)	Al ³⁺	H	I	H	H
						Negatively charged ion (c-37)	Al ³⁺	H	H	I	H
Negatively charged ion (c-38)	Al ³⁺	H	CH ₃	H	H
						Negatively charged ion (c-39)	Al ³⁺	H	OCH ₃	H	H
Negatively charged ion (c-40)	Al ³⁺	OH	H	H	H
						Negatively charged ion (c-41)	Al ³⁺	H	OH	H	H
Negatively charged ion (c-42)	Al ³⁺	H	H	OH	H
						Negatively charged ion (c-43)	Al ³⁺	H	H	H	OH
Negatively charged ion (c-44)	Al ³⁺	H	F	H	H
						Negatively charged ion (c-45)	Al ³⁺	H	NO ₂	H	H
Negatively charged ion (c-46)	Al ³⁺	H	H	CF ₃	H
						Negatively charged ion (c-47)	Al ³⁺	H	Cl	H	Cl
Negatively charged ion (c-48)	Al ³⁺	H	Br	H	Br

[table 3]

Negatively charged ion M ^n-	M ²	n _a
			Negatively charged ion (c-53)	Cu ²⁺	2
Negatively charged ion (c-54)	Ni ²⁺	2
			Negatively charged ion (c-55)	Co ²⁺	2
Negatively charged ion (c-56)	Zn ²⁺	2
			Negatively charged ion (c-57)	Mg ²⁺	2
Negatively charged ion (c-58)	Ba ²⁺	2
			Negatively charged ion (c-59)	Ca ²⁺	2
Negatively charged ion (c-60)	Fe ³⁺	1

[table 4]

Negatively charged ion M ^n-	M ³	n _b
			Negatively charged ion (c-61)	Cu ²⁺	2
Negatively charged ion (c-62)	Ni ²⁺	2

[table 5]

Negatively charged ion M ^n-	M ⁴	n _c
			Negatively charged ion (c-63)	Co ²⁺	2
Negatively charged ion (c-64)	Zn ²⁺	2

[table 6]

Negatively charged ion M ^n-	M ⁵	n _d
			Negatively charged ion (c-65)	Cu ²⁺	2
Negatively charged ion (c-66)	Ni ²⁺	2

[table 7]

Negatively charged ion M ^n-	M ⁶	n _e
			Negatively charged ion (c-67)	Co ²⁺	2
Negatively charged ion (c-68)	Zn ²⁺	2

[table 8]

Negatively charged ion M ^n-	M ⁷	n _f
			Negatively charged ion (c-69)	Ba ²⁺	3
Negatively charged ion (c-70)	Fe ³⁺	2

[table 9]

Negatively charged ion M ^n-	M ⁸	n _g
			Negatively charged ion (c-71)	Cu ²⁺	1
Negatively charged ion (c-72)	Ni ²⁺	1

Especially, as negatively charged ion M ^n-, preferred anionic (c-2), negatively charged ion (c-6) ~ negatively charged ion (c-9), negatively charged ion (c-14) ~ negatively charged ion (c-17), negatively charged ion (c-21), negatively charged ion (c-22), negatively charged ion (c-24) ~ negatively charged ion (c-26), negatively charged ion (c-28), negatively charged ion (c-32) ~ negatively charged ion (c-35), negatively charged ion (c-40) ~ negatively charged ion (c-43), negatively charged ion (c-47), negatively charged ion (c-48), negatively charged ion (c-50) ~ negatively charged ion (c-62) negatively charged ion (c-65) and negatively charged ion (c-66), more preferably negatively charged ion (c-2), negatively charged ion (c-21), negatively charged ion (c-22), negatively charged ion (c-26), negatively charged ion (c-28), negatively charged ion (c-47), negatively charged ion (c-48) and negatively charged ion (c-52), further preferred anionic (c-28).If these negatively charged ion, then salt of the present invention has the tendency of the dissolving excellence at organic solvent.

As salt of the present invention, such as, for example there are salt (I-1) salt (I-60) etc.

[table 10]

Salt	Derive from the positively charged ion of dyestuff	M ^n-
			Salt (I-1)	The positively charged ion that formula (1-2) represents	c-28
Salt (I-2)	The positively charged ion that formula (1-10) represents	c-28
			Salt (I-3)	C.I. the positively charged ion of Blue 7	c-28
Salt (I-4)	C.I. the positively charged ion of alkaline purple 3	c-28
			Salt (I-5)	C.I. the positively charged ion of alkali blue 18	c-28
Salt (I-6)	C.I. the positively charged ion of alkali blue 26	c-28
			Salt (I-7)	C.I. the positively charged ion of alkaline purple 10	c-28
Salt (I-8)	C.I. the positively charged ion of alkali violet 11:1	c-28
			Salt (I-9)	C.I. the positively charged ion of alkali red 1:1	c-28
Salt (I-10)	C.I. the positively charged ion of alkali blue 22	c-28
			Salt (I-11)	The positively charged ion that formula (1-18) represents	c-2
Salt (I-12)	The positively charged ion that formula (1-10) represents	c-2
			Salt (I-13)	C.I. the positively charged ion of Blue 7	c-2
Salt (I-14)	C.I. the positively charged ion of alkaline purple 3	c-2
			Salt (I-15)	C.I. the positively charged ion Application of alkali blue 18	c-2
Salt (I-16)	C.I. the positively charged ion of alkali blue 26	c-2
			Salt (I-17)	C.I. the positively charged ion of alkaline purple 10	c-2
Salt (I-18)	C.I. the positively charged ion of alkali violet 11:1	c-2
			Salt (I-19)	C.I. the positively charged ion of alkali red 1:1	c-2
Salt (I-20)	C.I. the positively charged ion of alkali blue 22	c-2
			Salt (I-21)	The positively charged ion that formula (1-18) represents	c-53
Salt (I-22)	The positively charged ion that formula (1-10) represents	c-54
			Salt (I-23)	C.I. the positively charged ion of Blue 7	c-55
Salt (I-24)	C.I. the positively charged ion of alkaline purple 3	c-56

Connect [table 10]

Salt	Derive from the positively charged ion of dyestuff	M ^n-
			Salt (I-25)	C.I. the positively charged ion of alkali blue 18	c-57
Salt (I-26)	C.I. the positively charged ion of alkali blue 26	c-58
			Salt (I-27)	C.I. the positively charged ion of alkaline purple 10	c-59
Salt (I-28)	C.I. the positively charged ion of alkali violet 11:1	c-60
			Salt (I-29)	C.I. the positively charged ion of alkali red 1:1	c-61
Salt (I-30)	C.I. the positively charged ion of alkali blue 22	c-62

[table 11]

Salt	Derive from the positively charged ion of dyestuff	M ^n-
			Salt (I-31)	The positively charged ion that formula (h-1) represents	c-28
Salt (I-32)	The positively charged ion that formula (h-2) represents	c-28
			Salt (I-33)	The positively charged ion that formula (h-3) represents	c-28
Salt (I-34)	The positively charged ion that formula (h-4) represents	c-28
			Salt (I-35)	The positively charged ion that formula (h-7) represents	c-28
Salt (I-36)	The positively charged ion that formula (h-8) represents	c-28
			Salt (I-37)	The positively charged ion that formula (h-9) represents	c-28
Salt (I-38)	The positively charged ion that formula (h-10) represents	c-28
			Salt (I-39)	The positively charged ion that formula (h-17) represents	c-28
Salt (I-40)	The positively charged ion that formula (h-18) represents	c-28
			Salt (I-41)	The positively charged ion that formula (h-65) represents	c-28
Salt (I-42)	The positively charged ion that formula (h-66) represents	c-28
			Salt (I-43)	The positively charged ion that formula (h-67) represents	c-28
Salt (I-44)	The positively charged ion that formula (h-68) represents	c-28
			Salt (I-45)	The positively charged ion that formula (h-79) represents	c-28
Salt (I-46)	The positively charged ion that formula (h-80) represents	c-28
			Salt (I-47)	The positively charged ion that formula (h-81) represents	c-28
Salt (I-48)	The positively charged ion that formula (h-82) represents	c-28
			Salt (I-49)	The positively charged ion that formula (h-83) represents	c-28
Salt (I-50)	The positively charged ion that formula (h-84) represents	c-28
			Salt (I-51)	The positively charged ion that formula (h-86) represents	c-28
Salt (I-52)	The positively charged ion that formula (h-105) represents	c-28
			Salt (I-53)	The positively charged ion that formula (h-1) represents	c-2

Connect [table 11]

Salt	Derive from the positively charged ion of dyestuff	M ^n-
			Salt (I-54)	The positively charged ion that formula (h-2) represents	c-2
Salt (I-55)	The positively charged ion that formula (h-4) represents	c-2
			Salt (I-56)	The positively charged ion that formula (h-65) represents	c-2
Salt (I-57)	The positively charged ion that formula (h-66) represents	c-2
			Salt (I-58)	The positively charged ion that formula (h-67) represents	c-2
Salt (I-59)	The positively charged ion that formula (h-83) represents	c-2
			Salt (I-60)	The positively charged ion that formula (h-84) represents	c-2
Salt (I-61)	The positively charged ion that formula (g-1) represents	c-28
			Salt (I-62)	The positively charged ion that formula (g-4) represents	c-28

Salt of the present invention can by mixing colouring agent and compound (1) manufacture in a solvent.

As the solvent used during mixing, for example there are N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, methyl-sulphoxide, acetonitrile, vinyl acetic monomer, toluene, methyl alcohol, ethanol, Virahol, acetone, tetrahydrofuran (THF), diox, water and chloroform etc.

Especially, preferred DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, methyl-sulphoxide, methyl alcohol, ethanol, Virahol and water.If these solvents, then the solubleness of dyestuff and compound (1) has high tendency.

When solvent is water, in order to make dyestuff and compound (1) be dissolved in solvent, the acid such as acetic acid or hydrochloric acid can be added.

The mixing of dyestuff and compound (1), carries out both can dissolving, also can not dissolve and just mix in above-mentioned solvent.But, be dissolved with both solvents by use and make it dissolving to carry out, salt of the present invention can be obtained by high yield.

The mixing temperature of dyestuff and compound (1), preferably 0 DEG C ~ 150 DEG C, more preferably 10 DEG C ~ 120 DEG C, preferably 20 DEG C ~ 100 DEG C further.

Again, mixing time preferably 1 hour ~ 72 hours, more preferably 2 hours ~ 24 hours, preferably 3 hours ~ 12 hours further.

When solvent for mixing is the solvent molten with aqueous phase, in this solution, adding ion exchanged water, stirring 1 ~ 3 hour further.Then, obtain precipitate by filtration, just can obtain salt of the present invention.As required, ion-exchange water washing can be used.

When solvent for mixing is not molten with aqueous phase solvent, in this solution, adding ion exchanged water, stirring 1 ~ 3 hour further.Then, obtain organic layer by separatory, just can obtain the solution containing salt of the present invention.As required, ion-exchange water washing can be used.By removing desolventizing from the solution containing salt of the present invention, salt of the present invention can be obtained.

Further, salt of the present invention can be dissolved in the solvent of acetonitrile, vinyl acetic monomer, toluene, methyl alcohol, ethanol, Virahol, acetone, chloroform etc., carry out purifying by recrystallization.

Dyestuff can use commercially available product, such as thin Tian Fengzhu " theoretical manufacture dyestuff chemistry ", skill report hall, 396 ~ 402,357 ~ 366,369 ~ 377 and 235 ~ 241 pages, pine occupy just setting supervision " functional pigmented synthesis and utilisation technology ", シ mono-エ system シ mono-publishes, 89 ~ 96 pages, Synlett, 2010, No.1, p.89-92, J.OrganicChemistry, the material that the known method that 2008, Vol.73,8711-8718 etc. record manufactures.

Compound (1) can use commercially available product, that such as, records in Japanese Patent Laid-fair 8-10360 or JP 2002-258537 and experimental chemistry lecture 5 editions 22 volume 312-313 pages etc. is such, can be undertaken reacting manufacturing by making to become the compound of ligand and the vitriol of metal or muriate.

The salt of the present invention of such acquisition is useful as dyestuff.Again, dyestuff of the present invention solvability is in organic solvent high, therefore, especially useful as the dyestuff used in the colour filter of the display unit such as liquid crystal indicator.

The dyestuff that dyestuff of the present invention is is effective constituent with salt of the present invention.

Coloured composition of the present invention, containing dyestuff of the present invention as tinting material (also claiming " tinting material (A) " below), further also containing resin (B).Coloured composition of the present invention is more preferably containing polymerizable compound (C) and polymerization starter (D) and molten drug (E)).

Tinting material (A), also can further containing pigment and/or the dyestuff being different from dyestuff of the present invention except containing except dyestuff of the present invention.

The dyestuff being different from dyestuff of the present invention for example there are in Colour Index (ColourIndex) (TheSocietyofDyersandColourists publication) dyestuff etc. being classified as solvent (Solvent), acid (Acid), alkali (property) (Basic), active (reactive), directly (Direct), dispersion (Disperse) or reducing (Vat).More specifically, the dyestuff of following Colour Index (C.I.) number can be exemplified, but be not limited to these.

C.I. solvent yellow 25,79,81,82,83,89;

C.I. turmeric yellow 7,23,25,42,65,76;

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

C.I. direct Huang 4,28,44,86,132;

C.I. DISPERSE YELLOW 54,76;

C.I. solvent orange 41,54,56,99;

C.I. von Muller's indicator 56,74,95,108,149,162;

C.I. reactive orange 16;

C.I. direct orange 26;

C.I. solvent red 24,49,90,91,118,119,122,124,125,127,130,132,160,218;

C.I. Xylene Red 73,91,92,97,138,151,211,274,289;

C.I. acid violet 102;

C.I. solvent green 1,5;

C.I. acid green 3,5,9,25,28;

C.I. alkali green 1;

C.I. Vat green 1 etc.

Pigment can be enumerated, and is generally used for pigment dyestuff or the mineral dye of colo(u)rant dispersion resist.Mineral dye can be enumerated, the metallic compound of metal oxide or metallic complex salt class, can enumerate metal oxide or the complex metal oxidess such as iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony particularly.In addition, pigment dyestuff and mineral dye specifically can exemplify, and are classified as the compound of pigment (Pigment) in Colour Index (ColourIndex) (TheSocietyofDyersandColourists publication).More specifically, the pigment that following Colour Index (C.I.) is numbered can be exemplified, but and not mean that only for scheduling these.

C.I. Pigment Yellow 73 20,24,31,53,83,86,93,94,109,110,117,125,137,138,139,147,148,150,153,154,166,173 and 180;

C.I. pigment Orange 13,31,36,38,40,42,43,51,55,59,61,64,65 and 71;

C.I. Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192,215,216,224,242,254,255 and 264;

C.I. pigment violet 14,19,23,29,32,33,36,37 and 38;

C.I. pigment Green 7,10,15,25,36,47 and 58 etc.

It is 5 ~ 60 quality % that the content of tinting material (A) is preferably relative to the solids component in coloured composition.Herein, solids component to refer in coloured composition the total of composition in addition to the solvents.

Content preferably 3 ~ 100 quality % of dyestuff of the present invention contained in tinting material (A).

The dyestuff different from dyestuff of the present invention and pigment separately or can combine two or more and dyestuff of the present invention and use.

Resin (B) is not particularly limited, and can use any resin.Resin (B) is alkali soluble resin preferably, the resin more preferably containing the structural unit of being derived by (methyl) vinylformic acid.Herein, (methyl) vinylformic acid represents vinylformic acid and/or methacrylic acid.

Resin (B) concrete example has methacrylic acid/benzyl methacrylate multipolymer, methacrylic acid/benzyl methacrylate/styrol copolymer, methacrylic acid/benzyl methacrylate/isobornyl methacrylate multipolymer, methacrylic acid/styrene/methacrylic acid benzene methyl N-phenylmaleic anhydride contracting imine copolymer, methacrylic acid/styrene/methacrylic acid glycidyl ester copolymer etc.

The polystyrene conversion weight-average molecular weight of resin (B) preferably 5,000 ~ 35,000, more preferably 6,000 ~ 30,000.

Acid number preferably 50 ~ 150mg-KOH/g, the more preferably 60 ~ 135mg-KOH/g of resin (B).

The content of resin (B), relative to the solids component of coloured composition, is preferably 7 ~ 65 quality %, more preferably 13 ~ 60 quality %.

Polymerizable compound (C) is as long as just can be not particularly limited by the compound of the polymerization such as living radical, acid produced from polymerization starter (D).Such as, there is the compound etc. of polymerizability ethene unsaturated link(age).

Described polymerizable compound (C) preferably has the polymerizable compound of more than 3 polymerizable groups.The polymerizable compound with more than 3 polymerizable groups can exemplify, pentaerythritol tetracrylate, pentaerythritol tetramethacrylate, five vinylformic acid dipentaerythritol ester, pentamethyl-vinylformic acid dipentaerythritol ester, six vinylformic acid dipentaerythritol ester, hexamethyl vinylformic acid dipentaerythritol ester etc.Above-mentioned polymerizable compound can be used alone or in combination of two or more kinds.

The content of polymerizable compound (C), relative to the solids component of coloured composition, preferably 5 ~ 65 quality %, more preferably 10 ~ 60 quality %.

Above-mentioned polymerization starter (D) can exemplify living radical and produce agent, acidogenic agent etc.Living radical produces agent by dissociation produces active free radical that is hot or light.Above-mentioned living radical produces agent can exemplified by alkyl groups benzophenone compound, thioxanthone compounds, triazine based compound, oxime compound etc.

Abovementioned alkyl benzophenone compound can exemplify, such as 2-methyl-2-morpholine-1-(4-methylsulfonyl phenyl)-1-acetone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, benzil dimethyl ketal, 2-hydroxy-2-methyl-1-(4-(2-hydroxyl-oxethyl) phenyl)-1-acetone, 1-hydroxycyclohexylphenylketone etc.

Above-mentioned thioxanthone compounds can exemplify, such as ITX, ITX, 2,4-diethyl thioxanthones, 2,4-bis-clopenthixal ketones, the chloro-4-propoxythioxanthone of 1-etc.

Above-mentioned triaizine compounds can exemplify, such as 2, 4-bis-(trichloromethyl)-6-(4-p-methoxy-phenyl)-1, 3, 5-triazine, 2, 4-bis-(trichloromethyl)-6-(4-methoxyl group naphthyl)-1, 3, 5-triazine, 2, 4-bis-(trichloromethyl)-6-(4-methoxyl-styrene)-1, 3, 5-triazine, 2, 4-bis-(trichloromethyl)-6-(2-(5-methyl furan-2-base) vinyl)-1, 3, 5-triazine, 2, 4-bis-(trichloromethyl)-6-(2-(furans-2-base) vinyl)-1, 3, 5-triazine, 2, 4-bis-(trichloromethyl)-6-(2-(4-diethylamino-2-aminomethyl phenyl) vinyl)-1, 3, 5-triazine, 2, 4-bis-(trichloromethyl)-6-(2-(3, 4-Dimethoxyphenyl) vinyl)-1, 3, 5-triazine etc.

Above-mentioned oxime compound can exemplify; O-acyl group oxime compound; for example there are; N-benzoyloxy-1-(4-phenyl sulfonyl phenyl)-1-butanone-2-imines, N-benzoyloxy-1-(4-phenyl sulfonyl phenyl)-1-octanone-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-dioxy cyclopentylmethoxy) benzoyl }-9H-carbazole-3-base] ethane-1-imines etc.

In addition; living radical produces agent and can use such as; 2,4,6-trimethylbenzoyldiphenyl oxide compound, 2; 2 '-two (Chloro-O-Phenyl)-4; 4 ', 5,5 '-tetraphenyl-1; 2 '-diimidazole, 10-butyl-2-chloro-acridine ketone, 2-ethyl-anthraquinone, benzil, 9,10-phenanthrenequione, camphorquinone, phenylglyoxalates methyl ester, two cyclopentadiene titanium compounds etc.

Above-mentioned acidogenic agent can exemplify, the salt, tosic acid nitrobenzyl ester (or salt) class, tosic acid benzoin ester (or salt) class etc. of 4-hydroxy phenyl dimethyl sulfonium tosilate, 4-hydroxy phenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl dimethyl sulfonium tosilate, 4-acetoxyl group phenyl methyl benzyl sulfonium hexafluoro antimonate, triphenylsulfonium tosilate, triphenylsulfonium hexafluoro antimonate, phenylbenzene iodine tosilate, phenylbenzene iodine hexafluoro antimonate etc.

Described polymerization starter can be used alone and also can two or more combinationally use.

The content of polymerization starter (D), relative to total amount 100 mass parts of resin (B) and polymerizable compound (C), preferably 0.1 ~ 30 mass parts, more preferably 1 ~ 20 mass parts.The content of polymerization starter is in above-mentioned scope, and high-sensitivity, the time shutter shortens, and productivity improves, therefore preferably.

Solvent (E) can exemplify, ethers, aromatic hydrocarbon based, ketone, alcohols, ester class, amides etc.

Above-mentioned ethers can exemplify, tetrahydrofuran (THF), tetrahydropyrans, 1, 4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol list propyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, Diethylene Glycol dipropyl ether, diethylene glycol dibutyl ether, 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, TC acetic ester, diethylene glycol monobutyl ether acetic ester etc.

Above-mentionedly aromatic hydrocarbon basedly benzene,toluene,xylene, sym-trimethylbenzene etc. can be enumerated.

Above-mentioned ketone can enumerate acetone, 2-butanone, 2-heptanone, 3-heptanone, dipropyl ketone, 4-methyl-2 pentanone, 4-hydroxy-4-methyl-2-pentanone, cyclopentanone, pimelinketone etc.

Above-mentioned alcohols can enumerate methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, hexalin, ethylene glycol, glycerol etc.

Above-mentioned ester class can enumerate vinyl acetic monomer, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, n-Butyl lactate, Methoxy Methyl Acetate, 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, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, Propyl pyruvate, methyl acetoacetate, ethyl 3-oxobutanoate, 3-methoxybutyl acetic ester, 3-methyl-3-methoxybutyl acetic ester, gamma-butyrolactone etc.

Above-mentioned amides can enumerate DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone etc.

These solvents can be used alone and also can two or more combinationally use.

The content of solvent (E) in coloured composition, relative to coloured composition, preferably 70 ~ 95 quality %, more preferably 75 ~ 90 quality %.

The various additives that coloured composition of the present invention also can contain tensio-active agent as required, weighting agent, other macromolecular compounds, contiguity promotor, antioxidant, UV light absorber, photostabilizer, chain move agent etc.

Salt of the present invention is useful as dyestuff.Salt of the present invention is high due to molar absorptivity, and shows high solvability in organic solvent, therefore especially can be useful as the dyestuff used in the colour filter of the display unit such as liquid crystal indicator.

In addition, coloured composition containing salt of the present invention, can be applied to using known state and there is colour filter as in the various machine associated with rendered image such as display unit (such as, known liquid crystal indicator, organic El device etc.), solid-state imager of its a part of component parts.

Embodiment

Below, according to embodiment in detail the present invention is described in detail." % " and " part " in embodiment and comparative example unless otherwise specified, just refers to quality % and mass parts.

In following examples, the structure ultimate analysis (VARIO-EL of compound; (エレメ Application タ mono-Le (strain) system)) confirm.

Embodiment 1

Compound (BONTRON (registered trademark) E-108, オリエ Application ト chemical industry (strain) (ORIENTCHEMICALINDUSTRIESCO. that formula (1) is represented, LTD) make) 0.85 part be dissolved in N, in dinethylformamide 50 parts, make solution (s1).In addition, the compound (CasOrganic society system) 1.02 parts formula (d-1) represented is dissolved in DMF 10 parts, makes solution (t1).At 25 DEG C, add the solution of (t1) in (s1), be then warming up to 80 DEG C, stir 8 hours.After making this mixed solution be cooled to room temperature, add ion exchanged water 500 parts, stir 1 hour further.Then, obtain precipitate through suction filtration, with ion exchanged water 100 parts cleaning, obtain the salt 1.18 parts that formula (I-1) represents.

The qualification of the salt that formula (I-1) represents

(ultimate analysis) C:77.7H:8.0N:2.6

Further, the compound 0.35g that the formula used as raw material (f-1) represents is dissolved in chloroform, makes volume be 250cm ³, with chloroform dilution 2cm wherein ³, make 100cm ³, be adjusted to the solution of concentration 0.028g/L.About this solution, use ultraviolet-visible pectrophotometer (V-650DS; Japan's light splitting (strain) system) (quartz container, optical length; 1cm) be determined at the absorbancy in the maximum absorption wavelength of 400 ~ 900nm and maximum absorption wavelength, maximum absorption wavelength is 425nm, and absorbancy is 0.0019.

Embodiment 2

The compound (BONTRON (registered trademark) E-108, オリエ Application ト chemical industry (strain) make) 1.0 parts formula (f-1) represented is dissolved in N, in dinethylformamide 70 parts, make solution (s2).In addition, the compound (PVC Network トリアピユア Block Le one BO, ア Le De リ t チ society system) 3.92 parts formula (d-2) represented is dissolved in DMF 90 parts, makes solution (t2).At 25 DEG C, add the solution of (t2) in (s2), be then warming up to 80 DEG C, stir 8 hours.After making this mixed solution be cooled to room temperature, with saturated aqueous common salt 100 parts, then add ion exchanged water 1000 parts, stir 1 hour further.Then, obtain precipitate through suction filtration, with ion exchanged water 100 parts and hexane 100 parts cleaning, obtain the salt 1.70 parts that formula (I-3) represents.

The qualification of the salt that formula (I-3) represents

(ultimate analysis) C:75.6H:7.9N:4.2

Embodiment 3

The compound (BONTRON (registered trademark) E-108, オリエ Application ト chemical industry (strain) make) 2.0 parts formula (f-1) represented is dissolved in N, in dinethylformamide 120 parts, make solution (s3).In addition, 1.96 parts, ORIENT (registered trademark) Oil indigo plant 613 (mixture of C.I. solvent blue 5 and resin, オリエ Application ト chemical industry (strain) system) is dissolved in N, in dinethylformamide 24 parts, make solution (t3).At 25 DEG C, add the solution of (t3) in (s3), be then warming up to 80 DEG C, stir 8 hours.After making this mixed solution be cooled to room temperature, add ion exchanged water 700 parts, stir 1 hour further.Then, obtain precipitate through suction filtration, with ion exchanged water 100 parts cleaning, obtain the salt 2.27 parts that formula (I-3) represents.

The synthesis example 1 of compound (1)

Add 250 parts, water to 3,5,6-tri-chloro-salicylic acid 5.00 parts, stir and dissolve under 60 degree, adding sodium hydroxide further, regulate pH to be 7.Be added on the solution having dissolved 2.03 parts, chromium sulphate hydrate in 200 parts, water further, stirring 5 hours under 90 degree.After this mixed solution is cooled to room temperature, filters unreacted 3,5,6-tri-chloro-salicylic acids, in filtrate, add saturated aqueous common salt 500 parts, stir 1 hour.Precipitate is obtained, with saturated aqueous common salt cleaning, as Z through suction filtration ⁺for the mixture of the compound of hydrionic compound and sodium ion, obtain the compound 2.02 parts that formula (f-2) represents.

By the method same with the compound that formula (f-1) represents, the maximum absorption wavelength of compound at 400 ~ 900nm that mensuration formula (f-2) represents and the absorbancy of maximum absorption wavelength, maximum absorption wavelength is 400nm, and absorbancy is 0.0066.

The synthesis example 2 of compound (1)

Add 250 parts, water to 3,5-dibromosalicylic acid 10.00 parts, stir and dissolve under 60 degree, adding sodium hydroxide further, regulate pH to be 7.Be added on the solution having dissolved 2.90 parts, chromium sulphate hydrate in 400 parts, water further, stirring 5 hours under 90 degree.After this mixed solution is cooled to room temperature, filter unreacted 3,5-dibromosalicylic acids, in filtrate, add 1000 parts, water, stir 1 hour.Precipitate is obtained, with water cleaning, as Z through suction filtration ⁺for the mixture of the compound of hydrionic compound and sodium ion, obtain the compound 4.89 parts that formula (f-3) represents.

By the method same with the compound that formula (f-1) represents, the maximum absorption wavelength of compound at 400 ~ 900nm that mensuration formula (f-3) represents and the absorbancy of maximum absorption wavelength, maximum absorption wavelength is 400nm, and absorbancy is 0.031.

The synthesis example 3 of compound (1)

Add 150 parts, water to 3,5,6-tri-chloro-salicylic acid 10.00 parts, stir and dissolve under 60 degree, adding sodium hydroxide further, regulate pH to be 7.Be added on the solution having dissolved 4.06 parts, Tai-Ace S 150 in 200 parts, water further, stirring 5 hours under 90 degree.After this mixed solution is cooled to room temperature, filter unreacted 3,5,6-tri-chloro-salicylic acids, add saturated aqueous common salt 500 parts, stir 1 hour.Precipitate is obtained, with water cleaning, as Z through suction filtration ⁺mixture for the compound of hydrionic compound and sodium ion obtains the compound 6.02 parts that formula (f-4) represents.

By the method same with the compound that formula (f-1) represents, the maximum absorption wavelength of compound at 400 ~ 900nm that mensuration formula (f-4) represents and the absorbancy of maximum absorption wavelength, maximum absorption wavelength is 400nm, and absorbancy is 0.0036.

The synthesis example 4 of compound (1)

Add 250 parts, water to 3,5-dibromosalicylic acid 10.00 parts, stir and dissolve under 60 degree, adding sodium hydroxide further, regulate pH to be 7.Be added on the solution having dissolved 2.89 parts, Tai-Ace S 150 in 200 parts, water further, stirring 6 hours under 90 degree.After this mixed solution is cooled to room temperature, filter unreacted 3,5-dibromosalicylic acids, in filtrate, add 1000 parts, water, stir 1 hour.Precipitate is obtained, with water cleaning, as Z through suction filtration ⁺for the mixture of the compound of hydrionic compound and sodium ion, obtain the compound 10.02 parts that formula (f-5) represents.

By the method same with the compound that formula (f-1) represents, the maximum absorption wavelength of compound at 400 ~ 900nm that mensuration formula (f-5) represents and the absorbancy of maximum absorption wavelength, maximum absorption wavelength is 637nm, and absorbancy is 0.0049.

The synthesis example 5 of compound (1)

Add 250 parts, water to 2,4-resorcylic acid 10.00 parts, stir and dissolve under 60 degree, adding sodium hydroxide further, regulate pH to be 7.Be added on the solution having dissolved 5.55 parts, Tai-Ace S 150 in 200 parts, water further, stirring 6 hours under 90 degree.After this mixed solution is cooled to room temperature, filter unreacted 2,4-resorcylic acids, in filtrate, add 1000 parts, water, stir 1 hour.Precipitate is obtained, with water cleaning, as Z through suction filtration ⁺mixture for the compound of hydrionic compound and sodium ion obtains the compound 6.51 parts that formula (f-6) represents.

By the method same with the compound that formula (f-1) represents, the maximum absorption wavelength of compound at 400 ~ 900nm that mensuration formula (f-6) represents and the absorbancy of maximum absorption wavelength, maximum absorption wavelength is 400nm, and absorbancy is 0.022.

The synthesis example 6 of compound (1)

Add 250 parts, water to DHB 10.00 parts, stir and dissolve under 60 degree, adding sodium hydroxide further, regulate pH to be 7.Be added on the solution having dissolved 5.55 parts, Tai-Ace S 150 in 200 parts, water further, stirring 6 hours under 90 degree.After this mixed solution is cooled to room temperature, filter unreacted DHB, in filtrate, add 1000 parts, water, stir 1 hour.Precipitate is obtained, with water cleaning, as Z through suction filtration ⁺mixture for the compound of hydrionic compound and sodium ion obtains the compound 10.01 parts that formula (f-7) represents.

By the method same with the compound that formula (f-1) represents, the maximum absorption wavelength of compound at 400 ~ 900nm that mensuration formula (f-7) represents and the absorbancy of maximum absorption wavelength, maximum absorption wavelength is 400nm, and absorbancy is 0.048.

Embodiment 4

(BONTRON (registered trademark) E-81, オリエ Application ト chemical industry (strain) (system) 2.00 parts is dissolved in N to compound formula (f-8) represented, in dinethylformamide 150 parts, make solution (s4).In addition, 1.80 parts, ORIENT (registered trademark) Oil indigo plant 613 (mixture of C.I. solvent blue 5 and resin, オリエ Application ト chemical industry (strain) system) is dissolved in N, in dinethylformamide 25 parts, make solution (t4).At 25 DEG C, add the solution of (t3) in (s3), be then warming up to 80 DEG C, stir 8 hours.After making mixed solution be cooled to room temperature.Add ion exchanged water 500 parts, stir 1 hour further.Then, obtain precipitate through suction filtration, with ion exchanged water 100 parts cleaning, obtain the salt 2.11 parts that formula (I-4) represents.

Embodiment 5

The compound 2.10 parts formula (f-3) represented is dissolved in DMF 150 parts, makes solution (s5).In addition, the conjunction (CasOrganic society system) 1.99 parts formula (d-1) represented is dissolved in DMF 19 parts, makes solution (t5).At 25 DEG C, add the solution of (t5) in (s5), be then warming up to 80 DEG C, stir 8 hours.After making mixed solution be cooled to room temperature, add ion exchanged water 500 parts, stir 1 hour further.Then, obtain precipitate through suction filtration, with ion exchanged water 100 parts cleaning, obtain the salt 2.50 parts that formula (I-5) represents.

The qualification of the salt that formula (I-5) represents

(ultimate analysis) C:53.7H:4.1N:2.3

Embodiment 6

The compound 2.00 parts formula (f-4) represented is dissolved in DMF 150 parts, makes solution (s6).In addition, the compound (CasOrganic society system) 1.49 parts formula (d-1) represented is dissolved in DMF 30 parts, makes solution (t6).At 25 DEG C, add the solution of (t6) in (s6), be then warming up to 80 DEG C, stir 8 hours.After this mixed solution is cooled to room temperature, add saturated aqueous common salt 50 parts, stir 1 hour, add ion exchanged water 300 parts further, stir 2 hours.Then, obtain precipitate through suction filtration, with ion exchanged water 100 parts cleaning, obtain the salt 2.53 parts that formula (I-6) represents.

The qualification of the salt that formula (I-6) represents

(ultimate analysis) C:60.7H:4.5N:2.6

Embodiment 7

The compound 1.60 parts formula (f-6) represented is dissolved in DMF 130 parts, makes solution (s7).In addition, 1.98 parts, ORIENT (registered trademark) Oil indigo plant 613 (mixture of C.I. solvent blue 5 and resin, オリエ Application ト chemical industry (strain) system) is dissolved in N, in N-dimethyl formyl 40 parts, make solution (t7).At 25 DEG C, add the solution of (t7) in (s7), be then warming up to 80 DEG C, stir 8 hours.After making mixed solution be cooled to room temperature, add saturated aqueous common salt 200 parts, then add ion exchanged water 600 parts, stir 1 hour further.Then, obtain precipitate through suction filtration, with ion exchanged water 100 parts cleaning, obtain the salt 1.31 parts that formula (I-7) represents.

Embodiment 8

The compound (BONTRON (registered trademark) E-108, オリエ Application ト chemical industry (strain) make) 3.0 parts formula (f-1) represented is dissolved in N, in dinethylformamide 200 parts, make solution (s8).In addition, the polymerisable compounds 3.49 parts following formula (h-1) represented is dissolved in DMF 40 parts, makes solution (t8).At 25 DEG C, add the solution of (t8) in (s8), be then warming up to 80 DEG C, stir 8 hours.After making mixed solution be cooled to room temperature, add saturated aqueous common salt 50 parts, then add ion exchanged water 300 parts, stir 1 hour further.Then, obtain precipitate through suction filtration, with ion exchanged water 100 parts and hexane 100 parts cleaning, obtain the salt 3.15 parts that formula (I-31) represents.

The qualification of the salt that formula (I-31) represents

(ultimate analysis) C:69.7H:7.7N:2.6

Embodiment 9

The compound (BONTRON (registered trademark) E-108, オリエ Application ト chemical industry (strain) make) 1.50 parts formula (f-1) represented is dissolved in N, in dinethylformamide 120 parts, make solution (s9).In addition, the polymerisable compounds 1.30 parts following formula (h-2) represented is dissolved in DMF 30 parts, makes solution (t9).At 25 DEG C, add the solution of (t9) in (s9), be then warming up to 80 DEG C, stir 6.5 hours.After making mixed solution be cooled to room temperature, add saturated aqueous common salt 100 parts, then add ion exchanged water 700 parts, stir 1 hour further.Then, obtain precipitate through suction filtration, with ion exchanged water 100 parts and hexane 100 parts cleaning, obtain the salt 1.50 parts that formula (I-32) represents.

The qualification of the salt that formula (I-32) represents

(ultimate analysis) C:70.7H:7.6N:2.6

Embodiment 10

In 50 parts, 98% sulfuric acid, add 7.83 parts, 2-(4-diethylamino-2-hydroxy benzoyl) phenylformic acid (Tokyo changes into industry (strain) system) at leisure and mix, so that the temperature of mixture reaches less than 30 DEG C in mixing.Make the solution obtained be cooled to 5 DEG C, wherein add 3-(isopropylamino) phenol (the method manufacture recorded according to the flat 9-169708 publication of Japanese Laid-Open Patent Publication) 5.37 parts.Then, this mixture is stirred 65 hours at 5 DEG C.In frozen water 250 parts, add reaction mixture, obtain precipitate through suction filtration.Dissolved residue in chloroform 180 parts, adds ion exchanged water 300 parts, makes water layer be pH10 further, stir 1 hour with 10% aqueous sodium hydroxide solution.Separation obtains chloroform layer, with ion exchanged water 200 parts, dewaters with magnesium sulfate.Under reduced pressure, from the solution that removing magnesium sulfate obtains, distillation removing chloroform, obtains the compound 5.50 parts that formula (hx-83) represents.

The chloroform 30 parts that dewaters is added, stirred at ambient temperature 1 hour in the compound 3.00 parts represented in formula (hx-83), triethylene glycol (Tokyo changes into industry (strain) system) 3.16 parts, dimethyl aminopyridine (pharmaceutical worker's industry (strain) system pure with light) 0.24 part, (1s)-(+)-10-camphorsulfonic acid (Northeast chemistry (strain) system) 0.18 part.1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride ((strain) colleague chemical research is made) 1.83 parts is dissolved in the solution in dehydration chloroform 7.2 parts by instillation, to be no more than 30 DEG C, stirred at ambient temperature 5 hours.To this chloroformic solution, with 1N hydrochloric acid 300 parts, then use 10% salt solution, 200 parts of separatory, dewater with magnesium sulfate.Under reduced pressure, from the solution that removing magnesium sulfate obtains, distillation removing chloroform, obtains the compound 3.59 parts that following formula (h-83) represents.

The compound (BONTRON (registered trademark) E-108, オリエ Application ト chemical industry (strain) make) 1.50 parts formula (f-1) represented is dissolved in N, in dinethylformamide 120 parts, make solution (s10).In addition, the polymerisable compounds 1.79 parts following formula (h-83) represented is dissolved in DMF 100 parts, makes solution (t10).At 25 DEG C, add the solution of (t10) in (s10), be then warming up to 80 DEG C, stir 6 hours.After making mixed solution be cooled to room temperature, add saturated aqueous common salt 100 parts, then add ion exchanged water 700 parts, stir 1 hour further.Then, obtain precipitate through suction filtration, ion exchanged water 100 parts and hexane 100 parts cleaning, obtain the salt 1.93 parts that formula (I-49) represents.

The qualification of the salt that formula (I-49) represents

(ultimate analysis) C:70.1H:7.7N:2.5

Embodiment 11

1 is mixed under room temperature, 1,7,7-tetramethyl--8-hydroxyl julolidine (with OrgacicLetters, No. 21st, the 10th volume, 4799-4801 page, 2008. the method manufacture of record) 15.00 parts, butyric acid 250 parts, Tetra hydro Phthalic anhydride (Tokyo changes into industry (strain) system) 4.50 parts and 1.20 parts, 9.8% sulfuric acid, this mixing solutions is warming up to 140 DEG C, stirs 15 hours.After making this mixed solution be cooled to room temperature, be injected in hexane 3000 parts.The tarry solid that removing supernatant liquid obtains is dissolved in chloroform 340 parts, with ion exchanged water 300 parts to chloroformic solution separatory, uses sodium sulfate.Under reduced pressure, from the solution that removing magnesium sulfate obtains, distillation removing chloroform, obtains the compound 4.00 parts that formula (hx-17) represents.

The compound that hybrid (hx-17) represents 3.00 parts, triethylene glycol (Tokyo changes into industry (strain) system) 3.34 parts, dimethyl aminopyridine (pharmaceutical worker industry (strain) system pure with light) 0.09 part, (1s)-(+)-10-camphorsulfonic acid (Northeast chemistry (strain) system) 0.14 part and dehydration chloroform 70 parts, stirred at ambient temperature 1 hour.1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride ((strain) colleague chemical research is made) 1.38 parts is dissolved in the solution in dehydration chloroform 30 parts by instillation, to be no more than 30 DEG C, stirred at ambient temperature 5 hours.To this chloroformic solution, with 1N hydrochloric acid 50 parts, then with 10% salt solution 50 parts cleaning, dewater with magnesium sulfate.Under reduced pressure, from the solution that removing magnesium sulfate obtains, distillation removing chloroform, obtains the compound 2.90 parts that following formula (h-17) represents.

Compound (BONTRON (registrar) mark) E-108, オリエ Application ト chemical industry (strain) (system) 1.07 parts formula (f-1) represented is dissolved in N, in dinethylformamide 70 parts, make solution (s11).In addition, the polymerisable compounds 1.50 parts following formula (h-17) represented is dissolved in DMF 70 parts, makes solution (t11).At 25 DEG C, add the solution of (t11) in (s11), be then warming up to 80 DEG C, stir 8 hours.After making mixed solution be cooled to room temperature, add saturated aqueous common salt 50 parts, then add ion exchanged water 300 parts, stir 1 hour further.Then, obtain precipitate through suction filtration, with ion exchanged water 100 parts and hexane 100 parts cleaning, obtain the salt 1.50 parts that formula (I-39) represents.

The qualification of the salt that formula (I-39) represents

(ultimate analysis) C:72.4H:7.9N:2.2

Embodiment 12

Dehydration chloroform 120 parts is added, stirred at ambient temperature 1 hour in alkaline purple 10 (rhodamine B, Tokyo change into industry (strain) system) 10.00 parts, triethylene glycol monomethyl ether (Tokyo changes into industry (strain) system) 10.28 parts, dimethyl aminopyridine (pharmaceutical worker's industry (strain) system pure with light) 0.77 part, (1S)-(+)-10-camphorsulfonic acid (Northeast chemistry (strain) system) 0.58 part.1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride ((strain) colleague chemical research is made) 5.80 parts is dissolved in the solution in dehydration chloroform 49.3 parts by instillation, to be no more than 30 DEG C, stirred at ambient temperature 5 hours.To this chloroformic solution, with 1N hydrochloric acid 107 parts, then use 10% salt solution, 171 parts of separatory, dewater with magnesium sulfate.Under reduced pressure, from the solution that removing magnesium sulfate obtains, distillation removing chloroform, obtains the compound 11.50 parts that following formula (h-82) represents.

At 25 DEG C, the compound 11.50 parts that formula (h-82) represents is dissolved in N, in dinethylformamide 334 parts, the compound (BONTRON (registered trademark) E-108, オリエ Application ト chemical industry (strain) make) 11.12 parts that adding type (f-1) represents, stirs 4 hours.Add ion exchanged water 1668 parts, stir 1 hour further.Then, obtain precipitate through suction filtration, with ion exchanged water 334 parts and hexane 100 parts cleaning, obtain the salt 9.70 parts that formula (I-48) represents.

The qualification of the salt that formula (I-48) represents

(ultimate analysis) C:70.2H:7.7N:2.6

Embodiment 13

Dehydration chloroform 120 parts is added, stirred at ambient temperature 1 hour in alkaline purple 10 (rhodamine B, Tokyo change into industry (strain) system) 10.00 parts, 1-amylalcohol (Northeast chemistry (strain) system) 5.89 parts, dimethyl aminopyridine (pharmaceutical worker's industry (strain) system pure with light) 0.77 part, (1S)-(+)-10-camphorsulfonic acid (Northeast chemistry (strain) system) 0.58 part.1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride ((strain) colleague chemical research is made) 5.80 parts is dissolved in the solution in dehydration chloroform 49.3 parts by instillation, to be no more than 30 DEG C, stirred at ambient temperature 5 hours.To this chloroformic solution, with 1N hydrochloric acid 107 parts, then use 10% salt solution, 171 parts of separatory, dewater with magnesium sulfate.Under reduced pressure, from the solution that removing magnesium sulfate obtains, distillation removing chloroform, obtains the compound 10.80 parts that following formula (h-86) represents.

At 25 DEG C, the compound 10.80 parts that formula (h-86) represents is dissolved in N, in dinethylformamide 357 parts, the compound (BONTRON (registered trademark) E-108, オリエ Application ト chemical industry (strain) make) 11.89 parts that adding type (f-1) represents, stirs 4 hours.Add ion exchanged water 1784 parts, stir 1 hour further.Then, obtain precipitate through suction filtration, with ion exchanged water 357 parts and hexane 100 parts cleaning, obtain the salt 10.70 parts that formula (I-51) represents.

The qualification of the salt that formula (I-51) represents

(ultimate analysis) C:72.9H:7.9N:2.7

Embodiment 14

At 25 DEG C, C.I. alkali violet 11:1 (AizenCathilonBrilliantPinkCD-BH, hodogaya chemical industry (strain) system) 2.00 parts is dissolved in N, in dinethylformamide 66 parts, the compound (BONTRON (registered trademark) E-108, オリエ Application ト chemical industry (strain) make) 2.21 parts that adding type (f-1) represents, stirs 4 hours.Add ion exchanged water 332 parts, stir 1 hour further.Then, obtain precipitate through suction filtration, with ion exchanged water 66 parts and hexane 100 parts cleaning, obtain the salt 1.90 parts that formula (I-8) represents.

The qualification of the salt that formula (I-8) represents

(ultimate analysis) C:72.4H:7.6N:2.8

Embodiment 15

Compound (BONTRON (registrar) mark) E-108, オリエ Application ト chemical industry (strain) formula (f-1) represented makes) 2.29 parts be dissolved in N, in dinethylformamide 92 parts, make solution (s15).In addition, make alkaline purple 10 (rhodamine B, Tokyo change into industry (strain) system) 8.00 parts of solution (t15) be dissolved in DMF 280 parts.At 25 DEG C, add the solution of (t15) in (s15), be then warming up to 40 DEG C, stir 8 hours.After making this mixed solution be cooled to room temperature, add ion exchanged water 744 parts, stir 1 hour further.Then, obtain precipitate through suction filtration, with ion exchanged water 372 parts and hexane 100 parts cleaning, obtain the salt 4.95 parts that formula (I-7) represents.

The qualification of the salt that formula (I-7) represents

(ultimate analysis) C:72.0H:7.4N:2.8

Embodiment 16

Make compound (Rhodamine 101 inner salt, ACROSORGANICS society system) the 2.00 parts of solution (t16) be dissolved in 6N hydrochloric acid 70 parts formula (h-105) represented.The compound (BONTRON (registered trademark) E-108) formula (f-1) represented, オリエ Application ト chemical industry (strain) make) 2.14 parts be dissolved in N, in dinethylformamide 70 parts, make solution (s16).At 25 DEG C, add the solution of (t16) in (s16), stirred at ambient temperature 6.5 hours.With chloroform 225 parts, 2 separatory are extracted to this mixed solution, with magnesium sulfate, this chloroform is dewatered.From the solution that magnesium sulfate obtains, evaporated under reduced pressure removing chloroform.With the oily mater that hexane 20 parts of cleanings obtain, obtain the salt 3.82 parts that formula (I-52) represents.

The qualification of the salt that formula (I-52) represents

(ultimate analysis) C:73.2H:7.3N:2.7

Embodiment 17

Under ice bath, in alkaline purple 10 (rhodamine B, Tokyo change into industry (strain) system) 10.00 parts, add dehydration chloroform 50 parts, DMF 3.05 parts, stir 1 hour under ice bath.Thionyl chloride of dripping under ice bath (pharmaceutical worker industry (strain) system pure with light) 5.46 parts, is then warming up to 40 DEG C, stirs 3 hours.After being cooled to room temperature, the tetramethyleneimine that drips under ice bath (pharmaceutical worker industry (strain) system pure with light) 5.94 parts, is then warming up to 40 DEG C, stirs 2 hours.After this mixed solution is cooled to room temperature, add ion exchanged water 100 parts and chloroform 150 parts, separatory, divide and get chloroform layer.Add chloroform 150 parts in water layer, separatory, obtains chloroform layer.2 kinds of chloroform layers are merged, dewaters with magnesium sulfate.From the solution distillation removing chloroform that removing magnesium sulfate obtains under decompression, clean the solid obtained with vinyl acetic monomer 142 parts, obtain the compound 10.76 parts that following formula (h-65) represents.

Compound (BONTRON (registrar) mark) E-108, オリエ Application ト chemical industry (strain) formula (f-1) represented makes) 9.86 parts be dissolved in N, in dinethylformamide 394 parts, be warming up to 80 DEG C, make the solution (s17) dissolved.In addition, the polymerisable compounds 10.00 parts following formula (h-65) represented is dissolved in DMF 350 parts, makes solution (t17).At 80 DEG C, in (s17), add the solution of (t17), stir 6.5 hours at 80 DEG C.After making this mixed solution be cooled to room temperature, add ion exchanged water 1488 parts, stir 1 hour further.Then, obtain precipitate through suction filtration, with ion exchanged water 744 parts and hexane 383 parts cleaning, obtain the salt 9.08 parts that formula (I-41) represents

The qualification of the salt that formula (I-41) represents

(ultimate analysis) C:73.0H:7.7N:4.1

Embodiment 18

Under ice bath, in alkaline purple 10 (rhodamine B, Tokyo change into industry (strain) system) 10.00 parts, add dehydration chloroform 50 parts, DMF 3.05 parts, stir 1 hour under ice bath.Thionyl chloride of dripping under ice bath (pharmaceutical worker industry (strain) system pure with light) 5.46 parts, is then warming up to 40 DEG C, stirs 5.5 hours.After being cooled to room temperature, the piperidines that drips under ice bath (pharmaceutical worker industry (strain) system pure with light) 7.11 parts, is then warming up to 40 DEG C, stirs 2 hours.After this mixed solution is cooled to room temperature, add ion exchanged water 100 parts and chloroform 150 parts, separatory, divide and get chloroform layer.Add chloroform 150 parts in water layer, separatory, obtains chloroform layer.2 kinds of chloroform layers are merged, dewaters with magnesium sulfate.From the solution that removing magnesium sulfate obtains, under reduced pressure distillation removing chloroform, obtains the compound 11.93 parts that following formula (h-66) represents.

Compound (BONTRON (registrar) mark) E-108, オリエ Application ト chemical industry (strain) formula (f-1) represented makes) 2.88 parts be dissolved in N, in dinethylformamide 115 parts, be warming up to 80 DEG C, make the solution (s18) dissolved.In addition, the compound 3.00 parts following formula (h-66) represented is dissolved in DMF 105 parts, makes solution (t18).At 80 DEG C, in (s18), add the solution of (t18), stir 6.5 hours at 80 DEG C.After making this mixed solution be cooled to room temperature, add ion exchanged water 440 parts, stir 1 hour further.Then, obtain precipitate through suction filtration, with ion exchanged water 220 parts and hexane 114 parts cleaning, obtain the salt 3.15 parts that formula (I-42) represents.

The qualification of the salt that formula (I-42) represents

(ultimate analysis) C:73.1H:7.7N:4.1

Embodiment 19

Under ice bath, in alkaline purple 10 (rhodamine B, Tokyo change into industry (strain) system) 10.00 parts, add dehydration chloroform 200 parts, DMF 3.05 parts, stir 1 hour under ice bath.Thionyl chloride of dripping under ice bath (is made 7.45 parts with the pure pharmaceutical worker's industry (strain) of light, is then warming up to 40 DEG C, stir 5 hours.After being cooled to room temperature, hexamethyl of dripping under ice bath imines (pharmaceutical worker industry (strain) system pure with light) 10.35 parts, is then warming up to 40 DEG C, stirs 2 hours.After this mixed solution is cooled to room temperature, add ion exchanged water 200 parts, chloroform 300 parts, saturated aqueous common salt 100 parts, separatory, obtains chloroform layer, dewaters with magnesium sulfate.From the solution distillation removing chloroform that removing magnesium sulfate obtains under decompression, clean the solid obtained with vinyl acetic monomer 132 parts, obtain the compound 12.37 parts that following formula (h-67) represents.

Compound (BONTRON (registrar) mark) E-108, オリエ Application ト chemical industry (strain) (system) 9.36 parts formula (f-1) represented is dissolved in N, in dinethylformamide 375 parts, be warming up to 80 DEG C, make the solution (s19) dissolved.In addition, the polymerisable compounds 10.00 parts following formula (h-67) represented is dissolved in DMF 350 parts, makes solution (t19).At 80 DEG C, in (s19), add the solution of (t19), stir 6.5 hours at 80 DEG C.After making this mixed solution be cooled to room temperature, add ion exchanged water 1450 parts, stir 1 hour further.Then, obtain precipitate through suction filtration, with ion exchanged water 725 parts and hexane 374 parts cleaning, obtain the salt 9.90 parts that formula (I-43) represents.

The qualification of the salt that formula (I-43) represents

(ultimate analysis) C:73.2H:7.9N:4.0

Embodiment 20

At 25 DEG C, the compound 2.73 parts that formula (h-66) represents is dissolved in N, in dinethylformamide 96 parts, the compound (BONTRON (registered trademark) E-81, オリエ Application ト chemical industry (strain) make) 2.75 parts that adding type (f-8) represents, stirs 16 hours.Add ion exchanged water 383 parts, stir 1 hour further.Then, obtain precipitate through suction filtration, with ion exchanged water 96 parts and hexane 96 parts cleaning, obtain the salt 3.06 parts that formula (I-57) represents.

The qualification of the salt that formula (I-57) represents

(ultimate analysis) C:71.4H:7.7N:4.0

Embodiment 21

3-bromine fluorobenzene (Tokyo changes into industry (strain) system) 3.30 parts, diethylamine 6.00 parts, copper powder (Northeast chemistry (strain) system) 0.064 part, cupric iodide (I) 0.19 part, 9.20 parts, Tripotassium phosphate n hydrate (Northeast chemistry (strain) system) and 2-(dimethylamino) ethanol (Tokyo changes into industry (strain) system) 20.0 parts is mixed under room temperature, be warming up to 80 DEG C, stir 72 hours.After this mixed solution is cooled to room temperature, add 200 parts, water and satisfy with chloroform 150 parts, separatory, obtains chloroform layer, dewaters with magnesium sulfate.From the solution that removing magnesium sulfate obtains, under reduced pressure distillation removing chloroform, obtains the compound 2.06 parts that following formula (gx-1) represents.

Mixing N, N-diethyl-3-monomethylaniline (Tokyo changes into industry (strain) system) 16.30 parts, Methylal(dimethoxymethane) (Tokyo changes into industry (strain) system) 19.00 parts and acetic acid 100 parts.To drip 300 parts, acetic acid/98% sulfuric acid (1/1) mixture to this mixing solutions, stirred at ambient temperature 10 minutes.Obtain precipitate by suction filtration, with ion exchanged water 1000 parts cleaning, obtain the compound 10.04 parts that following formula (gx-2) represents.

The compound that hybrid (gx-2) represents 6.70 parts, 20 parts, potassium permanganate (Northeast chemistry (strain) system), copper sulfate (II) pentahydrate (Northeast chemistry (strain) system) 20 parts, stirred at ambient temperature 6 hours.Chloroform 200 parts is added, filtering separation chloroform extraction solution in this reactant.Evaporated under reduced pressure removing chloroform, obtains the compound 6.20 parts that following formula (gx-3) represents.

The compound that hybrid under room temperature (gx-3) represents 14.10 parts, the compound that formula (gx-1) represents 34.50,50 parts, hydroxy chloride phosphorus (Northeast chemistry (strain) system), be warming up to 100 DEG C, stir 3 hours.After this mixed solution is cooled to room temperature, joins in the mixed solvent of vinyl acetic monomer 120 parts/10 parts, mistake chloric acid, stir 1 hour.Obtain precipitate by suction filtration, with vinyl acetic monomer 200 parts cleaning, obtain the salt 8.64 parts that following formula (g-1) represents.

Compound (BONTRON (registrar) mark) E-108, オリエ Application ト chemical industry (strain) (system) 1.54 parts formula (f-1) represented is dissolved in N, in dinethylformamide 61 parts, make solution (s21).In addition, the salt 1.50 parts following formula (g-1) represented is dissolved in DMF 15 parts, makes solution (t21).At 25 DEG C, add the solution of (t21) in (s21), stirred at ambient temperature 2 hours.Add ion exchanged water 382 parts in this mixed solution, stir 1 hour further.Then, through attracting filtration to obtain precipitate, with ion exchanged water 127 parts cleaning, the salt 1.78 parts that formula (I-61) represents is obtained.

The qualification of the salt that formula (I-61) represents

(ultimate analysis) C:73.7H:8.4N:4.1

(mensuration of absorbancy)

Being dissolved in solvent by the mixture 0.35g of salt or saliferous makes volume become 250cm ³, with solvent cut 2cm wherein ³volume is made to become 100cm ³, be adjusted to the solution of concentration 0.028g/L.About this solution, use ultraviolet-visible pectrophotometer (V-650DS; Japan's light splitting (strain) system) (quartz container, optical length, 1cm) be determined at the absorbancy of maximum absorption wavelength (λ max) and maximum absorption wavelength (λ max).The solvent used is shown in table 12 together with result.

[table 12]

Connect [table 12]

(deliquescent evaluation)

About the salt obtained respectively in embodiment 1 ~ 21 or the mixture containing salt, formula (d-1), formula (d-2), formula (h-1), formula (h-2), formula (h-83), formula (h-17), formula (h-82), formula (h-86), formula (h-105), formula (h-65), formula (h-66) and) and the compound that represents respectively of formula (h-67), alkaline purple 10, the compound that alkali violet 11:1 and formula (g-1) represent, try to achieve propylene glycol monomethyl ether (being slightly designated as PGMEA below) by following, propylene glycol monomethyl ether (being slightly designated as PGME below), ethyl lactate (being slightly designated as EL below), N, solubleness in dinethylformamide (being slightly designated as DMF below).

In 50ml sample hose, in following ratio by compound and above-mentioned solvent, then, fill in tight sample hose, vibrate 3 minutes with ultra-sonic oscillation machine at 30 DEG C.Then, after ambient temperatare puts 30 minutes, filter, its residue of visual observations.When not confirming insolubles residue, be judged as favorable solubility, when can confirm insolubles, be judged as that solvability is bad.The peak concentration being judged as favorable solubility is described in table 13.Result is as shown in table 13.× mean 1%, bad.

1% salt or mixture 0.01g, solvent 1g

3% salt or mixture 0.03g, solvent 1g

5% salt or mixture 0.05g, solvent 1g

7% salt or mixture 0.07g, solvent 1g

10% salt or mixture 0.10g, solvent 1g

20% salt or mixture 0.20g, solvent 1g

[table 13]

	Salt or mixture	PGMEA	PGME	EL	DMF
						Embodiment 1	I-1	5％	1％	1％	10％
Embodiment 2	I-3	7％	10％	10％	10％
						Embodiment 3	Containing the mixture of I-3	7％	10％	10％	10％
Embodiment 4	Containing the mixture of I-4	7％	10％	10％	10％
						Embodiment 5	I-5	×	×	1％	10％
Embodiment 6	I-6	5％	5％	5％	7％
						Embodiment 7	Containing the mixture of I-7	×	5％	7％	10％
Comparative example 1	d-1	×	×	×	10％
						Comparative example 2	d-2	×	×	×	7％
Embodiment 8	I-31	×	5％	10％	10％
						Comparative example 3	h-1	×	5％	7％	10％

Connect [table 13]

	Salt or mixture	PGMEA	PGME	EL	DMF
						Embodiment 9	I-32	×	5％	10％	10％
Comparative example 4	h-2	×	5％	7％	10％
						Embodiment 10	I-49	×	10％	10％	10％
Comparative example 5	h-83	×	5％	5％	7％
						Embodiment 11	I-39	7％	×	5％	10％
Comparative example 6	h-17	×	×	1％	5％
						Embodiment 12	I-48	15％	10％	10％	10％
Comparative example 7	h-82	×	5％	5％	7％
						Embodiment 13	I-51	1％	5％	5％	10％
Comparative example 8	h-86	×	×	×	5％
						Embodiment 14	I-8	×	3％	5％	10％
Comparative example 9	Alkali violet 11:1	×	×	×	5％
						Embodiment 15	I-7	×	7％	2％	7％
Comparative example 10	Alkaline purple 10	×	×	×	5％
						Embodiment 16	I-52	×	20％	20％	20％
Comparative example 11	h-105	×	×	1％	5％
						Embodiment 17	I-41	10％	7％	7％	10％
Comparative example 12	h-65	×	1％	1％	5％
						Embodiment 18	I-42	10％	7％	7％	10％
Comparative example 13	h-66	×	1％	1％	5％
						Embodiment 19	I-43	10％	7％	7％	10％
Comparative example 14	h-67	×	1％	1％	5％
						Embodiment 20	I-57	10％	7％	7％	10％
Embodiment 21	I-61	3％	×	×	7％
						Comparative example 15	g-1	×	×	×	3％

Embodiment 22

(preparation of coloured composition)

Mixing (A) tinting material: salt (I-1): the salt 20 parts that embodiment 1 is synthesized

(B-1) resin: methacrylic acid/benzyl methacrylate multipolymer (mol ratio; 30/70;

Weight-average molecular weight 10700, acid number 70mgKOH/g) 70 parts

(C-1) polymerizable compound: dipentaerythritol acrylate

(Japanese chemical drug society system) 30 parts

(D-1) Photoepolymerizationinitiater initiater: benzil dimethyl ketal (イ Le ガキユア

651; BASF ジヤパ Application society system) 15 parts

(E-1) solvent: DMF 680 parts

And obtain coloured composition.

(making of colour filter)

Adopt spin-coating method to coat on glass by the coloured composition of above-mentioned acquisition, volatile component is volatilized.After cooling, the figuratum silica glass photomask of apparatus and exposure machine carry out rayed.After rayed, with potassium hydroxide aqueous solution development, in baking oven, be heated to 200 DEG C, obtain colour filter.

Embodiment 23

Except the compound (I-1) of synthesis in embodiment 1 being replaced with the compound (I-3) of synthesis in embodiment 2, carry out the experiment identical with embodiment 3, obtain coloured composition and colour filter.

As can be known from the results of Table 2, the salt of embodiment demonstrates very high solubleness at organic solvent.Again, the generation of the coloured composition foreign matter containing this salt is few, can make high-quality colour filter.

Industry utilizes possibility

Claims

1. a salt, is characterized in that, is the n valency organometallic anions M of the atoms metal containing the metal ion that can form more than divalent ^n-, and derive from and can form the cationic salt of the dyestuff of salt with this organometallic anions,

And this organometallic anions has to derive from and can have substituent salicylic structure, and meet following prerequisite A for during compound shown in formula (1),

M ^n-nZ ⁺(1)

In formula (1), M ^n-represent described organometallic anions, Z ⁺represent hydrogen ion or alkali metal cation, n represents the integer of 1 ~ 3, when n is the integer of more than 2, and multiple Z ⁺can identical mutually also can be different,

Described positively charged ion is ammonium cation, oxo positively charged ion, sulfo group positively charged ion Huo phosphonium cation, is derive from the positively charged ion of triarylmethane dye or derive from the positively charged ion of xanthene dye,

2. salt according to claim 1, described n valency organometallic anions M ^n-in the contained atoms metal that can form the above metal ion of divalent be Al, Cr or Co.

3. a dyestuff, using the salt of claim 1 or 2 record as effective constituent.

4. a coloured composition, containing the dyestuff that claim 3 is recorded.