CN102618085A

CN102618085A - Salts and dyes

Info

Publication number: CN102618085A
Application number: CN2012100256733A
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: 2012-08-01
Anticipated expiration: 2032-01-17
Also published as: JP2012233151A; JP6019580B2; KR101940107B1; TW201237117A; CN102618085B; KR20120084262A; TWI516550B

Abstract

Provided is a salt, containing N-valent organic metal negative ion Mn- capable of forming metal atom of the bivalent-plus metal ion and Weng cationic capable of forming salt dyes with the organic metal negative ion. When the organic metal negative ion is the compound indicated in the formula (1) that meets specific requirements. The solvent performance of the salt in the organic solution is excellent.

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 for example filamentary material, liquid crystal indicator, ink-jet and recording materials etc.

As such dyestuff; Known for example have the open communique spy of Japanese Patent open the 2008-106111 communique and the open communique spy of Japanese Patent opens 2011-100114 communique and Wuhan University's journal, version of science, the 51st the 6th phase of volume, 699-703 page or leaf, 2005 as the compound of following formula (d-1) expression, the compound of formula (d-2) expression and the compound of formula (h-1) expression.

Summary of the invention

Satisfied the solvability organic solvent surely from differ sometimes with regard to known above-claimed cpd in the past.

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

[1] a kind of salt is characterized in that, is the n valency organo-metallic negatively charged ion M that contains the atoms metal that can form the above metals ion of divalent ^N-, and derive from can with the salt of the positively charged ion (oniumcation) of the salifiable dyestuff of this organo-metallic negatively charged ion shape, and this organo-metallic negatively charged ion satisfies following prerequisite A when being the compound shown in the formula (1).

M ^n-nZ ⁺ (1)

[in the formula (1), M ^N-Represent above-mentioned organo-metallic negatively charged ion.Z ⁺Expression hydrogen ion (hydron) or alkali metal cation.N representes 1～3 integer.When n is the integer more than 2, a plurality of Z ⁺Can be identical mutually also can be different.]

Prerequisite A: with the compound concentrations of formula (1) expression is that the absorbancy of the measured in solution of 0.028g/L is below 0.05 in 400～900nm district.

[2] salt of [1] record, said positively charged ion are positively charged ion, the positively charged ion that derives from triarylmethane (triarymethane) dyestuff, positively charged ion that derives from xanthene (xanthene) dyestuff that derives from cyanin (cyanine) dyestuff or the positively charged ion that derives from anthraquinone (anthraquinone) dyestuff.

[3] [1] perhaps [2] record salt, said n valency organo-metallic negatively charged ion M ^N-Be organo-metallic negatively charged ion with the structure that derives from following compound, said compound have a plurality of can have substituent Whitfield's ointment (salicylicAcid) or with the ethyloic (carboxymethyl) of amino bonded.

The salt of any record of [4] [1]～[3], said n valency organo-metallic negatively charged ion M ^N-In the contained atoms metal that can form the above metals ion of divalent be Al, Cr or Co.

[5] a kind of dyestuff, with the salt of any record in [1]～[4] as effective constituent.

[6] a kind of coloured composition contains the dyestuff that [5] are put down in writing.

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 organo-metallic negatively charged ion M that contains the atoms metal that can form the above metals ion of divalent ^N--and derive from can with the cationic salt of the salifiable dyestuff of this organo-metallic negatively charged ion shape, and this organo-metallic negatively charged ion satisfies following prerequisite A when being the compound (following claim sometimes " compound (1) ") that satisfies formula (1) expression.

M ^n-nZ ⁺ (1)

[in the formula (1), M ^N-Represent above-mentioned organo-metallic negatively charged ion.Z ⁺Expression hydrogen ion or alkali metal cation.N representes 1～3 integer.When n is the integer more than 2, a plurality of Z ⁺Can be the same or different.]

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

As can with the salifiable dyestuff of this organo-metallic negatively charged ion shape, 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. are arranged for example.Wherein, preferred anthocyanin dye, triarylmethane dye, xanthene dye and anthraquinone dye.Salt of the present invention like this constitutes through the positively charged ion that origin comes from dyestuff, shows as the useful color characteristics of dyestuff.

As positively charged ion, the ammonium cation that for example derives from above-mentioned dyestuff respectively, oxo positively charged ion, sulfo group positively charged ion 、 phosphonium cation etc. are arranged for example.

Below, just constitute the positively charged ion of salt of the present invention, enumerate the concrete illustration of the dyestuff that becomes its source.

As the positively charged ion that derives from anthocyanin dye, have for example for example to have respectively with the positively charged ion of the skeleton of formula (1-1)～formula (1-42) expression etc.Also have, " n-Pr " expression n-propyl in the formula, " n-Bu " representes normal-butyl, " s-Bu " representes sec.-butyl.

As anthocyanin dye, have for example respectively with the positively charged ion of formula (1-1)～formula (1-42) expression and the salt that above-mentioned counter anion forms.As counter anion, halide ions (for example Cl-, Br-, I-) is arranged for example, 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.

Derive from the cationic dyestuff of triarylmethane dye as guiding, for example have for example respectively that, C.I. alkaline purple 1 red 9 with C.I. alkalescence, C.I. alkalescence are purple 2, C.I. alkaline purple 3, C.I. alkalescence are purple 4, C.I. alkaline purple 13, C.I. basic violet 14, C.I. alkalescence are purple 23, the pigment of C.I. reflex blue 1, C.I. reflex blue 5, C.I. Blue 7, C.I. reflex blue 8, C.I. reflex blue 11, C.I. reflex blue 15, C.I. reflex blue 18, C.I. reflex blue 20, C.I. reflex blue 21, C.I. reflex blue 24, C.I. alkali blue 26, C.I. 4 b,asi,c g,ree,n 41, C.I. 4 b,asi,c g,ree,n 44 and following formula (g-1)～(g-7) expression.In addition, also can have for example the dyestuff of the presoma that can become them, like C.I. solvent blue 5 (can become the presoma of C.I. Blue 7) etc.

So-called guiding derive from xanthene dye cationic dyestuff, be that xanthene dye is the general name that intramolecularly has the dyestuff of xanthene skeleton.Preferably on this xanthene skeleton, having one at least can substituted amino, and more preferably having two can substituted amino.The positively charged ion that salt of the present invention contained preferably can substituted amino nitrogen-atoms be positively charged ion with the structure of carrying positive charge, more preferably imines positively charged ion.

As related xanthene dye, eosin (Eosin) based dye, resorcinolphthalein (Fluorescein) based dye, rhodamine (Rhodamine) based dye, pyronine (Pyronine) based dye, red alkalescence (Rosamine) based dye etc. are arranged for example.Again, for example just like at Synlett, 2010, No., the Sauerstoffatom of the xanthene skeleton of p.89-92 being put down in writing is by the substituted rhodamine of sulphur atom, selenium atom or tellurium atom (Rhodamine) based dye or red alkalescence (Rosamine) based dye etc.

Xanthene dye has Cl-or PF usually ₆ ^-Deng inorganic anion, perhaps have carboxylic acid ion (COO in the molecule ^-) or sulfonate ion (SO ₃ ^-) acidic-group that waits.The former situation, xanthene dye are so-called basic dyestuffs, and the positively charged ion that derives from xanthene dye has normally been removed the positively charged ion of part or all (all preferred) inorganic anion from xanthene dye.The latter's situation, xanthene dye are so-called inner salt, derive from the positively charged ion of the structure that the acidic groups that inside salt that the positively charged ion of xanthene dye normally relates to has part or all (all preferred) be neutralized.Here, acidic groups for example is 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 ₃H) or its salt (SO ₃Na etc.).

In the xanthene dye,, C.I. alkalescence red 2 with C.I. alkali red 1:1, C.I. alkalescence as specifically giving an example of basic dyestuff is red 3, C.I. alkalescence is red 4, alkalescence is red 8, the dyestuff of 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) expression etc.

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

Derive from the cationic dyestuff of anthraquinone dye as guiding, C.I. reflex blue 22, C.I. Basic Blue 35, C.I. reflex blue 45, C.I. reflex blue 47 etc. are arranged for example.

The anionic compound (1) of guiding salt of the present invention satisfies following prerequisite A.

Prerequisite A: with the concentration of compound (1) is that the absorbancy of the measured in solution of 0.028g/L is below 0.05 in 400～900nm district.

Make compound (1) be dissolved in ethyl lactate, chloroform, N, in any in dinethylformamide, ion exchanged water, methyl alcohol, ethanol and the toluene, make the solution that is used to measure absorbancy.

Absorbancy for this measured in solution 400～900nm.This absorbancy, is preferably below 0.035 below 0.05 in the whole zone of 400～900nm, and is further preferred below 0.005.

Satisfy prerequisite A through compound (1), salt of the present invention has maintenance as the color characteristics of cationic dyestuff and in the excellent tendency of the solvability of organic solvent.

Basic metal with in the compound of formula (1) expression has sodium and potassium etc. for example.

M ^n-nZ ⁺ (1)

[in the formula (1), M ^N-Expression contains the n valency organo-metallic negatively charged ion of the above atoms metal of divalent.Z ⁺Expression hydrogen ion or alkali metal cation.N representes 1～3 integer.When n is the integer more than 2, a plurality of Z ⁺Can be the same or different each other.]

Above-mentioned organo-metallic negatively charged ion has between the atoms metal that can form the above metals ion of divalent and the organic cpds through ionic linkage or co-ordination bond bonded structure.

As above-mentioned organic cpds, have for example and can have substituent Whitfield's ointment, have the ethyloic of a plurality of and amino bonded compound, can have substituent benzilic acid, can have substituent racemic melic acid and can have substituent VPP etc.As organo-metallic negatively charged ion M ^N-, the organo-metallic negatively charged ion that preferably has the structure that derives from compound, said compound have a plurality of can have substituent Whitfield's ointment or with the compound of the ethyloic of amino bonded.

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

Compound as the ethyloic with a plurality of and above-mentioned amino bonded for example has for example

Deng.

As having said substituent benzilic acid, for example have for example

etc.

As having above-mentioned substituent racemic melic acid, for example have for example

Deng.

As having above-mentioned substituent VPP, for example have for example

Deng.

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

Especially, preferred Al, Cr and Co.

As the negatively charged ion M that constitutes compound (1) ^N-, for example negatively charged ion (c-1)～negatively charged ion (c-72) etc. is arranged for example.

[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, salt then of the present invention has in the excellent tendency of the dissolving of organic solvent.

As salt of the present invention, salt (I-1) salt (I-60) etc. is for example arranged for example.

[table 10]

Salt	Derive from the positively charged ion of dyestuff	M ^n-
			Salt (I-1)	The positively charged ion of formula (1-2) expression	c-28
Salt (I-2)	The positively charged ion of formula (1-10) expression	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 reflex 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 reflex blue 22	c-28
			Salt (I-11)	The positively charged ion of formula (1-18) expression	c-2
Salt (I-12)	The positively charged ion of formula (1-10) expression	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 reflex 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 reflex blue 22	c-2
			Salt (I-21)	The positively charged ion of formula (1-18) expression	c-53
Salt (I-22)	The positively charged ion of formula (1-10) expression	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 reflex 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 reflex blue 22	c-62

[table 11]

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

Connect [table 11]

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

Salt of the present invention can be made through mixing colouring agent in solvent and compound (1).

The solvent that uses during as mixing; N is arranged for example; Dinethylformamide, DMAC N,N, N-Methyl pyrrolidone, methyl-sulphoxide, acetonitrile, vinyl acetic monomer, toluene, methyl alcohol, ethanol, Virahol, acetone, THF 、 diox, water and chloroform etc.

Especially, preferred N, dinethylformamide, DMAC N,N, 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, be dissolved in the solvent, can add acid such as acetic acid or hydrochloric acid in order to make dyestuff and compound (1).

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

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

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

When being used for the blended solvent, in this solution, add ion exchanged water, further stirred 1～3 hour for the solvent that dissolves with water.Then, obtain precipitate, just can obtain salt of the present invention through filtration.As required, can use the IX water washing.

When being used for the blended solvent, in this solution, add ion exchanged water, further stirred 1～3 hour for the solvent that do not dissolve with water.Then, obtain organic layer, just can obtain containing the solution of salt of the present invention through separatory.As required, can use the IX water washing.Desolvate through removing, can obtain salt of the present invention from the solution that contains salt of the present invention.

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

Dyestuff can use commercially available article; For example thin Tian Fengzhu " the theoretical dyestuff chemistry of making ", skill newspaper hall, 396～402,357～366,369～377 and 235～241 pages, pine occupy and are just setting prison and repair that " functional pigmented synthetic and utilisation technology ", シ one エ system シ one publish, 89～96 pages, Synlett, and 2010, No.1; P.89-92, J.Organic Chemistry; 2008, Vol.73, the material that the known method of record such as 8711-8718 is made.

Compound (1) can use commercially available article; For example fair 8-10360 of Japanese Patent Laid or the special that kind of opening record in 2002-258537 and 5 editions 22 volumes of the experimental chemistry lecture 312-313 page or leaf etc., vitriol that can be through making the compound that becomes ligand and metal or muriate react to be made.

The salt of the present invention that obtains like this is useful as dyestuff.Again, the solvability of dyestuff of the present invention in organic solvent is high, and be therefore, especially useful as the dyestuff that in the colour filter of display unit such as liquid crystal indicator, uses.

Dyestuff of the present invention is to be the dyestuff of effective constituent with salt of the present invention.

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

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

The dyestuff that is different from dyestuff of the present invention have for example be classified as in the Colour Index (Colour Index) (The Society of Dyers andColourists publication) solvent (Solvent), acid (Acid), alkali (property) (Basic), active (reactive), directly (Direct), disperse the dyestuff of (Disperse) or reduction (Vat) etc.More specifically, the dyestuff of the following Colour Index (C.I.) number of can giving an example, but be not limited to these.

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

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

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

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

C.I. DISPERSE YELLOW 54,76;

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

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

C.I. reactive orange 16;

C.I. direct orange s 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, and 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. 4 b,asi,c g,ree,n 41;

C.I. 1, Va,t g,ree,n 11 etc.

Pigment can be enumerated, and is generally used for the pigment dyestuff or the mineral dye of colo(u)rant dispersion resist.Mineral dye can be enumerated, and the metallic compound of MOX or metallic complex salt class can be enumerated MOX or 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 be given an example, and in Colour Index (Colour Index) (The Society of Dyers and Colourists publication), are classified as the compound of pigment (Pigment).More specifically, the pigment of the following Colour Index (C.I.) of can giving an example numbering, but and do 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.

The content of tinting material (A) is 5～60 quality % with respect to the solids component in the coloured composition preferably.Here, solids component is meant the total of the composition outside desolventizing in the coloured composition.

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

Dyestuff different with dyestuff of the present invention and pigment can be distinguished individually or make up more than 2 kinds and also use with dyestuff of the present invention.

Resin (B) is not special to be limited, and can use any resin.Resin (B) is alkali soluble resin preferably, more preferably contains the resin of the structural unit of being derived by (methyl) vinylformic acid.Here, (methyl) vinylformic acid is represented vinylformic acid and/or methylacrylic acid.

Resin (B) specifically has methylacrylic acid/methylacrylic acid benzene methyl multipolymer, methylacrylic acid/methylacrylic acid benzene methyl/styrol copolymer, methylacrylic acid/methylacrylic acid benzene methyl/isobornyl methacrylate multipolymer, methylacrylic acid/styrene/methacrylic acid benzene methyl N-phenyl maleic anhydride contract imine copolymer, methylacrylic acid/styrene/methacrylic acid glycidyl ester copolymer etc. for example.

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

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

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

Polymerizable compound (C) so long as living radical that can be through producing, acid etc. from polymerization starter (D) polymeric compounds is just not special limits.For example, the compound etc. that has polymerizability ethene property unsaturated link(age).

Said polymerizable compound (C) preferably has the polymerizable compound of 3 above polymerizable groups.Polymerizable compound with 3 above polymerizable groups can be given an example, 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 use separately or make up more than 2 kinds and use.

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

Above-mentioned polymerization starter (D) living radical of can giving an example produces agent, acidogenic agent etc.Living radical produces the effect generation living radical of agent through heat or light.Above-mentioned living radical produces agent can exemplified by alkyl groups benzophenone compound, thioxanthone compound, triazine based compound, oxime compound etc.

Abovementioned alkyl benzophenone compound can be given an example, for example 2-methyl-2-morpholine-1-(4-methyl sulphonyl 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 compound can be given an example, for example 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxy-thioxanthone etc.

Above-mentioned triaizine compounds can be given an example, and for example 2,4-two (trichloromethyl)-6-(4-p-methoxy-phenyl)-1,3; 5-triazine, 2,4-two (trichloromethyl)-6-(4-methoxyl group naphthyl)-1,3,5-triazines, 2; 4-two (trichloromethyl)-6-(4-methoxyl-styrene)-1,3,5-triazines, 2,4-two (trichloromethyl)-6-(2-(5-methyl furan-2-yl) vinyl)-1; 3,5-triazine, 2,4-two (trichloromethyl)-6-(2-(furans-2-yl) vinyl)-1,3; 5-triazine, 2,4-two (trichloromethyl)-6-(2-(4-diethylamino-2-aminomethyl phenyl) vinyl)-1,3,5-triazines, 2; 4-two (trichloromethyl)-6-(2-(3, the 4-Dimethoxyphenyl) vinyl)-1,3,5-triazines etc.

Above-mentioned oxime compound can be given an example; O-acyl group oxime compound; Have for example; 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-yl] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-{2-methyl-4-(3; 3-dimethyl--2,4-dioxy cyclopentyl methoxyl group) benzoyl-}-9H-carbazole-3-yl] ethane-1-imines etc.

In addition, living radical produces agent and for example can use 2; 4,6-trimethylbenzoyl diphenyl phosphine oxide, 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, phenyl oxoethanoic acid methyl ester, two cyclopentadiene titanium compounds etc.

Above-mentioned acidogenic agent can be given an example, the salt 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., tosic acid nitrobenzyl ester (or salt) class, tosic acid benzoin ester (or salt) class etc.

Said polymerization starter can use separately also can make up use more than 2 kinds.

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

Solvent (E) can be given an example, ethers, aromatic hydrocarbon based, ketone, alcohols, ester class, amides etc.

Above-mentioned ethers can be given an example; THF, tetrahydropyrans, 1,4-dioxane, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol monomethyl propyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, TC, Diethylene Glycol single-butyl 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, Ucar 35 list ethyl ether acetic ester, Ucar 35 list propyl ether acetic ester, terepthaloyl moietie monomethyl ether acetate, ethylene glycol monomethyl ether acetate, TC acetic ester, Diethylene Glycol single-butyl ether acetic ester etc.

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

Above-mentioned ketone can be enumerated acetone, 2-butanone, 2-heptanone, 3-heptanone, dipropyl ketone, 4-methyl-2 pentanone, 4-hydroxy-4-methyl-2 pentanone, ketopentamethylene, pimelinketone etc.

Above-mentioned alcohols can be enumerated methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, hexalin, terepthaloyl moietie, USP Kosher etc.

Above-mentioned ester class can be enumerated vinyl acetic monomer; N-butyl acetate; Isobutyl acetate; Pentyl formate; Isoamyl acetate; Isobutyl acetate; Butyl propionate; Isopropyl butyrate; Ethyl n-butyrate; Butyl butyrate; Alkyl esters; Methyl lactate; Ethyl lactate; N-Butyl lactate; Methoxy Methyl Acetate; The Methoxy acetic acid ethyl ester; The Methoxy acetic acid butyl ester; The oxyethyl group ritalin; The oxyethyl group vinyl acetic monomer; 3-methoxypropionic acid methyl esters; 3-methoxy propyl acetoacetic ester; 3-ethoxy-propionic acid methyl esters; The 3-ethoxyl ethyl propionate; 2-methoxypropionic acid methyl esters; 2-methoxy propyl acetoacetic ester; 2-methoxy propyl propyl propionate; 2-ethoxy-propionic acid methyl esters; The 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-methoxyl group butylacetic acid ester; 3-methyl-3-methoxyl group butylacetic acid ester; Gamma-butyrolactone etc.

Above-mentioned amides can be enumerated N, dinethylformamide, DMAC N,N, N-Methyl pyrrolidone etc.

These solvents can use separately also can make up use more than 2 kinds.

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

Coloured composition of the present invention also can contain tensio-active agent, weighting agent, other macromolecular compounds as required, connects airtight promotor, inhibitor, UV light absorber, photostabilizer, chain move the various additives of agent etc.

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

In addition; The coloured composition that contains salt of the present invention; Can be applied to have colour filter as in the various machines related such as the display unit (for example, known liquid crystal indicator, organic El device etc.) of its a part of component parts, solid-state imager with known state with rendered image.

Embodiment

Below, according to embodiment the present invention is detailed." % " in embodiment and the comparative example and " part " short of special instruction just are meant quality % and mass parts.

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

Embodiment 1

(BONTRON (registered trademark) E-108, オリエ Application ト chemical industry (strain) (ORIENT CHEMICAL INDUSTRIES CO., LTD) system) are dissolved in N for 0.85 part, in 50 parts of the dinethylformamides, make solution (s1) with the compound of formula (1) expression.In addition, the compound (CasOrganic society system) of formula (d-1) expression is dissolved in N for 1.02 parts, in 10 parts of the dinethylformamides, makes solution (t1).Under 25 ℃, (s1) the middle solution that adds (t1) is warming up to 80 ℃ then, stirs 8 hours.After making this mixed solution be cooled to room temperature, add 500 parts of ion exchanged waters, further stirred 1 hour.Then, obtain precipitate through suction filtration,, obtain 1.18 parts of the salt that formula (I-1) representes with 100 parts of cleanings of ion exchanged water.

The evaluation of the salt of formula (I-1) expression

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

Also have, will be dissolved in the chloroform as the compound 0.35g that the formula (f-1) that raw material uses is represented, making volume is 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 beam split (strain) system) (quartz container, optical length; 1cm) be determined at the maximum absorption wavelength of 400～900nm and the absorbancy in the 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) system) of formula (f-1) expression is dissolved in N for 1.0 parts, in 70 parts of the dinethylformamides, makes 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) of formula (d-2) expression is dissolved in N for 3.92 parts, in 90 parts of the dinethylformamides, makes solution (t2).Under 25 ℃, (s2) the middle solution that adds (t2) is warming up to 80 ℃ then, stirs 8 hours.After making this mixed solution be cooled to room temperature, with 100 parts of saturated aqueous common salts, then add 1000 parts of ion exchanged waters, further stirred 1 hour.Then, obtain precipitate through suction filtration,, obtain 1.70 parts of the salt that formula (I-3) representes with 100 parts of ion exchanged waters and 100 parts of cleanings of hexane.

The evaluation of the salt of formula (I-3) expression

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

Embodiment 3

The compound (BONTRON (registered trademark) E-108, オリエ Application ト chemical industry (strain) system) of formula (f-1) expression is dissolved in N for 2.0 parts, in 120 parts of the dinethylformamides, makes solution (s3).In addition, blue 613 (mixture of C.I. solvent blue 5 and resin, オリエ Application ト chemical industry (strain) systems) of ORIENT (registered trademark) Oil are dissolved in N for 1.96 parts, in 24 parts of the dinethylformamides, make solution (t3).Under 25 ℃, (s3) the middle solution that adds (t3) is warming up to 80 ℃ then, stirs 8 hours.After making this mixed solution be cooled to room temperature, add 700 parts of ion exchanged waters, further stirred 1 hour.Then, obtain precipitate through suction filtration,, obtain 2.27 parts of the salt that formula (I-3) representes with 100 parts of cleanings of ion exchanged water.

Synthetic routine 1 of compound (1)

To 3,5,6-three chloro-salicylic acids add 250 parts of entry for 5.00 parts, and 60 degree stir down and dissolving, further add sodium hydroxide, and regulating pH is 7.Further be added on the solution that has dissolved 2.03 parts in chromium sulphate hydrate in 200 parts in the water, 90 degree stirred 5 hours down.After this mixed solution is cooled to room temperature, filter unreactedly 3,5,6-three chloro-salicylic acids add 500 parts of saturated aqueous common salts in the filtrating, stirred 1 hour.Obtain precipitate through suction filtration, clean with saturated aqueous common salt, as Z ⁺Be the mixture of hydrionic compound and composite and sodium ion composite, obtain 2.02 parts of the compounds of formula (f-2) expression.

Use the same method of representing with formula (f-1) of compound, the compound of mensuration formula (f-2) expression is in the absorbancy of maximum absorption wavelength and the maximum absorption wavelength of 400～900nm, and maximum absorption wavelength is 400nm, and absorbancy is 0.0066.

Synthetic routine 2 of compound (1)

To 3, the 5-dibromosalicylic acid adds 250 parts of entry for 10.00 parts, and 60 degree stir down and dissolving, further add sodium hydroxide, and regulating pH is 7.Further be added on the solution that has dissolved 2.90 parts in chromium sulphate hydrate in 400 parts in the water, 90 degree stirred 5 hours down.After this mixed solution is cooled to room temperature, filter unreactedly 3, the 5-dibromosalicylic acid adds 1000 parts in water in the filtrating, stirred 1 hour.Obtain precipitate through suction filtration, water cleans, as Z ⁺Be the mixture of hydrionic compound and composite and sodium ion composite, obtain 4.89 parts of the compounds of formula (f-3) expression.

Use the same method of representing with formula (f-1) of compound, the compound of mensuration formula (f-3) expression is in the absorbancy of maximum absorption wavelength and the maximum absorption wavelength of 400～900nm, and maximum absorption wavelength is 400nm, and absorbancy is 0.031.

Synthetic routine 3 of compound (1)

To 3,5,6-three chloro-salicylic acids add 150 parts of entry for 10.00 parts, and 60 degree stir down and dissolving, further add sodium hydroxide, and regulating pH is 7.Further be added on the solution that has dissolved 4.06 parts in Tai-Ace S 150 in 200 parts in the water, 90 degree stirred 5 hours down.After this mixed solution is cooled to room temperature, filter unreactedly 3,5,6-three chloro-salicylic acids add 500 parts of saturated aqueous common salts, stir 1 hour.Obtain precipitate through suction filtration, water cleans, as Z ⁺Obtain 6.02 parts of the compounds of formula (f-4) expression for the mixture of hydrionic compound and composite and sodium ion composite.

Use the same method of representing with formula (f-1) of compound, the compound of mensuration formula (f-4) expression is in the absorbancy of maximum absorption wavelength and the maximum absorption wavelength of 400～900nm, and maximum absorption wavelength is 400nm, and absorbancy is 0.0036.

Synthetic routine 4 of compound (1)

To 3, the 5-dibromosalicylic acid adds 250 parts of entry for 10.00 parts, and 60 degree stir down and dissolving, further add sodium hydroxide, and regulating pH is 7.Further be added on the solution that has dissolved 2.89 parts in Tai-Ace S 150 in 200 parts in the water, 90 degree stirred 6 hours down.After this mixed solution is cooled to room temperature, filter unreactedly 3, the 5-dibromosalicylic acid adds 1000 parts in water in the filtrating, stirred 1 hour.Obtain precipitate through suction filtration, water cleans, as Z ⁺Be the mixture of hydrionic compound and composite and sodium ion composite, obtain 10.02 parts of the compounds of formula (f-5) expression.

Use the same method of representing with formula (f-1) of compound, the compound of mensuration formula (f-5) expression is in the absorbancy of maximum absorption wavelength and the maximum absorption wavelength of 400～900nm, and maximum absorption wavelength is 637nm, and absorbancy is 0.0049.

Synthetic routine 5 of compound (1)

To 2, the 4-resorcylic acid adds 250 parts of entry for 10.00 parts, and 60 degree stir down and dissolving, further add sodium hydroxide, and regulating pH is 7.Further be added on the solution that has dissolved 5.55 parts in Tai-Ace S 150 in 200 parts in the water, 90 degree stirred 6 hours down.After this mixed solution is cooled to room temperature, filter unreactedly 2, the 4-resorcylic acid adds 1000 parts in water in the filtrating, stirred 1 hour.Obtain precipitate through suction filtration, water cleans, as Z ⁺Obtain 6.51 parts of the compounds of formula (f-6) expression for the mixture of hydrionic compound and composite and sodium ion composite.

Use the same method of representing with formula (f-1) of compound, the compound of mensuration formula (f-6) expression is in the absorbancy of maximum absorption wavelength and the maximum absorption wavelength of 400～900nm, and maximum absorption wavelength is 400nm, and absorbancy is 0.022.

Synthetic routine 6 of compound (1)

To 2, the 5-resorcylic acid adds 250 parts of entry for 10.00 parts, and 60 degree stir down and dissolving, further add sodium hydroxide, and regulating pH is 7.Further be added on the solution that has dissolved 5.55 parts in Tai-Ace S 150 in 200 parts in the water, 90 degree stirred 6 hours down.After this mixed solution is cooled to room temperature, filter unreactedly 2, the 5-resorcylic acid adds 1000 parts in water in the filtrating, stirred 1 hour.Obtain precipitate through suction filtration, water cleans, as Z ⁺Obtain 10.01 parts of the compounds of formula (f-7) expression for the mixture of hydrionic compound and composite and sodium ion composite.

Use the same method of representing with formula (f-1) of compound, the compound of mensuration formula (f-7) expression is in the absorbancy of maximum absorption wavelength and the maximum absorption wavelength of 400～900nm, and maximum absorption wavelength is 400nm, and absorbancy is 0.048.

Embodiment 4

With the compound of formula (f-8) expression (BONTRON (registered trademark) E-81, オリエ Application ト chemical industry (strain) (system) are dissolved in N for 2.00 parts, in 150 parts of the dinethylformamides, making solution (s4).In addition, blue 613 (mixture of C.I. solvent blue 5 and resin, オリエ Application ト chemical industry (strain) systems) of ORIENT (registered trademark) Oil are dissolved in N for 1.80 parts, in 25 parts of the dinethylformamides, make solution (t4).Under 25 ℃, (s3) the middle solution that adds (t3) is warming up to 80 ℃ then, stirs 8 hours.After making mixed solution be cooled to room temperature.Add 500 parts of ion exchanged waters, further stirred 1 hour.Then, obtain precipitate through suction filtration,, obtain 2.11 parts of the salt that formula (I-4) representes with 100 parts of cleanings of ion exchanged water.

Embodiment 5

The compound of formula (f-3) expression is dissolved in N for 2.10 parts, in 150 parts of the dinethylformamides, makes solution (s5).In addition, (the CasOrganic society system) 1.99 parts of closing of formula (d-1) expression is dissolved in N, in 19 parts of the dinethylformamides, makes solution (t5).Under 25 ℃, (s5) the middle solution that adds (t5) is warming up to 80 ℃ then, stirs 8 hours.After making mixed solution be cooled to room temperature, add 500 parts of ion exchanged waters, further stirred 1 hour.Then, obtain precipitate through suction filtration,, obtain 2.50 parts of the salt that formula (I-5) representes with 100 parts of cleanings of ion exchanged water.

The evaluation of the salt of formula (I-5) expression

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

Embodiment 6

The compound of formula (f-4) expression is dissolved in N for 2.00 parts, in 150 parts of the dinethylformamides, makes solution (s6).In addition, the compound (CasOrganic society system) of formula (d-1) expression is dissolved in N for 1.49 parts, in 30 parts of the dinethylformamides, makes solution (t6).Under 25 ℃, (s6) the middle solution that adds (t6) is warming up to 80 ℃ then, stirs 8 hours.After this mixed solution is cooled to room temperature, add 50 parts of saturated aqueous common salts, stirred 1 hour, further add 300 parts of ion exchanged waters, stirred 2 hours.Then, obtain precipitate through suction filtration,, obtain 2.53 parts of the salt that formula (I-6) representes with 100 parts of cleanings of ion exchanged water.

The evaluation of the salt of formula (I-6) expression

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

Embodiment 7

The compound of formula (f-6) expression is dissolved in N for 1.60 parts, in 130 parts of the dinethylformamides, makes solution (s7).In addition, blue 613 (mixture of C.I. solvent blue 5 and resin, オリエ Application ト chemical industry (strain) systems) of ORIENT (registered trademark) Oil are dissolved in N for 1.98 parts, in 40 parts of the N-dimethyl-formyls, make solution (t7).Under 25 ℃, (s7) the middle solution that adds (t7) is warming up to 80 ℃ then, stirs 8 hours.After making mixed solution be cooled to room temperature, add 200 parts of saturated aqueous common salts, then add 600 parts of ion exchanged waters, further stirred 1 hour.Then, obtain precipitate through suction filtration,, obtain 1.31 parts of the salt that formula (I-7) representes with 100 parts of cleanings of ion exchanged water.

Embodiment 8

The compound (BONTRON (registered trademark) E-108, オリエ Application ト chemical industry (strain) system) of formula (f-1) expression is dissolved in N for 3.0 parts, in 200 parts of the dinethylformamides, makes solution (s8).In addition, the combination compound of following formula (h-1) expression is dissolved in N for 3.49 parts, in 40 parts of the dinethylformamides, makes solution (t8).Under 25 ℃, (s8) the middle solution that adds (t8) is warming up to 80 ℃ then, stirs 8 hours.After making mixed solution be cooled to room temperature, add 50 parts of saturated aqueous common salts, then add 300 parts of ion exchanged waters, further stirred 1 hour.Then, obtain precipitate through suction filtration,, obtain 3.15 parts of the salt that formula (I-31) representes with 100 parts of ion exchanged waters and 100 parts of cleanings of hexane.

The evaluation of the salt of formula (I-31) expression

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

Embodiment 9

The compound (BONTRON (registered trademark) E-108, オリエ Application ト chemical industry (strain) system) of formula (f-1) expression is dissolved in N for 1.50 parts, in 120 parts of the dinethylformamides, makes solution (s9).In addition, the combination compound of following formula (h-2) expression is dissolved in N for 1.30 parts, in 30 parts of the dinethylformamides, makes solution (t9).Under 25 ℃, (s9) the middle solution that adds (t9) is warming up to 80 ℃ then, stirs 6.5 hours.After making mixed solution be cooled to room temperature, add 100 parts of saturated aqueous common salts, then add 700 parts of ion exchanged waters, further stirred 1 hour.Then, obtain precipitate through suction filtration,, obtain 1.50 parts of the salt that formula (I-32) representes with 100 parts of ion exchanged waters and 100 parts of cleanings of hexane.

The evaluation of the salt of formula (I-32) expression

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

Embodiment 10

In 50 parts in 98% sulfuric acid, add 7.83 parts in 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 below 30 ℃ in mixing.Make the solution that obtains be cooled to 5 ℃, wherein add 5.37 parts of 3-(sec.-propyl is amino) phenol (according to the method manufacturing of the flat 9-169708 communique record of Japanese Patent Publication Laid-Open).Then, this mixture was stirred 65 hours down at 5 ℃.In 250 parts of frozen water, add reaction mixture, obtain precipitate through suction filtration.Dissolved residue in 180 parts of chloroforms adds 300 parts of ion exchanged waters, further uses 10% aqueous sodium hydroxide solution to make water layer be pH10, stirs 1 hour.Separation obtains chloroform layer, with 200 parts of ion exchanged waters, dewaters with sal epsom.Under reduced pressure, chloroform is removed in distillation from remove the solution that sal epsom obtains, and obtains 5.50 parts of the compounds of formula (hx-83) expression.

In 0.18 part of 3.00 parts of compounds, 3.16 parts of triethylene glycols (Tokyo changes into industry (strain) system), 0.24 part of dimethyl aminopyridine (with the pure pharmaceutical worker's industry of light (strain) system), (1s)-(+)-10-camphorsulfonic acid (Northeast chemistry (strain) system) of formula (hx-83) expression, add 30 parts of dehydration chloroforms, stirred 1 hour under the room temperature.Splash into 1.83 parts of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochlorides ((strain) colleague chemical research is made) are dissolved in the solution that forms in 7.2 parts of the chloroforms of dehydration,, stirred 5 hours under the room temperature so that be no more than 30 ℃.To this chloroformic solution,, dewater with sal epsom with 300 parts of 1N hydrochloric acid, then with 200 parts of separatory of 10% salt solution.Under reduced pressure, chloroform is removed in distillation from remove the solution that sal epsom obtains, and obtains 3.59 parts of the compounds of following formula (h-83) expression.

The compound (BONTRON (registered trademark) E-108, オリエ Application ト chemical industry (strain) system) of formula (f-1) expression is dissolved in N for 1.50 parts, in 120 parts of the dinethylformamides, makes solution (s10).In addition, the combination compound of following formula (h-83) expression is dissolved in N for 1.79 parts, in 100 parts of the dinethylformamides, makes solution (t10).Under 25 ℃, (s10) the middle solution that adds (t10) is warming up to 80 ℃ then, stirs 6 hours.After making mixed solution be cooled to room temperature, add 100 parts of saturated aqueous common salts, then add 700 parts of ion exchanged waters, further stirred 1 hour.Then, obtain precipitate through suction filtration, 100 parts of ion exchanged waters and 100 parts of cleanings of hexane obtain 1.93 parts of the salt of formula (I-49) expression.

The evaluation of the salt of formula (I-49) expression

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

Embodiment 11

Mix 1 under the room temperature; 1; 7; 7-tetramethyl--8-hydroxyl julolidine (with OrgacicLetters, the 10th No. the 21st, volume, 4799-4801 page or leaf, 2008. the method manufacturing of record) 1.20 parts in 15.00 parts, 250 parts of butyric acid, 4.50 parts of Tetra hydro Phthalic anhydrides (Tokyo changes into industry (strain) system) and 9.8% sulfuric acid, this mixing solutions is warming up to 140 ℃, stirred 15 hours.After making this mixed solution be cooled to room temperature, be injected in 3000 parts of the hexanes.Be dissolved in 340 parts of the chloroforms removing tarry solid that supernatant liquid obtains, to the chloroformic solution separatory, dewater with sodium sulfate with 300 parts of ion exchanged waters.Under reduced pressure, chloroform is removed in distillation from remove the solution that sal epsom obtains, and obtains 4.00 parts of the compounds of formula (hx-17) expression.

70 parts of 3.34 parts of 3.00 parts of the compounds, triethylene glycol of hybrid (hx-17) expression (Tokyo changes into industry (strain) system), 0.09 part of dimethyl aminopyridine (with the pure pharmaceutical worker's industry of light (strain) system), 0.14 part of (1s)-(+)-10-camphorsulfonic acid (Northeast chemistry (strain) system) and dehydration chloroforms stirred 1 hour under the room temperature.Splash into 1.38 parts of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochlorides ((strain) colleague chemical research is made) are dissolved in the solution that forms in 30 parts of the chloroforms of dehydration,, stirred 5 hours under the room temperature so that be no more than 30 ℃.To this chloroformic solution,, dewater with sal epsom with 50 parts of 1N hydrochloric acid, then with 50 parts of cleanings of 10% salt solution.Under reduced pressure, chloroform is removed in distillation from remove the solution that sal epsom obtains, and obtains 2.90 parts of the compounds of following formula (h-17) expression.

Compound (BONTRON (registrar) mark) E-108, the オリエ Application ト chemical industry (strain) (system) of formula (f-1) expression are dissolved in N for 1.07 parts, in 70 parts of the dinethylformamides, making solution (s11).In addition, the combination compound of following formula (h-17) expression is dissolved in N for 1.50 parts, in 70 parts of the dinethylformamides, makes solution (t11).Under 25 ℃, (s11) the middle solution that adds (t11) is warming up to 80 ℃ then, stirs 8 hours.After making mixed solution be cooled to room temperature, add 50 parts of saturated aqueous common salts, then add 300 parts of ion exchanged waters, further stirred 1 hour.Then, obtain precipitate through suction filtration,, obtain 1.50 parts of the salt that formula (I-39) representes with 100 parts of ion exchanged waters and 100 parts of cleanings of hexane.

The evaluation of the salt of formula (I-39) expression

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

Embodiment 12

In 0.58 part of 10.00 parts of alkaline purple 10 (rhodamine B, Tokyo change into industry (strain) system), 10.28 parts of triethylene glycol monomethyl ether (Tokyo changes into industry (strain) system), 0.77 part of dimethyl aminopyridine (with the pure pharmaceutical worker's industry of light (strain) system), (1S)-(+)-10-camphorsulfonic acid (Northeast chemistry (strain) system), add 120 parts of dehydration chloroforms, stirred 1 hour under the room temperature.Splash into 5.80 parts of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochlorides ((strain) colleague chemical research is made) are dissolved in the solution that forms in 49.3 parts of the chloroforms of dehydration,, stirred 5 hours under the room temperature so that be no more than 30 ℃.To this chloroformic solution,, dewater with sal epsom with 107 parts of 1N hydrochloric acid, then with 171 parts of separatory of 10% salt solution.Under reduced pressure, chloroform is removed in distillation from remove the solution that sal epsom obtains, and obtains 11.50 parts of the compounds of following formula (h-82) expression.

Compound with formula (h-82) expression under 25 ℃ is dissolved in N for 11.50 parts, and in 334 parts of the dinethylformamides, 11.12 parts of the compounds of adding type (f-1) expression (BONTRON (registered trademark) E-108, オリエ Application ト chemical industry (strain) system) stirred 4 hours.Add 1668 parts of ion exchanged waters, further stirred 1 hour.Then, obtain precipitate through suction filtration,, obtain 9.70 parts of the salt that formula (I-48) representes with 334 parts of ion exchanged waters and 100 parts of cleanings of hexane.

The evaluation of the salt of formula (I-48) expression

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

Embodiment 13

In 0.58 part of 10.00 parts of alkaline purple 10 (rhodamine B, Tokyo change into industry (strain) system), 5.89 parts of 1-amylalcohols (Northeast chemistry (strain) system), 0.77 part of dimethyl aminopyridine (with the pure pharmaceutical worker's industry of light (strain) system), (1S)-(+)-10-camphorsulfonic acid (Northeast chemistry (strain) system), add 120 parts of dehydration chloroforms, stirred 1 hour under the room temperature.Splash into 5.80 parts of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochlorides ((strain) colleague chemical research is made) are dissolved in the solution that forms in 49.3 parts of the chloroforms of dehydration,, stirred 5 hours under the room temperature so that be no more than 30 ℃.To this chloroformic solution,, dewater with sal epsom with 107 parts of 1N hydrochloric acid, then with 171 parts of separatory of 10% salt solution.Under reduced pressure, chloroform is removed in distillation from remove the solution that sal epsom obtains, and obtains 10.80 parts of the compounds of following formula (h-86) expression.

Compound with formula (h-86) expression under 25 ℃ is dissolved in N for 10.80 parts, and in 357 parts of the dinethylformamides, 11.89 parts of the compounds of adding type (f-1) expression (BONTRON (registered trademark) E-108, オリエ Application ト chemical industry (strain) system) stirred 4 hours.Add 1784 parts of ion exchanged waters, further stirred 1 hour.Then, obtain precipitate through suction filtration,, obtain 10.70 parts of the salt that formula (I-51) representes with 357 parts of ion exchanged waters and 100 parts of cleanings of hexane.

The evaluation of the salt of formula (I-51) expression

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

Embodiment 14

Under 25 ℃; C.I. alkali violet 11:1 (AizenCathilonBrilliantPinkCD-BH, hodogaya chemical industry (strain) system) is dissolved in N for 2.00 parts; In 66 parts of the dinethylformamides; 2.21 parts of the compounds of adding type (f-1) expression (BONTRON (registered trademark) E-108, オリエ Application ト chemical industry (strain) system) stirred 4 hours.Add 332 parts of ion exchanged waters, further stirred 1 hour.Then, obtain precipitate through suction filtration,, obtain 1.90 parts of the salt that formula (I-8) representes with 66 parts of ion exchanged waters and 100 parts of cleanings of hexane.

The evaluation of the salt of formula (I-8) expression

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

Embodiment 15

Compound (BONTRON (registrar) mark) E-108, オリエ Application ト chemical industry (strain) system with formula (f-1) expression) 2.29 parts be dissolved in N, in 92 parts of the dinethylformamides, making solution (s15).In addition, make that alkaline purple 10 (rhodamine B, Tokyo change into industry (strain) system) is dissolved in N for 8.00 parts, the solution (t15) that forms in 280 parts of the dinethylformamides.Under 25 ℃, (s15) the middle solution that adds (t15) is warming up to 40 ℃ then, stirs 8 hours.After making this mixed solution be cooled to room temperature, add 744 parts of ion exchanged waters, further stirred 1 hour.Then, obtain precipitate through suction filtration,, obtain 4.95 parts of the salt that formula (I-7) representes with 372 parts of ion exchanged waters and 100 parts of cleanings of hexane.

The evaluation of the salt of formula (I-7) expression

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

Embodiment 16

Making is dissolved in 2.00 parts of the compounds (rhodamine 101 inner salt, ACROSORGANICS society system) of formula (h-105) expression the solution (t16) that forms in 70 parts of the 6N hydrochloric acid.Compound (BONTRON (registered trademark) E-108), オリエ Application ト chemical industry (strain) system with formula (f-1) expression) 2.14 parts be dissolved in N, in 70 parts of the dinethylformamides, make solution (s16).Under 25 ℃, (s16) the middle solution that adds (t16) stirred 6.5 hours under the room temperature.With 225 parts of chloroforms this mixed solution is extracted 2 separatory, this chloroform is dewatered with sal epsom.From the solution that sal epsom obtains, chloroform is removed in decompression distillation down.With the oily mater that 20 parts of cleanings of hexane obtain, obtain 3.82 parts of the salt of formula (I-52) expression.

The evaluation of the salt of formula (I-52) expression

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

Embodiment 17

Under the ice bath, in 10.00 parts of alkaline purple 1s 0 (rhodamine B, Tokyo change into industry (strain) system), add 50 parts of chloroforms of dehydration, N, 3.05 parts of dinethylformamides, ice bath stirred 1 hour down.Drip under the ice bath 5.46 parts of THIONYL CHLORIDE 97s (with the pure pharmaceutical worker of light industry (strain) system) are warming up to 40 ℃ then, stir 3 hours.After being cooled to room temperature, 5.94 parts of the tetramethyleneimine that drips under the ice bath (with the pure pharmaceutical worker's industry of light (strain) system) are warming up to 40 ℃ then, stir 2 hours.After this mixed solution is cooled to room temperature, add 100 parts of ion exchanged waters and 150 parts of chloroforms, separatory is obtained chloroform layer.Add 150 parts of chloroforms in the water layer, separatory obtains chloroform layer.2 kinds of chloroform layers are merged, dewater with sal epsom.Decompression is down removed chloroform from removing the solution distillation that sal epsom obtains, and cleans resulting solids for 142 parts with vinyl acetic monomer, obtains 10.76 parts of the compounds that following formula (h-65) representes.

Compound (BONTRON (registrar) mark) E-108, オリエ Application ト chemical industry (strain) system with formula (f-1) expression) 9.86 parts be dissolved in N, in 394 parts of the dinethylformamides, be warming up to 80 ℃, making dissolved solution (s17).In addition, the combination compound of following formula (h-65) expression is dissolved in N for 10.00 parts, in 350 parts of the dinethylformamides, makes solution (t17).Under 80 ℃, (s17) the middle solution that adds (t17), 80 ℃ were stirred 6.5 hours down.After making this mixed solution be cooled to room temperature, add 1488 parts of ion exchanged waters, further stirred 1 hour.Then, obtain precipitate through suction filtration,, obtain 9.08 parts of the salt that formula (I-41) representes with 744 parts of ion exchanged waters and 383 parts of cleanings of hexane

The evaluation of the salt of formula (I-41) expression

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

Embodiment 18

Under the ice bath, in 10.00 parts of alkaline purple 1s 0 (rhodamine B, Tokyo change into industry (strain) system), add 50 parts of chloroforms of dehydration, N, 3.05 parts of dinethylformamides, ice bath stirred 1 hour down.Drip under the ice bath 5.46 parts of THIONYL CHLORIDE 97s (with the pure pharmaceutical worker of light industry (strain) system) are warming up to 40 ℃ then, stir 5.5 hours.After being cooled to room temperature, 7.11 parts of the piperidines that drips under the ice bath (with the pure pharmaceutical worker's industry of light (strain) system) are warming up to 40 ℃ then, stir 2 hours.After this mixed solution is cooled to room temperature, add 100 parts of ion exchanged waters and 150 parts of chloroforms, separatory is obtained chloroform layer.Add 150 parts of chloroforms in the water layer, separatory obtains chloroform layer.2 kinds of chloroform layers are merged, dewater with sal epsom.From removing the solution that sal epsom obtains, chloroform is removed in distillation under reduced pressure, obtains 11.93 parts of the compounds of following formula (h-66) expression.

Compound (BONTRON (registrar) mark) E-108, オリエ Application ト chemical industry (strain) system with formula (f-1) expression) 2.88 parts be dissolved in N, in 115 parts of the dinethylformamides, be warming up to 80 ℃, making dissolved solution (s18).In addition, the compound of following formula (h-66) expression is dissolved in N for 3.00 parts, in 105 parts of the dinethylformamides, makes solution (t18).Under 80 ℃, (s18) the middle solution that adds (t18), 80 ℃ were stirred 6.5 hours down.After making this mixed solution be cooled to room temperature, add 440 parts of ion exchanged waters, further stirred 1 hour.Then, obtain precipitate through suction filtration,, obtain 3.15 parts of the salt that formula (I-42) representes with 220 parts of ion exchanged waters and 114 parts of cleanings of hexane.

The evaluation of the salt of formula (I-42) expression

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

Embodiment 19

Under the ice bath, in 10.00 parts of alkaline purple 1s 0 (rhodamine B, Tokyo change into industry (strain) system), add 200 parts of chloroforms of dehydration, N, 3.05 parts of dinethylformamides, ice bath stirred 1 hour down.The THIONYL CHLORIDE 97 that drips under the ice bath (with 7.45 parts of the pure pharmaceutical worker's industry of light (strain) systems, is warming up to 40 ℃ then, stirred 5 hours.After being cooled to room temperature, 10.35 parts of the hexamethyl of dripping under ice bath imines (with the pure pharmaceutical worker's industry of light (strain) system) are warming up to 40 ℃ then, stir 2 hours.After this mixed solution is cooled to room temperature, add 200 parts of ion exchanged waters, 300 parts of chloroforms, 100 parts of saturated aqueous common salts, separatory is obtained chloroform layer, dewaters with sal epsom.Decompression is down removed chloroform from removing the solution distillation that sal epsom obtains, and cleans resulting solids for 132 parts with vinyl acetic monomer, obtains 12.37 parts of the compounds that following formula (h-67) representes.

Compound (BONTRON (registrar) mark) E-108, the オリエ Application ト chemical industry (strain) (system) of formula (f-1) expression are dissolved in N for 9.36 parts, in 375 parts of the dinethylformamides, are warming up to 80 ℃, making dissolved solution (s19).In addition, the combination compound of following formula (h-67) expression is dissolved in N for 10.00 parts, in 350 parts of the dinethylformamides, makes solution (t19).Under 80 ℃, (s19) the middle solution that adds (t19), 80 ℃ were stirred 6.5 hours down.After making this mixed solution be cooled to room temperature, add 1450 parts of ion exchanged waters, further stirred 1 hour.Then, obtain precipitate through suction filtration,, obtain 9.90 parts of the salt that formula (I-43) representes with 725 parts of ion exchanged waters and 374 parts of cleanings of hexane.

The evaluation of the salt of formula (I-43) expression

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

Embodiment 20

Compound with formula (h-66) expression under 25 ℃ is dissolved in N for 2.73 parts, and in 96 parts of the dinethylformamides, 2.75 parts of the compounds of adding type (f-8) expression (BONTRON (registered trademark) E-81, オリエ Application ト chemical industry (strain) system) stirred 16 hours.Add 383 parts of ion exchanged waters, further stirred 1 hour.Then, obtain precipitate through suction filtration,, obtain 3.06 parts of the salt that formula (I-57) representes with 96 parts of ion exchanged waters and 96 parts of cleanings of hexane.

The evaluation of the salt of formula (I-57) expression

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

Embodiment 21

Mix 20.0 parts of 3.30 parts of 3-bromine fluorobenzenes (Tokyo changes into industry (strain) system), 6.00 parts of diethylamine, 0.064 part of copper powder (Northeast chemistry (strain) system), 0.19 part of cupric iodide (I), 9.20 parts in Tripotassium phosphate n hydrate (Northeast chemistry (strain) system) and 2-(dimethylamino) ethanol (Tokyo changes into industry (strain) system) under the room temperature; Be warming up to 80 ℃, stirred 72 hours.After this mixed solution was cooled to room temperature, it was full with 150 parts of chloroforms to add 200 parts of entry, and separatory is obtained chloroform layer, dewaters with sal epsom.From removing the solution that sal epsom obtains, chloroform is removed in distillation under reduced pressure, obtains 2.06 parts of the compounds of following formula (gx-1) expression.

Mix N, 100 parts of 16.30 parts of N-diethylammonium-3-monomethylaniline (Tokyo changes into industry (strain) system), 19.00 parts of Methylal(dimethoxymethane) (Tokyo changes into industry (strain) system) and acetic acid.To drip 300 parts of acetic acid/98% sulfuric acid (1/1) mixture of this mixing solutions, stirred 10 minutes under the room temperature.Obtain precipitate through suction filtration,, obtain 10.04 parts of the compounds of following formula (gx-2) expression with 1000 parts of cleanings of ion exchanged water.

6.70 parts of the compounds of hybrid (gx-2) expression, 20 parts in potassium permanganate (Northeast chemistry (strain) system), 20 parts of copper sulfate (II) pentahydrates (Northeast chemistry (strain) system) stirred 6 hours under the room temperature.Add 200 parts of chloroforms, filtering separation chloroform extraction solution in this reactant.Chloroform is removed in decompression down distillation, obtains 6.20 parts of the compounds of following formula (gx-3) expression.

14.10 parts of the compounds of hybrid under the room temperature (gx-3) expression, 50 parts in 34.50 ones of the compounds of formula (gx-1) expression, hydroxyl phosphorus chloride (Northeast chemistry (strain) system) are warming up to 100 ℃, stir 3 hours.After this mixed solution is cooled to room temperature, join in the mixed solvent of 10 parts of 120 parts of vinyl acetic monomers/mistake chloric acid, stirred 1 hour.Obtain precipitate through suction filtration,, obtain 8.64 parts of the salt of following formula (g-1) expression with 200 parts of cleanings of vinyl acetic monomer.

Compound (BONTRON (registrar) mark) E-108, the オリエ Application ト chemical industry (strain) (system) of formula (f-1) expression are dissolved in N for 1.54 parts, in 61 parts of the dinethylformamides, making solution (s21).In addition, the salt of following formula (g-1) expression is dissolved in N for 1.50 parts, in 15 parts of the dinethylformamides, makes solution (t21).Under 25 ℃, (s21) the middle solution that adds (t21) stirred 2 hours under the room temperature.Add 382 parts of ion exchanged waters in this mixed solution, further stirred 1 hour.Then, obtain precipitate,, obtain 1.78 parts of the salt that formula (I-61) representes with 127 parts of cleanings of ion exchanged water through attracting filtration.

The evaluation of the salt of formula (I-61) expression

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

(mensuration of absorbancy)

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

[table 12]

Connect [table 12]

(deliquescent evaluation)

About the salt that obtains respectively at embodiment 1～21 or contain salt mixture, 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 represented of formula (h-67) compound, alkaline purple 10, alkali violet 11:1 and the formula (g-1) represent respectively; Try to achieve in propylene glycol monomethyl ether (the following PGMEA that slightly is designated as), propylene glycol monomethyl ether (the following PGME that slightly is designated as), ethyl lactate (the following EL that slightly is designated as), N, the solubleness in the dinethylformamide (the following DMF that slightly is designated as) by following.

In the 50ml sample hose, with compound and above-mentioned solvent, then, fill in tight sample hose in following ratio, vibrated 3 minutes with the ultra-sonic oscillation machine down at 30 ℃.Then, the room temperature held was filtered its residue of visual observations after 30 minutes.When not confirming the insolubles residue, be judged as favorable solubility, in the time of confirming insolubles, it is bad to be judged as solvability.Put down in writing the peak concentration that is judged as favorable solubility in the table 13.The 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	The mixture that contains I-3	7％	10％	10％	10％
Embodiment 4	The mixture that contains I-4	7％	10％	10％	10％
						Embodiment 5	I-5	×	×	1％	10％
Embodiment 6	I-6	5％	5％	5％	7％
						Embodiment 7	The mixture that contains 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)

Mix (A) tinting material: 20 parts of salt (I-1): embodiment 1 synthetic salt

(B-1) resin: methylacrylic acid/methacrylic acid benzylester 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 part

(E-1) solvent: N, 680 parts of dinethylformamides

And obtain coloured composition.

(making of colour filter)

It is on glass to adopt spin-coating method that the coloured composition of above-mentioned acquisition is coated, and makes the volatile component volatilization.After the cooling, figuratum silica glass system photomask of apparatus and exposure machine carry out rayed.After the rayed, develop, in baking oven, be heated to 200 ℃, obtain colour filter with potassium hydroxide aqueous solution.

Embodiment 23

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

Can know that from the result of table 2 salt of embodiment demonstrates very high solubleness at organic solvent.Again, the coloured composition production of foreign matters that contains this salt is few, can make high-quality colour filter.

Utilize possibility on the industry

Claims

1. a salt is characterized in that, is the n valency organo-metallic negatively charged ion M that contains the atoms metal that can form the above metals ion of divalent ^N-, and derive from can with the cationic salt of the salifiable dyestuff of this organo-metallic negatively charged ion shape,

And this organo-metallic negatively charged ion satisfies following prerequisite A when being the compound shown in the formula (1),

M ^n-nZ ⁺ (1)

In the formula (1), M ^N-Represent said organo-metallic negatively charged ion, Z ⁺Expression hydrogen ion or alkali metal cation, n representes 1～3 integer, when n is the integer more than 2, a plurality of Z ⁺Can be identical mutually also can be different,

2. according to the salt of claim 1 record, said positively charged ion is positively charged ion, the positively charged ion that derives from triarylmethane dye, positively charged ion that derives from xanthene dye that derives from anthocyanin dye or the positively charged ion that derives from anthraquinone dye.

3. the salt of putting down in writing according to claim 1 or 2, said n valency organo-metallic negatively charged ion M ^N-Be organo-metallic negatively charged ion with the structure that derives from following compound, said compound have a plurality of can have substituent Whitfield's ointment or with the ethyloic of amino bonded.

4. according to the salt of any record of claim 1～3, said n valency organo-metallic negatively charged ion M ^N-In the contained atoms metal that can form the above metals ion of divalent be Al, Cr or Co.

5. dyestuff, with the salt of any record in the claim 1～4 as effective constituent.

6. a coloured composition contains the dyestuff that claim 5 is put down in writing.