CN100406525C - Coloring composition for image formation and method for improving ozone resistance of color image - Google Patents

Abstract

A coloring composition for imaging comprises aromatic azo dye containing N-containing six member heterocyclic ring. A jet ink composition comprises the coloring composition is provided. Also provided is an ink jet recording method including jetting the jet ink composition onto an image receiving medium having a base sheet and an ink receiving layer containing inorganic white pigment particles to form an image.

Description

The method of coloured composition that imaging is used and raising color picture ozone resistants

The application is dividing an application of the Chinese patent application No.02808008.4 that submitted on April 8th, 2002.

Technical field

The present invention relates to coloured composition that a kind of imaging that includes the azoic dyestuff of specific physical properties and ad hoc structure uses and uses thereof, inkjet ink composition (ink composite that ink-vapor recording is used) for example, a kind of ink jet recording method, a kind of hot tranfer recording material, a kind of color toner, a kind of colour filter and a kind of method that improves ozone resistants.

Background technology

The material that forms color picture has surpassed the material that forms soot-and-whitewash.They have found various uses, for example ink jet recording materials, hot tranfer recording material, electrophotographic recording material, transfer printing type photographic silver halide material, marking ink, stylus and in solid-state image pickup such as charge-coupled device (CCD) and the colour filter in indicating meter such as liquid-crystal display (LCD) and plasma display dish (PDP).

These color image recording materials and colour filter use the tinting material (dyestuff and pigment) of additive or subtractive primary to realize panchromatic duplicating or record.Yet, have the absorption characteristic that is applicable to favourable color rendering and resist the tinting material of the patience of various working conditionss or envrionment conditions also not obtain at present.

Because low material cost, at a high speed, low noise and be easy to colored record, so ink-vapor recording is popularized fast and will be further developed.Basically, ink-vapor recording is divided into the continuous processing that makes the ink droplet non-stop flight and makes the demand of the ink droplet flight method of dripping by image information signal.The machinery that forms ink droplet comprises by piezoelectric element to be exerted pressure with the piezoelectric system of spraying ink droplet, is subjected to the thermogenesis bubble with the hot system of spraying ink droplet, sound system, suck or the electrostatic system of ejection ink droplet by electrostatic force to printing ink.Jetted ink comprises water color ink, oil-based ink and solid ink (fusion).

The tinting material that is used for jetted ink requires to have (1) in printing ink solvent good solubleness or dispersiveness, and (2) form the ability of high-density image, (3) satisfactory color, (NO for example of the reactive gas in (4) anti-light, heat, the environment _x, oxidizing gas such as ozone, SO _xDeng) colour fastness, the patience of (5) anti-water or chemical substance, (6) good stationarity on medium has minimized burr, (7) stability in the printing ink goods, (8) are nontoxic, the purity that (9) are high and (10) are inexpensive.The tinting material that all these requirements are satisfied in acquisition is extremely difficult.Wish that exploitation has the oxidizing gas in favourable pinkish red color and fast light, wet, heat and the environment such as the tinting material of ozone especially always.Having the place that forms image on the medium that contains porous white inorganic pigment particulate ink receiving layer, especially to pay close attention to anti-oxidant gaseousness.

Use the color copy machine of electrophotographic system and color laser printer often to use to have dyestuff or pigment to be scattered in color toner in the resin glue as tinting material.Color toner requires to have the absorption characteristic that is applicable to favourable color rendition, high transmittance (transparency), in particular for the colour fastness of elevated projecting (OHP) and anti-various environment for use conditions.Contain the toning agent that is scattered in the pigment in the particle and be disclosed in JP-A-62-157051 (term used herein " JP-A " be meant " examine disclosed Japanese patent application), JP-A-62-255956 and JP-A-6-11 871 5.Although have excellent photostabilization, these toning agents are difficult for molten, easily assemble, and can cause the color of transparency reduction or transmitted light to change like this.The toning agent that contains dyestuff is disclosed in JP-A-3-276161, JP-A-7-209912 and JP-A-8-123085.Although they have high transparency and color does not change, existing problems aspect photostabilization.

Thermal transfer recording system has following advantage: size is little, makes cost reduce, easy handling and maintenance, and running cost is low.The tinting material that is used for hot tranfer recording requires to have the absorption characteristic that is applicable to favourable color rendition, the balance between the stationarity after hot transfer printing performance and the transfer printing, thermostability and to the colour fastness of various factors.There are not a kind of all these requirements of satisfying in the known tinting material.For example, JP-A-60-2398 has proposed a kind of hot tranfer recording material and a kind of image formation method, wherein with a kind of thermodiffusion tinting material and the transition metal ion chelating that joins in the visual receiver media.Yet the absorption characteristic of the chelate compound of formation is unsatisfactory.And using transition metal also is problem to environment.

Colour filter requires to have high transparency, by producing with dyeing.For example, stainable photo-resist is through scheming decent exposure and develop to form the pattern of each color, and obtains colour filter with dyestuff continuous dyeing separately.As U.S. Pat 4,808,510 and JP-A-6-35182 in instruction, also by using positive resist to produce colour filter.Use the colour filter of DYE PRODUCTION to present excellent optical, have high transmittance, but limited to the patience of light and heat.Therefore need to have various resistances and the high dyestuff of transparency always.On the other hand, use method that the pigment dyestuff of anti-light and heat replaces the DYE PRODUCTION colour filter widely known to, but be difficult to obtain this optical characteristics with dyestuff.

The performance that used tinting material needs jointly in using above is the absorption characteristic that (1) is applicable to color rendition, (2) colour fastness of anti-various environment for use conditions, for example fast light, hot, wet, oxidizing gas such as ozone and chemical substance such as sulphurous acid gas and (3) big molar absorptivity.

The one-tenth colour content that has been widely used in azoic dyestuff comprises phenol, aphthols and phenyl amines.JP-A-11-209673 discloses with Japanese Patent 3020660 and has used these azoic dyestuffs that becomes colour content to obtain, and they have satisfactory color, but photostabilization is poor.Afterwards, Japanese patent application 2000-220649 had proposed to have the sunproof dyestuff of satisfactory color and raising.Yet, by known all these tinting materials of the document extremely unsatisfactory aspect the patience of the oxidizing gas of for example ozone.

When searching had the tinting material of gratifying resistance to oxidation gas such as ozone, the inventor had drawn and has used nitrogen-containing heterocycle compound as the thought that becomes colour content, abandons using the thought of conventional one-tenth colour content such as phenol, aphthols and phenyl amines.With contain pyridine and become colour content or pyrazine to become the relevant patent application of the azoic dyestuff of colour content to comprise JP-A-49-74718, EP23309 and DE 2513949, DE 2832020 and DE2525505.In these patent applications of application, do not know that these dyestuffs can be used for by imaging such as ink-vapor recordings; And it is deficiency aspect the reactive gas of disclosed these azoic dyestuffs in fast light, hot, wet and environment in these disclosed documents, and also not enough as the color of magenta dye.

Summary of the invention

An object of the present invention is to provide the coloured composition that a kind of imaging is used, it provides the color picture or the coloured material of color and colour fastness excellence, and suitable preparation marking ink, for example dye bath used of the printing ink sheet of jetted ink, hot tranfer recording material, color toner that electrophotography is used, the colour filter of using as the indicating meter of LCD and PDP and as the solid-state image pickup of CCD and fabric.

Another object of the present invention provides a kind of inkjet ink composition and a kind of ink jet recording method, and it can form the color picture with reactive gas, particularly ozone gas in satisfactory color and highly fast light and the environment.

A further object of the present invention provides a kind of hot tranfer recording material, and it provides the color picture that has high photostabilization and know color.

Another purpose of the present invention provides a kind of color toner, and it provides a kind of color picture with excellent photostabilization, high-quality color rendition and high-clarity to OHP.

Another purpose of the present invention provides the colour filter of a kind of color rendition and photostabilization excellence.

An also purpose of the present invention provides a kind of method of new raising color picture ozone resistants, and it is to use a kind of compound that favourable color rendering as one of three kinds of primary colors is had excellent absorption characteristic and the reactive gas in light, heat, humidity and the environment had enough resistances.

A further object of the present invention provides a kind of method that improves the color picture ozone resistants, a kind of coloured composition of color picture or coloured material of color and fastness excellence of providing is provided for it, for example is used in particular for the marking ink composition of ink-vapor recording.

Above described purpose can realize by the material described in following (1)-(20) and method.

Symbol " R used herein ^X" and symbol " R _X" difference, wherein X represents an integer.

Symbol " Z used herein ⁿ" and symbol " Z _n" difference, wherein n represents an integer.

(1) a kind of imaging coloured composition comprises and has the nitrogenous 6-of aromatics unit heterocyclic azoic dyestuff as the quality component.

(2) a kind of coloured composition comprises oxidizing potential than the high 1.0V of SCE and to contain at least two pKa values in water are substituent azo-compounds of-10 to 5.

(3) a kind of method that improves the color picture ozone resistants, this method comprise uses a kind of oxidizing potential than the high 1.0V of SCE and show maximum absorption under the wavelength of 500nm-580nm, and half breadth is 150nm or narrower compound simultaneously.

(4) as top (1) described imaging coloured composition, wherein said azoic dyestuff is represented by formula (1):

Wherein A represents the heterocyclic diazo component A-NH of 5-unit ₂Residue; B ¹And B ²Representative-CR respectively ¹=and-CR ²=, perhaps B ¹And B ²In any one represents nitrogen-atoms, another representative-CR ¹=or-CR ²=; R ⁵And R ⁶Represent hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxy carbonyl, aryloxycarbonyl, formamyl, alkyl sulphonyl, aryl sulfonyl or sulfamyl independently of one another, condition is R ⁵And R ⁶Different times table hydrogen atom, wherein each group can have a substituting group; And G, R ¹And R ²Represent hydrogen atom independently of one another, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl, formamyl, alkoxy carbonyl, aryloxycarbonyl, acyl group, hydroxyl, alkoxyl group, aryloxy, siloxy-, acyloxy, formamyl oxygen base, heterocyclic oxy group, alkoxy-carbonyl oxy, aryloxycarbonyl oxygen base, with an alkyl, the amino that aryl or heterocyclic radical replace, acyl amino, urea groups, sulfamyl amino, alkoxycarbonyl amino, aryloxycarbonyl amino, alkyl sulfonyl-amino, arlysulfonylamino, nitro, alkylthio, arylthio, alkyl sulphonyl, aryl sulfonyl, alkyl sulphinyl, aryl sulfonyl kia, sulfamyl, sulfo group or heterocycle sulfenyl, wherein each group can have a substituting group; Perhaps R ⁵Can with R ¹Or R ⁶Link to each other and form a 5-or 6-unit ring.

(5) as top (1) or (2) described imaging coloured composition, wherein said azoic dyestuff is represented by formula (2):

Z wherein ¹Representing Hammett substituent constant σ p value is 0.20 or bigger electron-withdrawing group; Z ²Represent hydrogen atom, aliphatic group, aromatic group or heterocyclic group; R ¹, R ², R ⁵And R ⁶As definition in the claim 1; R ³And R ⁴Represent hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxy carbonyl, aryloxycarbonyl, formamyl, alkylsulfonyl or sulfamyl independently of one another; And Q represents hydrogen atom, aliphatic group, aromatic group or heterocyclic group; Z wherein ¹, Z ², R ¹, R ², R ³, R ⁴, R ⁵, R ⁶Can have a substituting group with each group of Q representative.

(6) a kind of imaging coloured composition comprises the represented azoic dyestuff of formula (AZ-1):

Wherein encircle J, ring L and ring M and represent 5-or 6-unit aromatic ring independently of one another; 1,2,3 and 4 numberings that are meant four atoms; And at basis set 6-31G ^*Or under the higher basis set under the stable and stereoscopic structure of energy that the DFT/B3LYP method is determined by quantum chemistry calculation, by the interfacial angle 1-2-3-4 of this four former sub-definites of numbering between 45 °-135 °.

(7) as top (6) described imaging coloured composition, wherein said azoic dyestuff is represented by formula (AZ-2):

Wherein encircle J, ring L, ring M, ring T and ring U and represent 5-or 6-unit aromatic ring independently of one another; 1,2,3 and 4 numberings that are meant four atoms; And at basis set 6-31G ^*Or under the higher basis set under the stable and stereoscopic structure of energy that the DFT/B3LYP method is determined by quantum chemistry calculation, by the interfacial angle 1-2-3-4 of this four former sub-definites of numbering between 45 °-135 °.

(8) as top (7) described imaging coloured composition, wherein encircling U is to replace or unsubstituted phenyl ring; Ring T is thiazole ring, imidazole ring Huo oxazole ring; Ring U and ring T condense each other; Ring J replaces or unsubstituted pyrazoles ring, replacement or unsubstituted imidazole ring, replacement or unsubstituted triazole ring, replacement or unsubstituted phenyl ring or replacement or unsubstituted pyrimidone ring; Ring L replaces or unsubstituted phenyl ring, replacement or unsubstituted pyridine ring or replacement or unsubstituted pyrazoles ring; And ring M replaces or unsubstituted aromatic ring or replacement or the first heterocycle of unsubstituted nitrogenous 6-.

(9) as top (6) or (7) described imaging coloured composition, wherein interfacial angle 1-2-3-4 is between 60 °-120 °.

(10) a kind of inkjet ink composition, a kind of hot tranfer recording material, a kind of color toner or a kind of colour filter comprise each described coloured composition in top (4)-(9).

(11) a kind of ink jet recording method is included in and has a substrate and in one containing on the visual receiver media of inorganic white pigment particulate ink receiving layer of forming on this substrate, with as top (10) described inkjet ink composition form an image.

(12) as top (1) described imaging coloured composition, wherein said azoic dyestuff is represented by formula (3):

Wherein the Z representative forms the required atomic group of heterocycle with carbon atom, nitrogen-atoms, X and Y; X represents nitrogen-atoms, Sauerstoffatom or carbon atom; Y represents nitrogen-atoms, Sauerstoffatom, sulphur atom or carbon atom, and condition is that Y is not a nitrogen-atoms when X is carbon atom; A ₁And A ₂Representative independently of one another replaces or unsubstituted carbon atom or nitrogen-atoms, and condition is A ₁And A ₂Different times table nitrogen-atoms and A ₂There is not nitro as substituting group; And R ₁, R ₂, R ₃And R ₄Represent hydrogen atom, alkyl, cycloalkyl, aralkyl, alkenyl, aryl, heterocyclic radical, alkylsulfonyl, acyl group, carboxyl or formamyl independently of one another, wherein each group can have a substituting group, and condition is R ₁And R ₂Different times table hydrogen atom, and R ₃And R ₄Different times table hydrogen atom.

(13) as top (1) described imaging coloured composition, wherein said azoic dyestuff is represented by formula (4):

Z wherein ₁Representative forms the required atomic group of heterocycle with carbon atom and sulphur atom; A ₁₁And A ₁₂Representative independently of one another replaces or unsubstituted carbon atom or nitrogen-atoms, and condition is A ₁₁And A ₁₂Different times table nitrogen-atoms; And R ₁₁, R ₁₂, R ₁₃And R ₁₄Represent hydrogen atom, alkyl, cycloalkyl, aralkyl, alkenyl, aryl, heterocyclic radical, alkylsulfonyl, acyl group, carboxyl or formamyl independently of one another, wherein each group can have a substituting group, and condition is R ₁₁And R ₁₂In at least one representative replace or unsubstituted aryl or replacement or unsubstituted heterocyclic and R ₁₃And R ₁₄Different times table hydrogen atom.

(14) as top (1) described imaging coloured composition, wherein said azoic dyestuff is represented by formula (5):

Z wherein ₂Representative forms the required atomic group of heterocycle with carbon atom and sulphur atom; R ₂₁Representative replaces or unsubstituted aryl or replacement or unsubstituted heterocyclic; R ₂₃And R ₂₄Represent hydrogen atom, alkyl, cycloalkyl, aralkyl, alkenyl, aryl, heterocyclic radical, alkylsulfonyl, acyl group, carboxyl or formamyl independently of one another, wherein each group can have a substituting group; And R ₂₅And R ₂₆Represent hydrogen atom or monovalence substituting group independently of one another.

(15) as top (1) described imaging coloured composition, wherein said azoic dyestuff is represented by formula (6):

Z wherein ₃Representative forms the required atomic group of heterocycle with carbon atom and sulphur atom; R ₃₁Representative replaces or unsubstituted aryl or heterocyclic radical; R ₃₃Represent alkyl, cycloalkyl, aralkyl, alkenyl, aryl, heterocyclic radical, alkylsulfonyl, acyl group, carboxyl or formamyl; R ₃₄Be H; And R ₃₅And R ₃₆Represent hydrogen atom or monovalence substituting group independently of one another.

(16) as top (2) described coloured composition, wherein said azo-compound is represented by formula (5-I):

Het(A ⁵)-N＝N-Het(B ⁵) (5-I)

Het (A wherein ⁵) monobasic 5-of representative or 6-unit heterocycle; And Het (B ⁵) heterocycle of representative formula (5-II) representative:

A wherein ₅₁And A ₅₂Represent carbon atom or nitrogen-atoms independently of one another, condition is their different times table nitrogen-atoms; R ⁵⁴And R ⁵⁵Represent hydrogen atom, halogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted aryl, halogen atom, carboxyl, formamyl, cyano group, alkoxy carbonyl or hydroxyl independently of one another; R ⁵⁶, R ⁵⁷, R ⁵⁸And R ⁵⁹Represent hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted aryl or replacement or unsubstituted heterocyclic independently of one another; Condition is that formula (5-I) has at least two pKa values in water and is-10 to 5 substituting group.

(17) a kind of inkjet ink composition comprises as (1), each described coloured composition in (2) and (4)-(16).

(18) a kind of ink jet recording method is included in a substrate and and contains on the visual receiver media of inorganic white pigment particulate ink receiving layer, sprays as top (1 7) described inkjet ink composition, forms an image.

(19) as the method for the ozone resistants of top (3) described raising color picture, wherein said compound is an azo-compound.

(20) as the method for the ozone resistants of top (19) described raising color picture, wherein said azo-compound is represented by formula (7):

A ⁶-N＝N-B ⁶ (7)

A wherein ⁶And B ⁶Representative independently of one another replaces or unsubstituted aryl or replacement or unsubstituted 5-or 6-unit heterocyclic radical.

First preferred implementation of the present invention comprises above-mentioned (1) and (4)-(15).

Second preferred implementation of the present invention comprises above-mentioned (16).

The 3rd preferred implementation of the present invention comprises above-mentioned (19) and (20) item.

The accompanying drawing summary

Fig. 1 has shown the absorption spectrum of Compound D 10 (solid line) and REF1 (dotted line).

Fig. 2 has shown the absorption spectrum of Compound D 13 (solid line) and REF2 (dotted line).

Detailed Description Of The Invention

First preferred implementation

Preferably have at least one phosphono and can be used in the formula (1) of the azo-compound of first preferred implementation of the present invention in representative, A represent the first heterocyclic diazo component A-NH of 5- ₂Residue.This 5-unit heterocyclic heteroatoms comprises N, O and S.The preferably nitrogenous 5-of heterocycle A unit heterocycle.This heterocycle can have one with its condensed aliphatic series ring, aromatic ring or heterocycle.

Heterocycle A preferably includes pyrazoles ring, imidazole ring, thiazole ring, isothiazole ring, thiadiazoles ring, benzothiazole ring, benzoxazole ring and benzisothiazole ring, and each ring can have substituting group.Preferably respectively by pyrazoles ring, imidazole ring, isothiazole ring, thiadiazoles ring and the benzothiazole ring of formula (a)-(f) representative.

R wherein ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹And R ²⁰Represent hydrogen atom separately or be selected from this paper back such as G, R ¹And R ²Described substituent substituting group.

In heterocycle (a)-(f), the isothiazole ring of the pyrazoles ring of preferred formula (a) or formula (b).The pyrazoles ring of special preferred formula (a).

B ¹And B ²Representative-CR respectively ¹=and-CR ²=, perhaps B ¹And B ²In any one represents nitrogen-atoms, another representative-CR ¹=or-CR ²=.B ¹And B ²Preferred representative-CR respectively ¹=and-CR ²

R ⁵And R ⁶Represent hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxy carbonyl, aryloxycarbonyl, formamyl, alkyl sulphonyl, aryl sulfonyl or sulfamyl separately, wherein each group can have a substituting group.R ⁵And R ⁶Preferably represent hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkyl sulphonyl or aryl sulfonyl separately; more preferably represent hydrogen atom, aromatic group, heterocyclic group, acyl group, alkyl sulphonyl or aryl sulfonyl, especially preferably represent hydrogen atom, aryl or heterocyclic group.Described each group can have substituting group.R ⁵And R ⁶Different times table hydrogen atom.

G, R ¹And R ²Represent hydrogen atom separately; halogen atom; aliphatic group; aromatic group; heterocyclic group; cyano group; carboxyl; formamyl; alkoxy carbonyl; aryloxycarbonyl; acyl group; hydroxyl; alkoxyl group; aryloxy; siloxy-; acyloxy; formamyl oxygen base; heterocyclic oxy group; alkoxy-carbonyl oxy; aryloxycarbonyl oxygen base; with an alkyl; the amino that aryl or heterocyclic radical replace; acyl amino; urea groups; sulfamyl amino; alkoxycarbonyl amino; aryloxycarbonyl amino; alkyl sulfonyl-amino; arlysulfonylamino; nitro; alkylthio; arylthio; the heterocycle sulfenyl; alkyl sulphonyl; aryl sulfonyl; alkyl sulphinyl; aryl sulfonyl kia; sulfamyl or sulfo group, wherein each group can have a substituting group.

Amino, acyl amino, urea groups, sulfamyl amino, alkoxycarbonyl amino, aryloxycarbonyl amino, alkylthio, arylthio or heterocycle sulfenyl that G preferably represents hydrogen atom, halogen atom, aliphatic group, aromatic group, hydroxyl, alkoxyl group, aryloxy, acyloxy, heterocyclic oxy group, replaces with an alkyl, aryl or heterocyclic radical.Amino or acyl amino that G more preferably represents hydrogen atom, halogen atom, alkyl, hydroxyl, alkoxyl group, aryloxy, acyloxy, replaces with an alkyl, aryl or heterocyclic radical.Preferred especially G represents hydrogen atom, fragrant amino or acyl amino.Each group G can have substituting group.

R ¹And R ²Preferably represent hydrogen atom, alkyl, alkoxy carbonyl, carboxyl, formamyl or cyano group separately.Each can have substituting group in these groups.

R ⁵Can with R ¹Or R ⁶Link to each other and form a 5-or 6-unit ring.

A, R ¹, R ², R ⁵, R ⁶The substituting group that can have with G comprises looks like G, R ¹And R ²Described atom (except that hydrogen atom) and group.

When the azo-compound of formula (1) representative was water-soluble dye, this compound was preferably at any A, R ¹, R ², R ⁵, R ⁶And have an ionic hydrophilic group on the G.Suitable ionic hydrophilic group comprises sulfo group, carboxyl and quaternary ammonium group.Preferred carboxyl and sulfo group.Preferred especially sulfo group.Carboxyl and sulfo group can be salt forms.The salifiable suitable counter ion of shape comprise alkalimetal ion (for example, sodium ion and potassium ion) and organic cation (for example tetramethyl guanidine ion).

Be described in more detail below G, R ¹And R ²The substituting group of representative.

Halogen atom comprises fluorine, chlorine and bromine.

Term " aliphatic group " comprises replacement or unsubstituted alkyl, replacement or unsubstituted alkenyl, replacement or unsubstituted alkynyl group and replacement or unsubstituted aralkyl.This aliphatic group can have branched structure or ring structure.Aliphatic group preferably contains 1-20, particularly 1-16 carbon atom.The aryl moiety of aralkyl is phenyl or naphthyl preferably, is more preferably phenyl.The suitable example of aliphatic group is methyl, ethyl, butyl, sec.-propyl, the tertiary butyl, hydroxyethyl, methoxy ethyl, cyano ethyl, trifluoromethyl, 3-sulfo group propyl group, 4-sulfo group butyl, cyclohexyl, benzyl, 2-styroyl, vinyl and allyl group.

Term " aromatic group " comprises and replacing or unsubstituted aryl.Aryl is phenyl or naphthyl preferably.More preferably phenyl.Aromatic group preferably contains 6-20, particularly 6-16 carbon atom.The suitable example of aromatic group be phenyl, right-tolyl, right-p-methoxy-phenyl, neighbour-chloro-phenyl-,-(3-sulfo group propyl group amino) phenyl.

Term used herein " heterocyclic group " comprise replacement with unsubstituted, it can be aliphatic ring, aromatic ring or with its condensed heterocycle.Heterocyclic group is 5-or 6-unit preferably.Suitable substituent on the heterocyclic group comprises aliphatic group, halogen atom, alkyl sulphonyl, aryl sulfonyl, acyl group, acyl amino, sulfamyl, formamyl and ionic hydrophilic group.The suitable example of heterocyclic group is 2-pyridyl, 2-thienyl, 2-thiazolyl, 2-[4-morpholinodithio base, 2-benzoxazolyl and 2-furfuryl group.

Term " formamyl " comprise replacement with unsubstituted.Suitable substituent on the formamyl comprises alkyl.The suitable example of formamyl is methylamino formyl radical and formyl-dimethylamino.

Term " alkoxy carbonyl " is meant and replaces or unsubstituted alkoxy carbonyl.Alkoxy carbonyl preferably contains 2-12 carbon atom.Ionic hydrophilic group is a suitable substituents.The example of alkoxy carbonyl is methoxycarbonyl and ethoxy carbonyl.

Term " aryloxycarbonyl " is meant and replaces or unsubstituted aryloxycarbonyl.The aryloxycarbonyl that preferably has 7-12 carbon atom.Suitable substituent on the aryloxycarbonyl comprises ionic hydrophilic group.Phenyloxycarbonyl is an example of aryloxycarbonyl.

Term " acyl group " comprises the acyl group and the unsubstituted acyl of replacement.Acyl group with 1-12 carbon atom is suitable.Ionic hydrophilic group is a suitable substituents.The suitable example of acyl group comprises ethanoyl and benzoyl.

Term " alkoxyl group " comprises the alkoxyl group and the unsubstituted alkoxyl group of replacement.The alkoxyl group that contains 1-12 carbon atom is suitable.Suitable substituent on the alkoxyl group comprises alkoxyl group, hydroxyl and ionic hydrophilic group.The example of alkoxyl group comprises methoxyl group, oxyethyl group, isopropoxy, methoxy ethoxy, hydroxyl-oxethyl and 3-carboxyl propoxy-.

Term " aryloxy " is meant and replaces or unsubstituted aryloxy.The aryloxy that preferably contains 6-12 carbon atom.Suitable substituent on the aryloxy comprises alkoxyl group and ionic hydrophilic group.The example of aryloxy is phenoxy group, right-methoxyl group phenoxy group and neighbour-methoxyl group phenoxy group.

Term " acyloxy " is meant and replaces or unsubstituted acyloxy.The acyloxy that preferably has 1-12 carbon atom.The suitable substituent of acyloxy comprises ionic hydrophilic group.The example of acyloxy is acetoxyl group and benzoyloxy.

Term " formamyl oxygen base " is meant and replaces or unsubstituted formamyl oxygen base.Substituting group on the formamyl oxygen base comprises alkyl.The example of formamyl oxygen base comprises N-methylamino formyl radical oxygen base.

Alkyl, aryl or heterocyclic radical on the amino that replaces can also have a substituting group.Alkylamino preferably contains 1-6 carbon atom.Substituting group on the alkylamino comprises ionic hydrophilic group.The example of alkylamino is methylamino and diethylamino.Arylamino preferably contains 6-12 carbon atom.Suitable substituent on the arylamino comprises halogen atom and ionic hydrophilic group.The example of arylamino is phenylamino and 2-chlorobenzene amino.

Term " acyl amino " comprise replacement with unsubstituted.The acyl amino that preferably contains 2-12 carbon atom.Ionic hydrophilic group is the substituent example on the acyl amino.The example of acyl amino comprises acetylamino, propionyl amino, benzoyl-amido, N-phenyl acetyl amino and 3,5-disulfo benzoyl-amido.

Term " urea groups " is meant and replaces or unsubstituted urea groups.The urea groups that preferably contains 1-12 carbon atom.The substituting group of urea groups comprises alkyl and aryl.The example of urea groups is a 3-methyl urea groups, 3,3-dimethyl urea groups and 3-phenyl urea groups.

Term " sulfamyl amino " expression replaces or unsubstituted sulfamyl amino.The substituting group of sulfamyl amino comprises alkyl.Sulfamyl amino comprises N, N-dipropyl sulfamyl.

Term " alkoxycarbonyl amino " is meant and replaces or unsubstituted alkoxycarbonyl amino.The alkoxycarbonyl amino that preferably has 2-12 carbon atom.Ionic hydrophilic group is a suitable substituents.Alkoxycarbonyl amino comprises ethoxy carbonyl amino.

Term " aryloxycarbonyl amino " comprises and replacing or unsubstituted aryloxycarbonyl amino.The aryloxycarbonyl amino that preferably has 7-12 carbon atom.Ionic hydrophilic group is a suitable substituents.The example of aryloxycarbonyl amino comprises phenyloxycarbonyl amino.

Term " alkyl sulfonyl-amino " and term " arlysulfonylamino " are meant respectively and replace or unsubstituted alkyl sulfuryl amino and replacement or unsubstituted arlysulfonylamino.Preferably contain those of 1-12 carbon atom.Alkyl-or the suitable substituent of arlysulfonylamino comprise ionic hydrophilic group.Alkyl-or the example of arlysulfonylamino comprise methylsulfonyl amino, N-phenyl methyl sulfuryl amino, benzenesulfonyl amino and 3-carboxyl phenyl sulfuryl amino.

Term " alkylthio ", " arylthio " and " heterocycle sulfenyl " are meant respectively and replace or unsubstituted alkylthio, replacement or unsubstituted arylthio and replacement or unsubstituted heterocycle sulfenyl.Preferably contain the alkyl of 1-12 carbon atom-, aryl-or heterocycle sulfenyl.Suitable substituent on these groups comprises ionic hydrophilic group.The example of these sulfenyls comprises methylthio group, thiophenyl and 2-pyridyl sulfenyl.

Term " alkyl sulphonyl " and " aryl sulfonyl " are meant respectively and replace or unsubstituted alkyl alkylsulfonyl and replacement or unsubstituted aryl sulfonyl.These examples of groups are methylsulfonyl and phenyl sulfonyl.

Term " alkyl sulphinyl " and " aryl sulfonyl kia " are meant respectively and replace or unsubstituted alkyl sulfinyl, for example methanesulfinyl and replacement or unsubstituted aryl sulfonyl kia, for example phenyl sulfinyl.

Term " sulfamyl " is meant and replaces or unsubstituted sulfamyl.Alkyl is a suitable substituents.Sulfamyl comprises dimethylamino alkylsulfonyl and two-(2-hydroxyethyl) sulfamyl.

In the azo-compound of formula (1) representative, those of preferred formula (2) representative.The azo-compound of formula (2) representative preferably has at least one phosphono.

In formula (2), Z ¹Representing Hammett substituent constant σ p value is 0.20 or bigger electron-withdrawing group.Z ¹This electron-withdrawing group of representative has preferred 0.30-1.0, more preferably 0.45-1.0, even the more preferably Hammett substituent constant σ p value of 0.60-1.0.Although suitable electron-withdrawing group Z will be enumerated in the back ¹But, Z ¹Preferably have acyl group, a 2-12 carbon atom of 2-12 carbon atom alkoxy carbonyl, nitro, cyano group, have 1-12 carbon atom alkyl sulphonyl, have 6-18 carbon atom aryl sulfonyl, have the formamyl of 1-12 carbon atom or have the haloalkyl of 1-12 carbon atom.Particularly preferably be cyano group in the middle of their, have the alkyl sulphonyl of 1-12 carbon atom or have the aryl sulfonyl of 6-18 carbon atom.Cyano group most preferably.

R ¹, R ², R ⁵And R ⁶Identical with top definition.

R ³And R ⁴Represent hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxy carbonyl, aryloxycarbonyl, formamyl, alkyl sulphonyl, aryl sulfonyl or sulfamyl separately.R ³And R ⁴Preferably represent hydrogen atom, aromatic group, heterocyclic group, acyl group, alkyl sulphonyl or aryl sulfonyl separately, more preferably represent hydrogen atom, aromatic group or heterocyclic group.

Z ²Represent hydrogen atom, aliphatic group, aromatic group or heterocyclic group.

Q represents hydrogen atom, aliphatic group, aromatic group or heterocyclic group.Q preferably represents and forms the required nonmetallic atom group of 5-to 8-unit ring, and it can be replacement or unsubstituted and saturated or undersaturated, preferably an aromatic ring or heterocycle.The preferred non-metallic atom that constitutes this ring comprises nitrogen, oxygen, sulphur and carbon.The example of 5-to 8-unit ring comprises phenyl ring, pentamethylene, hexanaphthene, suberane, cyclooctane, cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole ring, benzoglyoxaline Huan, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole Huan, oxane ring, tetramethylene sulfone ring and sulfane (thiane) ring.

Z ¹, Z ², R ¹, R ², R ³, R ⁴, R ⁵, R ⁶Can have substituting group with each group of Q representative.These substituting groups comprise as G, R ¹And R ²Described those, and ionic hydrophilic group.

Here sketch with regard to substituting group Z ¹The Hammett substituent constant σ p value of indication.The Hammett rule is the rule of thumb that L.P.Hammett proposed in nineteen thirty-five, thereby attempts discussing quantitatively reaction or the equilibrated influence of substituting group to benzene derivative, is considered to effective so far usually.Used substituent constant comprises σ p value and σ m value in the Hammett rule.These values can find in many general books, J.A.Dean (editor) for example, Lange ' s Handbook ofChemistry, the 12nd edition, McGraw-Hill (1979) and Kagaku-no-ryoiki, the 122nd phase special issue, the 96-103 page or leaf, Nankodo (1979).In the present invention, according to Hammett substituent constant σ p substituting group is limited or described.This does not also mean that required substituting group is limited to known in the literature those substituting groups of its σ p value, and required substituting group comprises that its σ p value does not find in the literature, but as if its σ p value falls into substituting group in the described scope when being fundamental measurement with the Hammett rule.Although formula of the present invention (1) and (2) comprise the compound that is not benzene derivative, the present invention uses measuring of the irrelevant substituent electronic effect of this σ p value conduct and the position of substitution.

Hammett substituent constant σ p value be 0.60 or bigger electron-withdrawing group comprise cyano group, nitro, alkyl sulphonyl (for example methylsulfonyl) and aryl sulfonyl (for example benzenesulfonyl).σ p value be 0.45 or bigger electron-withdrawing group also comprise acyl group (for example ethanoyl), alkoxy carbonyl (for example dodecyl oxygen base carbonyl), aryloxycarbonyl (for example-chlorophenoxy carbonyl), alkyl sulphinyl (for example n-propyl sulfinyl), aryl sulfonyl kia (for example phenyl sulfinyl), sulfamyl (for example N-ethyl sulfamyl and N, N-dimethylamino alkylsulfonyl) and haloalkyl (for example trifluoromethyl).

σ p value be 0.30 or bigger electron-withdrawing group also comprise acyloxy (for example acetoxyl group); formamyl (for example N-ethylamino formyl radical and N; N-dibutylamino formyl radical); halogenated alkoxy (for example trifluoromethoxy); halo aryloxy (for example penta fluoro benzene oxygen base); alkylsulfonyl oxygen base (for example methyl sulphonyl oxygen base); halogenated alkylthio (for example difluoro methylthio group); with two or more σ p values is 0.15 or the aryl that replaces of bigger electron-withdrawing group (for example 2,4-dinitrophenyl and five chlorophenyl); and heterocyclic radical (2-benzoxazolyl for example; 2-[4-morpholinodithio base and 1-phenyl-2-benzimidazolyl-).σ p value be 0.20 or bigger electron-withdrawing group also comprise halogen atom.

The azoic dyestuff of formula (1) representative preferably has following substituting group combination:

(a) R ⁵And R ⁶Preferably represent hydrogen atom, alkyl, aryl, heterocyclic radical, alkylsulfonyl or acyl group separately, more preferably represent hydrogen atom, aryl, heterocyclic radical or alkylsulfonyl, especially preferably represent hydrogen atom, aryl or heterocyclic radical, condition is R ⁵And R ⁶Different times table hydrogen atom.

(b) preferably hydrogen atom, halogen atom, alkyl, hydroxyl, amino or acyl amino of G is more preferably hydrogen atom, halogen atom, amino or acyl amino, especially preferably hydrogen atom, amino or acyl amino.

(c) preferably pyrazoles ring, imidazole ring, isothiazole ring, thiadiazoles ring or benzothiazole ring of A is more preferably pyrazoles ring or isothiazole ring, especially preferably the pyrazoles ring.

(d) B ¹And B ²Preferably be respectively-CR ¹=and-CR ²=, R wherein ¹And R ²Preferably hydrogen atom, halogen atom, cyano group, formamyl, carboxyl, alkyl, hydroxyl or alkoxyl group are more preferably hydrogen atom, cyano group, formamyl or alkyl separately.

In the compound of formula (1) representative, preferably at least one substituting group is selected from the compound of above-mentioned preferable range; More preferably a plurality of substituting groups are selected from the compound of preferable range separately; And preferred especially all substituting groups all are selected from the compound of preferable range separately.

Only in order to describe purpose (but being not limited thereto), below the specific examples of the azoic dyestuff of formula (1) representative is shown in.

Table 1

Table 1 (continuing)

Table 2

Table 3

Table 3 (continuing)

Table 3 (continuing)

Table 4

Table 4 (continuing)

Table 5

Table 5 (continuing)

Table 6

Table 7

Table 8

Table 9

Table 2-1

Table 2-2

Table 2-3

Table 2-4

Table 2-5

The synthetic example of the azoic dyestuff of following display type (1) representative.

Synthetic example 1

Synthesizing of compound a-1

1) intermediate a-1a's is synthetic

Under 5 ℃ internal temperature with 5-amino-3-tertiary butyl-4-cyano pyrazole (1) (8g, 48.7mmol), 15ml concentrated hydrochloric acid and 50ml water stirs.Portioning adds 3.36g (48.7mmol) Sodium Nitrite in this mixture in 10 minutes, then stirs 10 minutes under uniform temp, forms diazonium salt.Individually, 23.1g (40.6mmol) quality component (2) is put into three-necked flask, and add 50g sodium acetate, 50ml dimethyl formamide (DMF) and 50ml ethyl acetate and stirring.Under 5 ℃ internal temperature, in 10 minutes, above-mentioned diazonium salt solution is added drop-wise in this mixture.Add after the end, under this temperature, reaction mixture was stirred 30 minutes.(300ml) pours in the reaction mixture with saturated sodium-chloride water solution.Filter and collect the throw out that forms thus, obtain the compound a-1a of 24.2g (85%).

2) compound a-1 is synthetic

In 14.0g (20mmol) compound a-1a, add 4.4g (26mmol) hydridization agent (heterylating agent) (3), 2.8g salt of wormwood and 50ml N,N-DIMETHYLACETAMIDE (DMAc), under 100 ℃,, stir simultaneously this mixture heating up 1 hour.Reaction is cooled to room temperature with reaction mixture after finishing, and to wherein adding the 200ml saturated sodium-chloride water solution.Filter and collect the throw out that forms thus, and, obtain the azo-compound a-1 of 16.7g (80%) by the acetonitrile recrystallize.

λ _Max=545nm (DMF solution)

M/z (positive ion mode)=834

Synthetic example 2

Synthesizing of compound b-1

1g compound b-1a is scattered in the acetate and propionic acid mixture of 2/3 (volume) of 3.8ml, and this dispersion liquid is cooled to 0 ℃.41% nitrosyl-sulfuric acid that slowly adds 2.21g in this dispersion liquid then stirred 1 hour.Individually, 1.05g compound b-1b is dissolved in the mixture of 14ml DMF and 6ml ethyl acetate, and, then is cooled to 0 ℃ to wherein adding the 2.5g sodium acetate.The b-1a dispersant liquid drop that makes above is added in the b-1b suspension.After the dropping, reaction mixture was further reacted other 2 hours.Reaction adds entry after finishing in reaction mixture.Filter the crystallization of collecting precipitation, purify, obtain the dye composition b-1 of 750 mg (57.7%) by silica gel column chromatography.

λ _max＝545nm

Synthetic example 3

Dyestuff b-6's is synthetic

1g compound b-6a is scattered in the acetate and propionic acid mixture of 2/3 (volume) of 3.8ml, and this dispersion liquid is cooled to 0 ℃.41% nitrosyl-sulfuric acid that slowly adds 2.21g in this dispersion liquid then stirred 1 hour.Individually, 1.0g compound b-6b is dissolved in the mixture of 15ml DMF and 5ml ethyl acetate, and, then is cooled to 0 ℃ to wherein adding the 2.5g sodium acetate.The b-6a dispersant liquid drop that makes above is added in the b-6b suspension.After the dropping, reaction mixture was further reacted other 2 hours.Reaction adds entry after finishing in reaction mixture.The crystallization of filtration collecting precipitation also is dissolved among the 10ml DMF.In this solution, add 560mg salt of wormwood and 1.3g 2-chloro benzothiazole (b-6c), and this system was reacted 1 hour down at 110 ℃.Reaction adds entry after finishing.Filter the crystallization of collecting precipitation, purify, obtain the dye composition b-6 of 700mg (58.6%) by silica gel column chromatography.

λ _max＝550nm

Synthetic example 4

Compound 2-'s (a-6) is synthetic

1) intermediate 2-'s (a-6a) is synthetic

Under 5 ℃ internal temperature with 5-amino-3-tertiary butyl-4-cyano pyrazole 2-(1) (8g, 48.7mmol), 15ml concentrated hydrochloric acid and 50ml water stirs.Portioning adds 3.36g (48.7mmol) Sodium Nitrite in this mixture in 10 minutes, then stirs 10 minutes under uniform temp, forms diazonium salt.Individually, 14.6g (40.6mmol) quality component 2-(2) is put into three-necked flask, and add 50g sodium acetate and the stirring of 50ml pyrido.Under 5 ℃ internal temperature, in 10 minutes, above-mentioned diazonium salt solution is added drop-wise in this mixture.Drip after the end, under this temperature, reaction mixture was stirred 30 minutes.(300ml) pours in the reaction mixture with saturated sodium-chloride water solution.Filter and collect the throw out that forms thus, obtain the compound 2-(a-6a) of 24.2g (93%).

2) compound 2-'s (a-6) is synthetic

In 10.7g (20mmol) compound 2-(a-6a), add 15g (60mmol) hydridization agent 2-(3), 8.8g salt of wormwood and 50ml N,N-DIMETHYLACETAMIDE, under 100 ℃,, stir simultaneously this mixture heating up 1 hour.Reaction is cooled to room temperature with reaction mixture after finishing, and to the 1N HCl aqueous solution that wherein adds 200ml.Filter and collect the throw out that forms thus, and, obtain the azo-compound 2-(a-6) of 15.4g (80%) by the acetonitrile recrystallize.

λ _Max=558nm (dimethyl formamide solution)

M/z (positive ion mode)=960

In representing the formula of azo-compound of the present invention (3), the Z representative forms the required atomic group of heterocycle with carbon atom, nitrogen-atoms, X and Y; X represents nitrogen-atoms, Sauerstoffatom or carbon atom; And Y represents nitrogen-atoms, Sauerstoffatom, sulphur atom or carbon atom, and condition is that Y is not a nitrogen-atoms when X is carbon atom.

X preferably represents nitrogen-atoms or carbon atom.Y preferably represents nitrogen-atoms, carbon atom or sulphur atom.The preferred X and the Y combination of representing carbon atom or nitrogen-atoms that represents nitrogen-atoms.

The heterocycle that is obtained by X, Y and Z comprises pyridine ring, indole ring, imidazole ring, benzoglyoxaline ring, triazole ring, oxazole ring and benzoxazole ring, preferred imidazole ring and triazole ring.This heterocycle can have a substituting group at an arbitrary position.Substituting group on the heterocycle formation ring structure that can be connected with each other.Nitrogen-atoms on the heterocycle can be by seasonization.

Suitable substituent on the heterocycle comprises halogen atom; alkyl (comprising cycloalkyl and bicyclic alkyl); alkenyl (comprising cycloalkenyl and two cycloalkenyls); alkynyl group; aryl; heterocyclic radical; cyano group; hydroxyl; nitro; carboxyl; alkoxyl group; aryloxy; siloxy-; heterocyclic oxy group; acyloxy; formamyl oxygen base; alkoxy-carbonyl oxy; aryloxycarbonyl oxygen base; amino (comprising phenylamino); acyl amino; amino carbonyl amino; alkoxycarbonyl amino; aryloxycarbonyl amino; sulfamyl amino; alkyl sulfonyl-amino; arlysulfonylamino; sulfydryl; alkylthio; arylthio; the heterocycle sulfenyl; sulfamyl; sulfo group; alkyl sulphinyl; aryl sulfonyl kia; alkyl sulphonyl; aryl sulfonyl; acyl group; aryloxycarbonyl; alkoxy carbonyl; formamyl; the arylazo base; the heterocycle azo base; imino-; phosphino-; phosphinyl; phosphinyl oxygen base; phosphinyl amino and silyl.

Substituting group on the heterocycle is described in more detail.Halogen atom comprises chlorine, bromine and iodine.Term " alkyl " is meant and comprises replacement or not replacement, straight chain, side chain or cyclic alkyl, for example alkyl, cycloalkyl, bicyclic alkyl, tricyclic alkyl etc.Described alkyl under its narrow implication, preferably contains 1-30 carbon atom, comprises methyl, ethyl, n-propyl, sec.-propyl, the tertiary butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyano ethyl and 2-ethylhexyl.Cycloalkyl preferably contains 3-30 carbon atom, comprises cyclohexyl, cyclopentyl and 4-dodecyl cyclohexyl.Bicyclic alkyl preferably contains 5-30 carbon atom (that is, by remove the univalent perssad that a hydrogen atom obtains from two cycloalkanes with 5-30 carbon atom), comprises two ring [1,2,2] heptane-2-base and two ring [2,2,2] octane-3-bases.The term " alkyl " that occurs in the described substituting group in this paper back, for example " alkyl " in " alkylthio " has identical as mentioned above implication.

Term " alkenyl " is meant and replaces or do not replace, straight chain, side chain or cyclic alkenyl, comprise that alkenyl (preferably contains 2-30 carbon atom, vinyl for example, allyl group, general stupefied base (pulenyl), geranyl and oleyl), cycloalkenyl group (preferably contains 3-30 carbon atom, promptly from cyclenes, remove the univalent perssad that a hydrogen atom obtains with 3-30 carbon atom, for example 2-cyclopentenes-1-base and 2-tetrahydrobenzene-1-yl) and bicycloenyl (preferably have 5-30 carbon atom, promptly by from two cyclenes, removing the univalent perssad that a hydrogen atom obtains with two keys, for example two encircle [2,2,1] hept-2-ene"-1-base and two rings [2,2,2] oct-2-ene-4-yl).

Alkynyl group preferably has the replacement or the unsubstituted alkynyl group of 2-30 carbon atom, for example ethynyl, proyl and trimethyl silyl ethynyl.Aryl preferably has the replacement or the unsubstituted aryl of 6-30 carbon atom, for example phenyl, right-tolyl, naphthyl ,-chloro-phenyl-and neighbour-palmitoyl aminophenyl.Heterocyclic radical preferably by from replace or the 5-of not replacement, aromatics or non-aromatics or 6-membered heterocyclic compound remove the univalent perssad that a hydrogen atom obtains, be more preferably 5-or 6-unit aromatic heterocyclic group, for example 2-furfuryl group, 3-thienyl, 2-pyrimidyl and 2-[4-morpholinodithio base with 3-50 carbon atom.

Alkoxyl group preferably has the replacement or the unsubstituted alkoxyl group of 1-30 carbon atom, for example methoxyl group, oxyethyl group, isopropoxy, tert.-butoxy, n-octyloxy and 2-methoxy ethoxy.Aryloxy preferably has the replacement or the unsubstituted aryloxy of 6-30 carbon atom, for example phenoxy group, 2-methylphenoxy, 4-tertiary butyl phenoxy group, 3-nitro-phenoxy and 2-myristoyl amino-benzene oxygen.Siloxy-preferably contains 3-20 carbon atom, comprises trimethylsiloxy and t-butyldimethylsilyloxy base.Heterocyclic oxy group preferably contains the replacement or the unsubstituted heterocyclic oxy group of 2-30 carbon atom, for example 1-phenyltetrazole-5-oxygen base and 2-THP trtrahydropyranyl oxygen base.Acyloxy preferably includes formyl radical oxygen base; replacement or unsubstituted alkyl ketonic oxygen base with 2-30 carbon atom; for example acetoxyl group, valeryl oxygen base and stearyl-oxygen base; with replacement with 6-30 carbon atom or unsubstituted aryl carbonyl oxygen base, for example benzoyl oxygen base and right-p-methoxy-phenyl ketonic oxygen base.

Formamyl oxygen base preferably has the replacement or the unsubstituted formamyl oxygen base of 1-30 carbon atom; N for example; N-formyl-dimethylamino oxygen base, N; N-diethylacbamazine acyloxy, morpholinyl carbonyl oxygen base, N, N-two-n-octyl aminocarboxyl oxygen base and N-n-octyl formamyl oxygen base.Alkoxy-carbonyl oxy preferably has the replacement or the unsubstituted alkoxy-carbonyl oxy of 2-30 carbon atom, for example methoxycarbonyl oxygen base, ethoxy carbonyl oxygen base, tert-butoxycarbonyl oxygen base and n-octyl ketonic oxygen base.Aryloxycarbonyl oxygen base preferably has the replacement or the unsubstituted aryloxycarbonyl oxygen base of 7-30 carbon atom, for example phenyloxycarbonyl oxygen base, right-methoxyl group phenoxy group ketonic oxygen base and right-n-hexadecyl oxygen phenoxyl ketonic oxygen base.

Amino preferably includes unsubstituted amino, (for example have the replacement of 1-30 carbon atom or unsubstituted alkyl amino, methylamino, dimethylamino), phenylamino and have the substituted benzene amino (for example, N-methylbenzene amino and diphenyl amino) of 6-30 carbon atom.Acyl amino (for example preferably includes replacement with 1-30 carbon atom or unsubstituted alkyl carbonylamino; formyl radical amino, acetylamino, valeryl amino and lauroyl amino) and (for example have the replacement of 6-30 carbon atom or unsubstituted aryl-amino-carbonyl; benzoyl-amido, 3; 4,5-three n-octyl oxygen base phenylcarbonyl group amino).Amino carbonyl amino preferably includes replacement or the unsubstituted amino carbonyl amino with 1-30 carbon atom, for example formamyl amino, N, N-dimethylamino carbonylamino, N, N-diethylamino carbonylamino and morpholine carbonylamino.Alkoxycarbonyl amino preferably includes replacement or the unsubstituted alkoxycarbonyl amino with 2-30 carbon atom, for example methoxycarbonyl amino, ethoxy carbonyl amino, tert-butoxycarbonyl amino, positive octadecyl oxygen base carbonylamino and N-methyl-methoxycarbonyl amino.Aryloxycarbonyl amino preferably includes replacement or the unsubstituted aryloxycarbonyl amino with 7-30 carbon atom, for example phenyloxycarbonyl amino, right-chlorophenoxy carbonylamino and-(n-octyloxy) phenyloxycarbonyl amino.Sulfamyl amino preferably includes replacement or the unsubstituted sulfamyl amino that has up to 30 carbon atoms, for example sulfamyl amino, N, N-dimethylamino sulfuryl amino and N-n-octyl amino-sulfonyl amino.Alkyl sulfonyl-amino preferably includes replacement or the unsubstituted alkyl sulfuryl amino with 1-30 carbon atom, and for example methyl sulphonyl is amino and the butyl sulfuryl amino.Arlysulfonylamino preferably includes replacement or the unsubstituted arlysulfonylamino with 6-30 carbon atom, for example phenyl sulfonyl amino, 2,3,5-trichlorophenyl sulfuryl amino and right-aminomethyl phenyl sulfuryl amino.

Alkylthio preferably has the replacement or the unsubstituted alkylthio of 1-30 carbon atom, for example methylthio group, ethylmercapto group and positive hexadecyl sulfenyl.Arylthio preferably has the replacement or the unsubstituted arylthio of 6-30 carbon atom, for example phenyl sulfenyl, right-chloro-phenyl-sulfenyl and-the p-methoxy-phenyl sulfenyl.The heterocycle sulfenyl preferably has the replacement or the unsubstituted heterocycle sulfenyl of 2-30 carbon atom, for example 2-[4-morpholinodithio base sulfenyl and 1-phenyltetrazole-5-base sulfenyl.Sulfamyl preferably has up to the replacement of 30 carbon atoms or unsubstituted sulfamyl; for example N-ethyl sulfamyl, N-(3-dodecyl oxygen base propyl group) sulfamyl, N, N-dimethylamino alkylsulfonyl, N-ethanoyl sulfamyl, N-benzoyl sulfamyl and N-(N '-the phenyl amino formyl radical) sulfamyl.

Alkyl sulphinyl preferably includes replacement or the unsubstituted alkyl sulfinyl with 1-30 carbon atom, for example methylsulfinyl and ethyl sulfinyl.Aryl sulfonyl kia preferably includes replacement or the unsubstituted aryl sulfonyl kia with 6-30 carbon atom, for example phenyl sulfinyl and right-aminomethyl phenyl sulfinyl.Alkyl sulphonyl preferably includes replacement or the unsubstituted alkyl alkylsulfonyl with 1-30 carbon atom, for example methyl sulphonyl and ethylsulfonyl.Aryl sulfonyl preferably includes replacement or the unsubstituted aryl sulfonyl with 6-30 carbon atom, for example phenyl sulfonyl and right-aminomethyl phenyl alkylsulfonyl.

Acyl group preferably includes formyl radical, has replacement or unsubstituted alkyl carbonyl (for example ethanoyl, valeryl, 2-chloracetyl and stearyl-), the replacement with 7-30 carbon atom or the unsubstituted aryl carbonyl (for example benzoyl and right-n-octyl oxygen base phenylcarbonyl group) and replacement or unsubstituted heterocycle carbonyl (having the carbonyl that links to each other with the heterocycle carbon atom) (for example, 2-pyridyl carbonyl and 2-furfuryl group carbonyl) of 2-30 carbon atom.Aryloxycarbonyl preferably has the replacement or the unsubstituted aryloxycarbonyl of 7-30 carbon atom, for example phenyloxycarbonyl, right-the chlorophenoxy carbonyl ,-nitro-phenoxy carbonyl and right-tertiary butyl phenyloxycarbonyl.Alkoxy carbonyl preferably has the replacement or the unsubstituted alkoxy carbonyl of 2-30 carbon atom, for example methoxycarbonyl, ethoxy carbonyl, tert-butoxycarbonyl and positive octadecyl oxygen base carbonyl.

Formamyl preferably has the replacement or the unsubstituted formamyl of 1-30 carbon atom; for example formamyl, N-methylamino formyl radical, N; N-formyl-dimethylamino, N, N-two-n-octyl formamyl and N-(methyl sulphonyl) formamyl.Aryl-or the heterocycle azo base preferably include replacement or unsubstituted arylazo base with 6-30 carbon atom, for example phenylazo and right-chloro-phenyl-azo-group, the oxygen base has the replacement or the unsubstituting heterocycle azo-group of 3-30 carbon atom, 5-ethyl sulfenyl-1 for example, 3,4-thiadiazoles-2-base azo-group.Imino-preferably includes N-succinimido and N-phthalimido.

Phosphino-preferably includes replacement or the unsubstituted phosphino-with 2-30 carbon atom, for example dimethyl phosphino-, diphenylphosphino and methylphenoxy phosphino-.Phosphinyl preferably has the replacement or the unsubstituted phosphinyl of 2-30 carbon atom, for example phosphinyl, dioctyl oxygen base phosphinyl and diethoxy phosphinyl.Phosphinyl oxygen base preferably has the replacement or the unsubstituted phosphinyl oxygen base of 2-30 carbon atom, for example two phenoxy group phosphinyl oxygen bases and dioctyl oxygen base phosphinyl oxygen base.Phosphinyl amino preferably has the replacement or the unsubstituted phosphinyl amino of 2-30 carbon atom, and for example the dimethoxy phosphinyl is amino and dimethylamino phosphinyl amino.Siloxanes preferably has the replacement or the unsubstituted silyl of 3-30 carbon atom, for example trimethyl silyl, t-butyldimethylsilyl and phenyl dimetylsilyl.

As foregoing, the substituting group on the heterocycle also comprises cyano group, hydroxyl, nitro, carboxyl, sulfydryl and sulfo group.

In above-mentioned functional group, the functional group with hydrogen atom can have the hydrogen atom that replaces with above-mentioned substituting group.The functional group of these replacements comprises alkyl-carbonyl-amino alkylsulfonyl, aryl-amino-carbonyl alkylsulfonyl, alkyl sulfonyl-amino carbonyl and aryl sulfonyl amino carbonyl.Specific examples is methyl sulphonyl aminocarboxyl, right-the aminomethyl phenyl sulfonyl amino carbonyl, acetylamino alkylsulfonyl and benzoyl-amido alkylsulfonyl.

By the preferred substituents on the heterocycle of X, Y and Z acquisition is halogen atom, alkyl, aryl, heterocyclic radical, cyano group, nitro, carboxyl, sulfo group, alkyl sulphonyl, aryl sulfonyl and alkoxy carbonyl.When the substituting group on the heterocycle connects together when forming ring structure, this ring structure preferably with heterocyclic fused phenyl ring or pyridine ring.

In formula (3), A ₁And A ₂All represent to replace or unsubstituted carbon atom, perhaps a representative replaces or unsubstituted carbon atom in the middle of them, and another represents nitrogen-atoms, and condition is A ₂There is not nitro as substituting group.For better performance, preferred A ₁And A ₂All represent and replace or unsubstituted carbon atom.

Through the carbon atom A that replaces ₁Or A ₂Substituting group preferably include halogen atom, have 1-3 carbon atom alkyl, replacement or unsubstituted aryl, carboxyl, have alkyl-carboxylic acid ester group, alkoxy carbonyl, formamyl and the cyano group of 1-3 carbon atom.More preferred substituents is methyl, ethyl, cyano group, formamyl and carboxyl.

A ₁Carbon atom or have methyl preferably as substituent carbon atom.A ₂Carbon atom or have cyano group, formamyl or carboxyl preferably as substituent carbon atom.

In formula (3), R ₁, R ₂, R ₃And R ₄Represent hydrogen atom, alkyl, cycloalkyl, aralkyl, alkenyl, aryl, heterocyclic radical, alkylsulfonyl, acyl group, carboxyl or formamyl separately, wherein each group can have a substituting group.Will be further described below radicals R ₁, R ₂, R ₃And R ₄

Alkyl comprises the alkyl and the unsubstituted alkyl of replacement.Alkyl preferably contains 1-12, particularly 1-6 carbon atom.The substituting group of alkyl comprises hydroxyl, alkoxyl group, cyano group, halogen atom and ionic hydrophilic group.The specific examples of alkyl is methyl, ethyl, butyl, sec.-propyl, the tertiary butyl, hydroxyethyl, methoxy ethyl, cyano ethyl, trifluoromethyl, 3-sulfo group propyl group and 4-sulfo group butyl.

Cycloalkyl comprises and replacing or unsubstituted cycloalkyl, preferably contains 5-12 carbon atom, for example cyclohexyl.The substituting group of cycloalkyl comprises ionic hydrophilic group.

Aralkyl comprises and replacing or unsubstituted aralkyl, preferably contains 7-12 carbon atom, for example benzyl and 2-styroyl.The substituting group of aralkyl comprises ionic hydrophilic group.

Alkenyl comprises and replacing or unsubstituted alkenyl preferably have 5-12 carbon atom.The substituting group of alkenyl comprises ionic hydrophilic group.Non-limiting examples of alkenyls is vinyl and allyl group.

Aryl comprises and replacing or unsubstituted aryl preferably have 7-12 carbon atom.The substituting group of aryl comprises alkyl, alkoxyl group, halogen atom, alkylamino and ionic hydrophilic group.The example of aryl be phenyl, right-tolyl, right-p-methoxy-phenyl, neighbour-chloro-phenyl-and-(3-sulfo group propyl group amino) phenyl.

Heterocyclic radical comprises and replacing or unsubstituted heterocyclic.Preferred 5-or 6-unit heterocyclic group.The substituting group of heterocyclic radical comprises ionic hydrophilic group.The example of heterocyclic radical comprises 2-pyridyl, 2-thienyl, 2-thiazolyl, 2-[4-morpholinodithio base and 2-furfuryl group.Alkylsulfonyl comprises methylsulfonyl and phenyl sulfonyl.Acyl group comprises and replacing or unsubstituted acyl preferably have 1-12 carbon atom, for example ethanoyl and benzoyl.The substituting group of acyl group comprises ionic hydrophilic group.

R ₁, R ₂, R ₃And R ₄Preferably represent hydrogen atom, alkyl, aryl, alkylsulfonyl, acyl group or heterocyclic radical separately, more preferably represent alkylsulfonyl, acyl group, aryl or heterocyclic radical with 1-8 carbon atom.Note R ₁And R ₂Different times table hydrogen atom, and R ₃And R ₄Also different times table hydrogen atom.

Preferred especially R ₁And R ₃Represent aryl or heterocyclic radical separately, and R ₂It is hydrogen atom.As R ₁And R ₃The aryl that preferably replaces of aryl with following group: alkyl, alkoxyl group, aryloxy, alkoxy carbonyl, aryloxycarbonyl, sulfo group, halogen atom, sulfamyl, formamyl, formamyl oxygen base, alkoxy-carbonyl oxy, aryloxycarbonyl oxygen base, acyl amino, amino carbonyl amino, alkoxycarbonyl amino, aryloxycarbonyl amino, sulfamyl amino, alkyl sulfonyl-amino, arlysulfonylamino, acyl group etc.

Although the azo group in the azo-compound can be azo-type-N=N-or hydrodiazo type=N-NH-according to its structure, they all are described as azo-type in the present invention.

The azo-compound of formula (3) is prepared by the method that may further comprise the steps:

(a) with diazo reagent diazotization heterocycle primary amine form diazonium salt and

(b) make this diazonium salt and quality component reaction.

The diazotization reaction of heterocycle primary amine can reference example such as the 75th phase of Chemical Reviews the 241st page (1975) carry out.Operable diazo reagent comprises diluted hydrochloric acid aqueous solution, Isopentyl nitrite and the nitrosyl sulphuric acid of Sodium Nitrite.

The pyridine quality component that can be used for step (b) is by the described method synthetic of for example JP-A-51-83631, JP-A-49-74718 and JP-B-52-46230 (term used herein " JP-B " is meant " having examined Japanese patent publication ").

Only in order to describe purpose (but being not limited thereto), below the specific examples of the azo-compound of formula (3) representative listed in.

Table 3-1

Table 3-1 (continuing)

Table 3-2

Table 3-2 (continuing)

Table 3-3

Table 3-4

In the formula (4) of representative azo-compound of the present invention, Z ₁Representative forms the required atomic group of heterocycle with carbon atom and sulphur atom.By Z ₁Formed heterocycle preferably includes thiphene ring, thiazole ring, benzothiazole ring, isothiazole ring, benzisothiazole ring, 1,3,4-thiadiazoles ring and 1,2,4-thiadiazoles ring more preferably comprises thiazole ring, benzothiazole ring, isothiazole ring, benzisothiazole ring, 1,3,4-thiadiazoles ring and 1,2,4-thiadiazoles ring.Preferred especially isothiazole ring, 1,3,4-isothiazole ring and 1,2,4-isothiazole ring.Isothiazole ring most preferably.This heterocycle can have a substituting group at an arbitrary position.At heterocycle is when containing azo-cycle, and nitrogen-atoms can be by seasonization.

A ₁₁And A ₁₂Representative replaces or unsubstituted carbon atom or nitrogen-atoms separately, and condition is A ₁₁And A ₁₂Different times table nitrogen-atoms.A ₁₁And A ₁₂Preferred separately representative replaces or unsubstituted carbon atom.

Through the carbon atom A that replaces ₁₁Or A ₁₂The monovalence substituting group look like R under comprising ₁₁, R ₁₂, R ₁₃And R ₁₄Described group and cyano group.Alkyl, carboxyl, usefulness that these substituting groups preferably have 1-3 carbon atom have carboxyl, formamyl and the cyano group that 1-3 carbon atom replaces.

R ₁₁, R ₁₂, R ₁₃And R ₁₄Represent hydrogen atom, alkyl, cycloalkyl, aralkyl, alkenyl, aryl, heterocyclic radical, alkylsulfonyl, acyl group, carboxyl or formamyl separately, wherein each group can have a substituting group, and condition is R ₁₁And R ₁₂In at least one representative replace or unsubstituted aryl or replacement or unsubstituted heterocyclic and R ₁₃And R ₁₄Different times table hydrogen atom.Will be further described below these groups of group.

Alkyl comprises the alkyl and the unsubstituted alkyl of replacement.Alkyl preferably contains 1-12, particularly 1-6 carbon atom.The substituting group of the alkyl that process replaces comprises hydroxyl, alkoxyl group, cyano group, halogen atom and ionic hydrophilic group.The example of alkyl is methyl, ethyl, butyl, sec.-propyl, the tertiary butyl, hydroxyethyl, methoxy ethyl, cyano ethyl, trifluoromethyl, 3-sulfo group propyl group and 4-sulfo group butyl.

Cycloalkyl comprises and replacing or unsubstituted cycloalkyl.Cycloalkyl preferably contains 5-12 carbon atom.The substituting group of the cycloalkyl that process replaces comprises ionic hydrophilic group.The example of cycloalkyl comprises cyclohexyl.

Aralkyl comprises and replacing or unsubstituted aralkyl.Aralkyl preferably has 7-12 carbon atom.Substituting group comprises ionic hydrophilic group.The example of aralkyl comprises benzyl and 2-styroyl.

Alkenyl comprises and replacing or unsubstituted alkenyl.Alkenyl preferably has 5-12 carbon atom.The substituting group of alkenyl comprises ionic hydrophilic group.Non-limiting examples of alkenyls is vinyl and allyl group.

Aryl comprises and replacing or unsubstituted aryl.Aryl preferably contains 7-12 carbon atom.The substituting group of the aryl that process replaces comprises alkyl, alkoxyl group, halogen atom, alkylamino and ionic hydrophilic group.The example of aryl be phenyl, right-tolyl, right-p-methoxy-phenyl, neighbour-chloro-phenyl-and-(3-sulfo group propyl group amino) phenyl.

Heterocyclic radical comprises and replacing or unsubstituted heterocyclic.Preferred 5-or 6-unit heterocyclic group.The substituting group of heterocyclic radical comprises ionic hydrophilic group.The example of heterocyclic radical comprises 2-pyridyl, 2-thienyl, 2-thiazolyl, 2-[4-morpholinodithio base and 2-furfuryl group.

Alkylsulfonyl comprises methylsulfonyl and phenyl sulfonyl.Acyl group comprises and replacing or unsubstituted acyl.Acyl group preferably has 1-12 carbon atom.The substituting group of acyl group comprises ionic hydrophilic group.The example of acyl group is ethanoyl and benzoyl.

R ₁₁, R ₁₂, R ₁₃And R ₁₄Preferably represent hydrogen atom, alkyl, aryl, alkylsulfonyl, acyl group or heterocyclic radical separately, more preferably represent alkylsulfonyl, acyl group, aryl or heterocyclic radical with 1-8 carbon atom.As previously defined, R ₁₁And R ₁₂At least one is aryl or heterocyclic radical, and R ₁₃And R ₁₄Also different times table hydrogen atom.

Preferred especially R ₁₁And R ₁₃Represent aryl or heterocyclic radical separately, and R ₁₂Represent hydrogen atom.As R ₁₁And R ₁₃Aryl aryl preferably through replacing.The substituting group of this aryl comprises: alkyl, alkoxyl group, aryloxy, alkoxy carbonyl, aryloxycarbonyl, sulfo group, halogen atom, sulfamyl, formamyl, formamyl oxygen base, alkoxy-carbonyl oxy, aryloxycarbonyl oxygen base, acyl amino, amino carbonyl amino, alkoxycarbonyl amino, aryloxycarbonyl amino, sulfamyl amino, alkyl sulfonyl-amino, arlysulfonylamino and acyl group.

In the compound of formula (4) representative, the compound of preferred formula (5) representative:

Z wherein ₂Have and Z ₁Identical implication; R ₂₁Representative replaces or unsubstituted aryl or replacement or unsubstituted heterocyclic; R ₂₃And R ₂₄Represent hydrogen atom, alkyl, cycloalkyl, aralkyl, alkenyl, aryl, heterocyclic radical, alkylsulfonyl, acyl group, carboxyl or formamyl separately, wherein each group can have a substituting group; And R ₂₅And R ₂₆Represent hydrogen atom or monovalence substituting group separately.

Z ₂Preferable range and the Z in the formula (4) ₁Identical.R ₂₁, R ₂₃Or R ₂₄The substituting group that can have preferably include have 1-20 carbon atom the straight or branched alkyl (for example, methyl, ethyl, propyl group, butyl, hexyl and octyl group), straight or branched alkoxyl group with 1-20 carbon atom (for example, methoxyl group, oxyethyl group, propoxy-or butoxy) and ionic hydrophilic group (for example, carboxyl or its salt or sulfo group or its salt).

As R ₂₅And R ₂₆The monovalence substituting group preferably include and look like R ₁₁, R ₁₂, R ₁₃And R ₁₄Described group and cyano group.R ₂₅And R ₂₆Preferably represent hydrogen atom, the alkyl with 1-3 carbon atom, carboxyl separately, use carboxyl, formamyl and cyano group with 1-3 carbon atom replacement.Specifically, R ₂₅Preferably hydrogen atom, have a 1-3 carbon atom alkyl maybe can be with having the carboxyl that 1-3 carbon atom replaces; And R ₂₆Preferably hydrogen atom, formamyl and cyano group.

In the preferred compound of formula (5) representative, the more preferably compound of formula (6) representative:

Z wherein ₃Have and Z ₁Identical implication; R ₃₁Representative replaces or unsubstituted aryl or heterocyclic radical; R ₃₃Represent alkyl, cycloalkyl, aralkyl, alkenyl, aryl, heterocyclic radical, alkylsulfonyl, acyl group, carboxyl or formamyl, wherein each group can have a substituting group; R ₃₄Be H; And R ₃₅And R ₃₆Represent hydrogen atom or monovalence substituting group separately.

Z ₃Preferable range and the Z in the formula (4) ₁Identical.R ₃₁Or R ₃₃The substituting group that can have preferably include have 1-20 carbon atom the straight or branched alkyl (for example, methyl, ethyl, propyl group, butyl, hexyl and octyl group), straight or branched alkoxyl group with 1-20 carbon atom (for example, methoxyl group, oxyethyl group, propoxy-or butoxy) and ionic hydrophilic group (for example, carboxyl or its salt or sulfo group or its salt).

As R ₃₅And R ₃₆The monovalence substituting group preferably include and look like R ₁₁, R ₁₂, R ₁₃And R ₁₄Described group and cyano group.With R ₂₅Similarly, R ₃₅Preferably hydrogen atom, have a 1-3 carbon atom alkyl maybe can be with having the carboxyl that 1-3 carbon atom replaces.With R ₂₆Similarly, R ₃₆Preferably hydrogen atom, formamyl and cyano group.

In the compound of formula (6) representative, preferred R ₃₁And R ₃₃Represent the compound of the phenyl that replaces with the monovalence substituting group separately.Preferred especially R ₃₁Be phenyl, alkoxyl group or the ionic hydrophilic group that replaces with alkyl, and R ₃₃It is the compound of alkyl or the phenyl, alkoxyl group or the ionic hydrophilic group that replace with alkyl.Through the phenyl R that replaces ₃₁Or R ₃₃Substituting group preferably include have 1-20 carbon atom the straight or branched alkyl (for example, methyl, ethyl, propyl group, butyl, hexyl and octyl group), straight or branched alkoxyl group with 1-20 carbon atom (for example, methoxyl group, oxyethyl group, propoxy-or butoxy) and ionic hydrophilic group (for example, carboxyl or its salt or sulfo group or its salt).

The azo-compound of formula (4) is prepared by the method that may further comprise the steps:

(a) with diazo reagent diazotization heterocycle primary amine form diazonium salt and

(b) make this diazonium salt and quality component reaction.

The diazotization reaction of heterocycle primary amine can reference example such as the 75th phase of Chemical Reviews the 241st page (1975) carry out.Operable diazo reagent comprises diluted hydrochloric acid aqueous solution, Isopentyl nitrite and the nitrosyl sulphuric acid of Sodium Nitrite.

The pyridine quality component that can be used for step (b) is by the described method synthetic of for example JP-A-51-83631, JP-A-49-74718 and JP-B-52-46230.

Only in order to describe purpose (but being not limited thereto), below the specific examples of the azo-compound of formula (4) representative is shown in.

Table 4-1

Table 4-2

Table 4-3

Table 4-4

Table 4-4 (continuing)

Table 4-5

Table 4-5 (continuing)

Formula of the present invention (1), (2), (3), (4), (5), (6), (AZ-1) and (AZ-2) azoic dyestuff of representative can be used as the tinting material of image (particularly color picture) recording materials, these recording materials comprise ink jet recording materials, hot tranfer recording material, pressure sensitive recording material, electrophotographic recording material, transfer printing type photographic silver halide material, marking ink, stylus etc.Azoic dyestuff of the present invention is specially adapted to ink jet recording materials, hot tranfer recording material and electrophotographic recording material.It is the most effective to be used for ink jet recording materials.Azoic dyestuff of the present invention also finds to be used in the colour filter of solid-state image pickup such as CCD and indicating meter such as LCD and PDP, and the dye bath of textiles.

Azoic dyestuff of the present invention can have the substituting group of selection and use required physicals, for example solubleness, dispersity and hot movability so that present.These azo-compounds use to be fit to planning to use required form, for example solution or dispersion liquid (for example, emulsion or suspension).

In formula (AZ-1) with (AZ-2), the substituting group that aromatics or heterocycle can have comprises as to G, R in the formula (1) ¹And R ²Described those.

Quantum chemistry calculation also is referred to as Molecular Orbital Calculation, to obtain the interfacial angle of the present invention's definition, is undertaken by the B3LYP method, and this method ad initio is a kind of molecular orbital method commonly used, and basis set is 6-31G ^*Or more senior basis set.This B3LYP method is known as the DFT-HF hybrid method, is the theoretical mixing of density functional theories (DFT) and Hartree-Fock (HF).This B3LYP calculates and can use Gaussian 98 programs (software package of a kind of Gaussian of deriving from Inc) to carry out.

In brief, quantum chemistry calculation be between a kind of interaction, electronics and nucleus that calculates between electronic kinetic energy, the electronics interaction and with regard to whole molecule the interactional method between the nucleus, thereby measure the three-dimensional arrangement of minimum energy." three-dimensional arrangement of minimum energy " is meant the structure that molecule exists.With regard to theoretical details, many books can reference, Teijiro Yonezawa for example, Ryoshikagaku Nyumon, Kagaku Dojin (1983), Kiyoshi Mutai, Ryoshikagaku Bunshikidoho Nyumon, Shokodo (1991), Minoru Hirota, Bunshikidoho, Shokabo (1999) and Tim Clark, Keisankagaku Guidebook Sandai Bunshikeisan Program no Kaisetsu (translator of Japanese is translated by people such as Eiji Ohsawa), Maruzen (1988).

" physical chemistry magazine " A portion (Journal of Physical Chemistry Part A) has reported the example that compound is calculated in the 1214th page (2001), and it does not use basis set 6-31G in the present invention ^*In the scope by the B3LYP method.

The tolerance range of quantum chemistry calculation depends on method (for example, density functional approach or Hartree-Fock method) and basis set (for example, 6-31G ^*, 3-21G etc.).In the present invention, the calculating that is used to obtain the stable structure of energy is with basis set 6-31G by the DFT/B3LYP method ^*Or higher basis set, for example 6-31+G ^*, 6-31G ^*Or 6-311G ^*Carry out.The inventor finds that the first imido of formula (AZ-1) representative presents excellent performance when the interfacial angle 1-2-3-4 of computation structure is 45-135 ° in the time of preferred 60-120 °.In other words, found that absolute interfacial angle 1-2-3-4 presents narrower absorption band than the dyestuff near 90 ° in absorption spectrum, this is more favourable to reproducing colors.As one of dyestuff important fundamental characteristics is to have narrow absorption band.Also estimate along with interfacial angle more near the right angle, chromophoric group increases aspect rigidity, this will be useful for colour fastness.

The conventional instrument in stoichiometric calculation field has now been carried out and be to quantum chemistry calculation on workstation or computer.Yet,, therefore molding technique can be used for the part except that integral part because macromole is calculated the cost plenty of time.For example chain alkyl can replace with methyl, and the long-chain alkoxy base can replace with methoxyl group.When can similarly replacing in case of necessity.

What list below is the examples for compounds of formula (AZ-1) representative, with its called after D1-D14.The interfacial angle of definition in the formula (AZ-1) (unit: °) be shown in the bracket.REF1 that shows below and REF2 are the comparison example of calculating.All calculate all according to the B3LYP method by using the routine package that obtains from Gaussian company with basis set 6-31G ^*Carry out.This tabulation only is used for descriptive purpose, is not limited to the present invention.

The azoic dyestuff of formula (AZ-1) and (AZ-2) representative can formula (1) mode identical with the compound of (2) synthesize.

The absorption characteristic that is used for azoic dyestuff of the present invention is preferably such, and at N, the absorption spectrum of measuring in dinethylformamide (DMF) solution has the absorbancy in the wavelength region of 380nm-450nm aWith the absorbancy in the wavelength region of 500nm-580nm bRatio a/b less than 0.4.The absorbancy that the present invention is used aWith bBe under the following conditions with the spectrophotometric determination that defines among the JIS Z8120-86.Measure temperature and be selected from 15-30 ℃.Using path length is the unit of 10mm.The sample compound of specified rate (being converted into molecular weight) is diluted to the concentration that for example shows an absorbancy with DMF, wherein a(380nm-450nm) and b(500nm-580nm) that higher is 0.8-1.0.Absorbancy is to be obtained by the absorption spectrum of the compound solution under this adjustment concentration than a/b.

Fig. 1 and 2 is the example of the absorption spectrum among the DMF, is ordinate zou with absorbancy (Abs) wherein and is that X-coordinate is drawn with wavelength (nm).Fig. 1 has shown the spectrum of Compound D 10 (solid line) and REF1 (dotted line), and Fig. 2 has shown the spectrum of Compound D 13 (solid line) and REF2 (dotted line).The molar absorptivity of D10, D13, REF1 and REF2 is respectively 52000,48000,34000 and 40000.In these specific exampless, these compounds (analysis) are with DMF dilution, so that can be 1.0 at the absorption peak (peak b) of the wavelength zone of 500-580nm (can the scope at 0.8-1.0 in).Therefore, absorbancy than a/b simply the absorption peak of the wavelength zone by reading out in 380-450nm easily obtain.

With regard to azoic dyestuff of the present invention, have and mean as tinting material than a/b less than 0.4 absorbancy and to have guaranteed color reprodubility (color).This absorbancy is more preferably less than 0.35 than a/b, and preferred especially 0.3 or littler.

Second preferred implementation

The azo-compound that can be used for coloured composition of the present invention has the oxidizing potential than the high 1.0V of SCE.Oxidizing potential is high more, and is good more.Preferred oxidizing potential is higher than the compound of 1.1V (SCE relatively).More preferably oxidizing potential is higher than the compound of 1.2V (SCE relatively).

In the research to the ozone resistants of color picture, the inventor has found to exist a relation between the oxidizing potential of the coloring compound that is used to form color picture and ozone resistants.They find out that ozone resistants can improve by the azo-compound that uses oxidizing potential to be higher than 1.0V (relative saturation mercurous chloride electrode (SCE)).They find out that also containing at least two pKa values is that-10 to 5 substituting group and the azo-compound with above-mentioned oxidizing potential show unexpected high anti-ozone gas performance.

Improve the assessed in relation between the minimum occupied molecular orbital (LUMO) of highest occupied molecular orbital (HOMO) that the ozone resistants of color picture can be by compound and ozone gas by compound with specific oxidizing potential.That is, between the LUMO of the HOMO of coloring compound and ozone, react, thereby with the coloring compound oxidation, this is considered to cause the ozone resistants of color picture to reduce.Therefore, thus ozone resistants improve to be to reduce it with the reactivity foundation of ozone by the HOMO that reduces coloring compound.

Oxidizing potential is represented the movability of electronics from the sample to the electrode.Oxidizing potential is high more, and electron migration is more little, and promptly sample is low more to the susceptibility of oxidation.About chemical structure, oxidizing potential increases with the electron-withdrawing group that adds wherein, and reduces with the electron-donating group that adds wherein.

Oxidizing potential is meant that compound in the voltammetry that is described in detail later loses the anodic current potential of its electronics.Think that oxidizing potential approximates the energy level of compound at the HOMO of its ground state.

Oxidizing potential is with DC polarogram system or cyclic voltammetric systems measurement.With sample to be determined with 1x10 ^-4-1x10 ^-6Mol.dm ^-3Concentration be dissolved in the solution of supporting electrolyte of for example sodium perchlorate in the solvent of dimethyl formamide for example or acetonitrile or perchloric acid tetrapropyl ammonium, and use SCE to measure the current potential of working electrode as reference electrode.Oxidizing potential per sample or solubleness are selected suitable electrolyte and solvent.Details with regard to these selections can be with reference to P.Delalhay, New Instrumental Methods in Electrochemistry, Interscience Publishers (1954), A.J.Bard etc., Electrochemical Methods, John Willey ﹠amp; Sons (1980) and Akira Fujishima etc., DenkikagakuSokuteiho 101-118 page or leaf Gihodo (1984).

By the influence of the potential difference between the different liqs, the resistance of sample etc., oxidizing potential is measured may differ about tens millivolts.Can use standard model (for example quinhydrones) to proofread and correct this species diversity to this, thereby guarantee the reproducibility of mensuration.

In the present invention, oxidizing potential mensuration is to use by the DC polarography to contain 0.1mol.dm ^-3The perchloric acid tetrapropyl ammonium is as supporting electrolyte and 1x10 ^-3Mol.dm ^-3The N of sample compound, dinethylformamide solution uses SCE as reference electrode, uses Graphite Electrodes as working electrode, and uses platinum electrode to carry out as counter electrode.

The operation that is used to obtain to have high oxidation potential comprise (i) select to have inherently high oxidation potential compound structure, (ii) add electron-withdrawing group (promptly to the optional position of compound, have the group of big Hammett substituent constant σ p value, this paper back is described).Not only from the angle of ozone resistants, and from being easy to add any electrophilic or the photoelectron group angle with the molecular designing of adjusting colour fastness, color and physicals, the dye structure of selecting to have inherently high oxidation potential is a preferred operations.

Join the optional position of compound structure when electron-withdrawing group, thereby make oxidizing potential higher, therefore reduce with the time, can use Hammett substituent constant σ p value as substituent electrophilic or measuring to Electronic Performance as the ozone of electrophilic reagent reactive.The substituting group that has big σ p value by adding can make oxidizing potential higher.

Here explain Hammett substituent constant σ p value briefly.The Hammett rule is the rule of thumb that L.P.Hammett proposed in nineteen thirty-five, thereby attempts discussing quantitatively reaction or the equilibrated influence of substituting group to benzene derivative, is considered to effective so far usually.Used substituent constant comprises σ p value and σ m value in the Hammett rule.These values can find in many general books, J.A.Dean (editor) for example, Lange ' s Handbook of Chemistry, the 12nd edition, McGraw-Hill (1979) and Kagaku-no-ryoiki, the 122nd phase special issue, the 96-103 page or leaf, Nankodo (1979).

It is-10 to 5 that the azo-compound that can be used for coloured composition of the present invention should have at least two pKa values in water, preferred-9 to 5, is more preferably-8 to 5 substituting group." the pKa value is-10 to 5 substituting group " is that the substituting group that the pKa value is the proton dissociation part of-10 to 5 compound is measured in a kind of representative in water.

The pKa value is a kind of for example at Yasuhiko Saawaki, the value of definition in the Kisokagaku CourseButuriyukikagaku 47-60 page or leaf, Maruzen (1999).The pKa value of chemical compound lot is shown in M.B.Smith﹠amp; J.March, the 5th edition the 329th page table 8.1 of March ' s Advanced OrganicChemistry, John Wiley ﹠amp; Sons (2001), and be introduced into this paper, can obtain substituent pKa value thus.The pKa value of the compound that does not find in the document can be according to The Chemical Sociaty of Japan (editor), the method of instruction is defined as the basis acquisition with the pKa value among the 115th page of the JikkenKagaku Koza 1 Kihon Sosa I (the 4th edition), Maruzen (1990).Faintly acid pKa value can be according to YasuhikoSaawaki, the 50th page of Kisokagaku Course Buturiyukikagaku, and the method described in the Maruzen (1999) obtains with relative value.Because the pKa value changes with the environment of for example solvent, therefore can be according to The Chemical Sociaty of Japan (editor), the 286th page of Jikken KagakuKoza9Denki.Jiki (the 4th edition), the method described in the Maruzen (1991).

Notice that any substituent pKa value in the compound is subjected to the influence of structure of compound big, actual value may be with different by the value of another compound estimation like this.Although can use aforesaid method to measure the pKa value of the group that dissociates of compound, because the part except that the group that dissociates can influence this mensuration, so when this measured value of assignment for example, be not easy systematically to understand this measured value.

Therefore, in the present invention, any substituent pKa value of compound is not by to the value representation of compound practical measurement, but the conventional pKa value representation by corresponding functional group.The pKa value of the group that dissociates of the structure of the approaching group that dissociates of preferred utilization and compound similar compounds to be evaluated is estimated, so that substituting group influence or three-dimensional influence are minimized.For example, in order to explain the pKa value of the carboxyl in a certain compd A that carboxyl links to each other with phenyl ring, can use the pKa value of similar phenylformic acid (=4.2) or derivatives thereof of substituent type on the phenyl ring and position and compd A.The used pKa value of the present invention that is used for the quantitative definition compound is measured at water.

The pKa value comprises sulfo group, carboxyl, thiocarboxyl group, sulfino, phosphono and dihydroxyl phosphino-at-10 to 5 substituting group, wherein preferred sulfo group and carboxyl.

Group is expressed with non-separation form or salt form in the present invention although dissociate, and compound in fact can separate stage, non-separation state or exist with the separation/non-separation admixture of any ratio.The virtual condition of group of dissociating depends on the residing environment of compound.

The substituent quantity of pKa value between-10 to 5 is 2 or more in each molecule, preferred 3 or more, and more preferably 4 or more.The pKa value can be connected any position of azo-compound independently of one another for-10 to 5 substituting group.When these substituting groups are water soluble group, according to Kazuo Kondo (managing editor), Senshoku (the 3rd edition) about directly acting on the instruction of cellulosic fibre factor, separately is an ideal with their spaces among the TokyoDenki University Publishing Dep. (1987).

Preferably on each side of azo group-N=N-at least one is arranged, particularly two or more pKa values are substituting groups of-10 to 5.The preferred azo-compound of employing formula (5-I) representative this means Het (A ⁵) and Het (B ⁵) respectively carrying at least one, particularly two or more pKa values are substituting groups of-10 to 5.

Specific azo-compound to the raising of the ozone resistants of color picture can be by being positioned at correct position suitable dissociate group and specific oxidizing potential above-mentioned of suitable quantity influence evaluation.Think that the particular solution in the azo-compound has increased the direct degree of compound from this configuration of group.Then the azo-compound in the printing ink can be fixed on the desired location of visual receiver media.In other words, as if the dissociate this configuration of group produces a kind of mordant dyeing effect between azo-compound and visual receiver media.This is consistent with water-repellancy result among the embodiment that this paper provides later.The high water-repellancy of color picture of supposing azoic dyestuff can be estimated dyeing power so owing to the firm mordant dyeing between azoic dyestuff and the visual receiver media in waterproof test.In fact, the embodiment that this paper provides later confirms that the image with gratifying ozone resistants also has gratifying water-repellancy, and this has confirmed relation certain between mordant dyeing and the ozone resistants.

The azo-compound that can be used for coloured composition of the present invention is the compound of formula (5-I) representative preferably:

Het(A ⁵)-N＝N-Het(B ⁵) (5-I)

Het (B wherein ⁵):

In formula (5-I), Het (A ⁵) monobasic 5-of representative or 6-unit heterocycle.The heterocyclic example is thiphene ring, furan nucleus, pyrazoles ring, thiazole ring, oxazole ring, imidazole ring, isothiazole ring, isoxazole ring, pyrazoles ring, thiadiazoles Huan, oxadiazole ring, triazole ring, pyridine ring, pyridazine ring, pyrimidine ring and pyrazine ring.Wherein preferred thiazole ring, isothiazole ring, pyrazoles ring, thiadiazoles ring, pyridine ring and pyrazine ring.More preferably isothiazole ring, pyrazoles ring, 1,2,4-thiadiazoles ring, 1,3,4-thiadiazoles ring and pyridine ring.Preferred especially pyrazoles ring.

Het (A ⁵) heterocycle of representative can have the substituting group except that the above-mentioned pKa of having value is-10 to 5 substituting group.The suitable substituent that heterocycle can have comprises halogen atom; alkyl (comprising cycloalkyl and bicyclic alkyl); alkenyl (comprising cycloalkenyl and two cycloalkenyls); alkynyl group; aryl; heterocyclic radical; cyano group; hydroxyl; nitro; carboxyl; alkoxyl group; aryloxy; siloxy-; heterocyclic oxy group; acyloxy; formamyl oxygen base; alkoxy-carbonyl oxy; aryloxycarbonyl oxygen base; amino (comprising phenylamino); acyl amino; amino carbonyl amino; alkoxycarbonyl amino; aryloxycarbonyl amino; sulfamyl amino; alkyl sulfonyl-amino; arlysulfonylamino; sulfydryl; alkylthio; arylthio; the heterocycle sulfenyl; sulfamyl; sulfo group; alkyl sulphinyl; aryl sulfonyl kia; alkyl sulphonyl; aryl sulfonyl; acyl group; aryloxycarbonyl; alkoxy carbonyl; formamyl; the arylazo base; the heterocycle azo base; imino-; phosphino-; phosphono; phosphinyl; phosphinyl oxygen base; phosphinyl amino and silyl.

In containing these substituting groups of hydrogen atom, can also replace with above-mentioned substituting group.These substituent examples that heterocycle can have comprise alkyl-carbonyl-amino alkylsulfonyl, aryl-amino-carbonyl alkylsulfonyl, alkyl sulfonyl-amino carbonyl and aryl sulfonyl amino carbonyl.

These substituting groups on the heterocycle can be connected with each other and form replacement or a unsubstituted hydrocarbon or a heterocyclic fused ring.As Het (A ⁵) the nitrogen heterocyclic ring group nitrogen-atoms that can have seasonization.When heterocycle showed tautomerism, this compound comprised two tautomers, even only describe one of their intermediary.

Representing Het (B ⁵) formula (5-II) in, A ₅₁And A ₅₂Represent carbon atom or nitrogen-atoms independently of one another, condition is their different times table nitrogen-atoms; Preferred A ₅₁And A ₅₂All represent carbon atom.

R ⁵⁴And R ⁵⁵Represent hydrogen atom, halogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted aryl, halogen atom, carboxyl (can replace), formamyl, cyano group, alkoxy carbonyl or hydroxyl separately with alkyl with 1-3 carbon atom.R ⁵⁴And R ⁵⁵Preferably represent hydrogen atom, halogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted aryl, carboxyl (can replace), alkoxy carbonyl, formamyl or cyano group separately with alkyl with 1-3 carbon atom with 1-3 carbon atom.R ⁵⁴And R ⁵⁵More preferably represent hydrogen atom, methyl, ethyl, cyano group, formamyl or carboxyl separately.Specifically, R ⁵⁴Preferably hydrogen atom, replacement or unsubstituted alkyl, aryl, carboxyl or alkoxy carbonyl are more preferably hydrogen atom or replacement or unsubstituted alkyl, especially preferably hydrogen atom or methyl; And R ⁵⁵Preferably hydrogen atom, cyano group, formamyl or carboxyl are more preferably hydrogen atom, cyano group or formamyl, especially preferably hydrogen atom or cyano group.

R ⁵⁶, R ⁵⁷, R ⁵⁸And R ⁵⁹Represent hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted aryl or replacement or unsubstituted heterocyclic separately.R ⁵⁶, R ⁵⁷, R ⁵⁸And R ⁵⁹Preferably represent hydrogen atom, replacement or unsubstituted aryl or replacement or unsubstituted heterocyclic separately.Specifically, R ⁵⁶And R ⁵⁷Preferred separately representative replaces or unsubstituted aryl; R ⁵⁸Preferred representative replaces or unsubstituted heterocyclic; And R ⁵⁹The preferred hydrogen atom of representing.

Be that-10 to 5 substituting group is at section H et (B when the pKa value ⁵) in the time, promptly be selected from R ⁵⁴, R ⁵⁵, R ⁵⁶, R ⁵⁷, R ⁵⁸And R ⁵⁹Arbitrary or a plurality of position the time, preferably be selected from R ⁵⁶, R ⁵⁷, R ⁵⁸And R ⁵⁹Arbitrary or a plurality of position, particularly be selected from R ⁵⁶Or R ⁵⁷Arbitrary or a plurality of position.

The pKa value is that-10 to 5 substituting group can directly link to each other or link to each other through divalent linker arbitrarily.Divalent linker comprises by above-mentioned monovalence substituting group by removing those that a hydrogen atom or substituting group obtain.The example of these linking groups be alkylidene group (for example; methylene radical; ethylidene; propylidene; butylidene or pentylidene); arylidene (for example; phenylene; naphthylidene or 2; 4; 6-trimethylammonium phenylene); alkenylene (for example; vinylidene or propenylidene); alkynylene (for example; ethynylene or inferior proyl); amido bond; ester bond; the sulfonamido key; the sulfonic acid ester bond; urea groups; alkylsulfonyl; sulfinyl; thioester bond; ehter bond; carbonyl; (Rq)-(wherein Rq represents hydrogen atom to-N; replacement or unsubstituted alkyl or replacement or unsubstituted aryl); divalent heterocycle (for example; benzothiazole-2; 6-two bases; 6-chloro-1; 3; 5-triazine-2; 4-two bases; pyrimidine-2,4-two basic Huo quinoxalines-2,3-two bases); and two kinds or multiple combination.These linking groups or key can have any substituting group.

Although the azo group in the azo-compound of second preferred implementation of the present invention can be azo-type-N=N-or hydrodiazo type=N-NH-according to its structure, they all are described as azo-type in the chemical structure that this paper provides.According to the residing environment of these azo-compounds, they can show tautomerism.Although only described a tautomer, another tautomer is also included within the scope of the present invention.

In the compound of formula (5-I) representative, the compound of special preferred formula (5-III) representative:

R wherein ⁵⁴, R ⁵⁵, R ⁵⁶, R ⁵⁷, R ⁵⁸And R ⁵⁹Definition as above; R ⁵¹And R ⁵²Have and R ⁵⁴And R ⁵⁵Identical implication; And R ⁵³Have and R ⁵⁶, R ⁵⁷, R ⁵⁸And R ⁵⁹Identical implication; Prerequisite is that this compound is being selected from R ⁵¹, R ⁵², R ⁵³, R ⁵⁴, R ⁵⁵, R ⁵⁶, R ⁵⁷, R ⁵⁸And R ⁵⁹To contain at least two pKa values are substituting groups of-10 to 5 in one or more positions.

In formula (5-III), R ⁵¹Preferably hydrogen atom, replacement or unsubstituted alkyl or replacement or unsubstituted aryl are more preferably replacement or unsubstituted alkyl.R ⁵²Preferably hydrogen atom, halogen atom, replacement or unsubstituted alkyl, aryl, formamyl or cyano group are more preferably cyano group.R ⁵³Preferably replace or unsubstituted aryl or replacement or unsubstituted heterocyclic, be more preferably replacement or unsubstituted heterocyclic.R ⁵⁴, R ⁵⁵, R ⁵⁶, R ⁵⁷, R ⁵⁸And R ⁵⁹Preferable range with above-mentioned identical.

The pKa value is that-10 to 5 substituent configuration is so ideally in formula (5-III), at least one, preferred two or more being positioned at is selected from R ⁵¹, R ⁵²And R ⁵³The position, and at least one, preferred two or more being positioned at is selected from R ⁵⁴, R ⁵⁵, R ⁵⁶, R ⁵⁷, R ⁵⁸And R ⁵⁹Position (at least two altogether).At position R ⁵¹, R ⁵²And R ⁵³In, optimum position R ⁵³At position R ⁵⁴, R ⁵⁵, R ⁵⁶, R ⁵⁷, R ⁵⁸And R ⁵⁹In, optimum position R ⁵⁶, R ⁵⁷, R ⁵⁸And R ⁵⁹More preferably R ⁵⁶Or R ⁵⁷

Only for purpose of description (but being not limited thereto), below the specific examples that can be used for the azo-compound of coloured composition of the present invention is listed in.

Table 5-1

Table 5-2

Table 5-3

Table 5-3 (continuing)

Table 5-4

Table 5-5

Table 5-5 (continuing)

Coloured composition of the present invention is not particularly limited, as long as it contains above-mentioned specific azo-compound.This coloured composition can contain other various components according to its required purposes.For example, in order to be used as ink composite, by this azo-compound being dissolved and/or being dispersed in the medium (or oil soluble or water miscible), and in this solution or dispersion liquid, add the described appropriate addn in this paper back giving required performance of ink composite and characteristic, thereby prepare this coloured composition.

This coloured composition can contain the component as the color toner composition, those disclosed among the JP-A-7-209912 for example, can contain component as the resistance composition of colour filter, those disclosed among the JP-A-6-35182 for example, perhaps can contain the component of supplying with material (printing ink sheet) as hot dye transfer, for example those disclosed among the JP-A-7-137466.

The azo-compound that is used for coloured composition of the present invention can have the substituting group of selection, plans to use required physicals, for example solubleness, dispersity and hot movability so that present.These azo-compounds show use, for example solution or dispersion liquid (for example emulsion or suspension) with the selection that is fit to plan to use.

Coloured composition of the present invention can be coated to various image recording materials, particularly on the color image recording material.Especially, this coloured composition can be coated on ink jet recording materials, thermo-sensitivity recording materials, pressure-sensitive recording materials, electrophotographic recording material, transfer printing type photographic silver halide material, marking ink goods, stylus, ink composite or the like.Be particularly suitable for ink composite and ink jet recording materials.This coloured composition also finds to can be used for the colour filter among solid-state image pickup such as CCD and display plotter such as LCD and the PDP and the dye bath of textiles.

The 3rd preferred implementation

Method according to the ozone resistants of the raising color picture of the 3rd preferred implementation of the present invention is characterised in that and uses the compound of oxidizing potential than the high 1.0V of SCE.The higher compound of oxidizing potential has better result.More preferably oxidizing potential is higher than the compound of 1.1V (SCE relatively).Preferred especially oxidizing potential is higher than the compound of 1.2V (SCE relatively).

When the ozone resistants of research color picture, the inventor finds, is used to form between the oxidizing potential of coloring compound of color picture and the ozone resistants to have a relation.They find out that ozone resistants can improve by the compound that uses oxidizing potential to be higher than 1.0V (relative saturation mercurous chloride electrode (SCE)).

Improve the assessed in relation between the minimum occupied molecular orbital (LUMO) of highest occupied molecular orbital (HOMO) that the ozone resistants of color picture can be by compound and ozone gas by compound of the present invention.That is, between the LUMO of the HOMO of coloring compound and ozone, react, thereby with the coloring compound oxidation, this is considered to cause the ozone resistants of color picture to reduce.Therefore, thus ozone resistants improve to be to reduce it with the reactivity foundation of ozone by the HOMO that reduces coloring compound.

Oxidizing potential E _OxRepresent the movability of electronics from the sample to the electrode.E _OxHigh more, electron migration is more little, and promptly sample is low more to the susceptibility of oxidation.About chemical structure, E _OxIncrease with the electron-withdrawing group that adds wherein, and reduce with the electron-donating group that adds wherein.

E _OxBe meant that compound in the voltammetry that is described in detail later loses the anodic current potential of its electronics.Think E _OxApproximate the energy level of compound at the HOMO of its ground state.

Eox can easily be measured by those skilled in the art.Can reference example such as P.Delahay, New Instrumental Methods in Electrochemistry, IntersciencePublishers (1954), A.J.Bard etc., Electrochemical Methods, John Wiley ﹠amp; Sons (1980) and Akira Fujishima etc., Denkikagaku SokuteiHo, Gihodo (1984).

Oxidizing potential is with DC polarogram system or cyclic voltammetric systems measurement.With sample to be determined with 1x10 ^-4-1x10 ^-6Mol.dm ^-3Concentration be dissolved in the solution of supporting electrolyte of for example sodium perchlorate in the solvent of dimethyl formamide for example or acetonitrile or perchloric acid tetrapropyl ammonium, and use SCE to measure the current potential of working electrode as reference electrode.Oxidizing potential per sample or solubleness are selected suitable electrolyte and solvent.Details with regard to these selections can be with reference to A.Fujishima etc., Denkikagaku Sokuteiho 101-118 page or leaf Gihodo (1984).

The influence of the resistance by the potential difference between the different liqs, sample etc., oxidizing potential is measured may differ about tens millivolts.Can use standard model (for example quinhydrones) to proofread and correct this species diversity to this, thereby guarantee the reproducibility of mensuration.

In the present invention, oxidizing potential mensuration is to use by the DC polarography to contain 0.1mol.dm ^-3The perchloric acid tetrapropyl ammonium is as supporting electrolyte and 1x10 ^-3Mol.dm ^-3The N of sample compound, dinethylformamide solution uses SCE as reference electrode, uses Graphite Electrodes as working electrode, and uses platinum electrode to carry out as counter electrode.

Oxidizing potential is also with the structural changes of compound.Not only from the angle of ozone resistants, and from being easy to add any electrophilic or photoelectron group angle with the molecular designing of adjusting colour fastness, color and physicals, in order to reduce the reactivity with ozone, preferred selection has the compound structure of high oxidation potential inherently.

For example, in order to reduce the reactivity with electrophilic ozone, it is desirable to electron-withdrawing group is joined the optional position of compound structure, thereby make oxidizing potential higher.Can use Hammett substituent constant σ p value as substituent electrophilic or measuring to electronics.The substituting group that has big σ p value by adding can make oxidizing potential higher.

Here sketch Hammett substituent constant σ p value.The Hammett rule is the rule of thumb that L.P.Hammett proposed in nineteen thirty-five, thereby attempts discussing quantitatively reaction or the equilibrated influence of substituting group to benzene derivative, is considered to effective so far usually.Used substituent constant comprises σ p value and σ m value in the Hammett rule.These values can find in many general books, J.A.Dean (editor) for example, Lange ' s Handbook of Chemistry, the 12nd edition, McGraw-Hill (1979) and Kagaku-no-ryoiki, the 122nd phase special issue, the 96-103 page or leaf, Nankodo (1979).

The maximum absorption wavelength and the half breadth that are used to characterize The compounds of this invention can easily be measured by those skilled in the art.For example can be with reference to The Chemical Sociaty ofJapan (editor), Jikken Kagaku Koza 7Bunko II the 4th edition, 175-199 page or leaf, Maruzen (1992).Specifically, can use two unit that get by quartz or glass, a dress sample solution, another adorns contrast, measures.The solvent of sample solution from can sample dissolution, estimating that wavelength zone does not absorb and too not high-volatilely selecting arbitrarily those.In the present invention, use N, dinethylformamide (DMF) is used for measuring.

As for the mensuration of the half breadth of absorption spectrum, can be with reference to Jikken Kagaku Koza 7Bunko II the 4th edition, the especially description in the 154th page.The half breadth representative of absorption spectrum is at the width of the absorption band of a half-peak absorbancy, and it is used to describe the shape of absorption band.Have the spectrum point of little half breadth, and have the spectral width of big half breadth.Because the unwanted absorption that exists in short and longer wavelength side does not have big influence to color rendition, color is preferably had the spectrographic dyestuff of less half value.Maximum absorption wavelength that the present invention is used and half breadth are to contain 5x10 ^-5Mol.dm ^-3Use those that path length measures as the quartzy unit of 1cm on the DMF solution of sample compound.

Having maximum absorption and half breadth under the wavelength with 500nm-580nm is that 150nm or the narrower used compound of the present invention are used as magenta dye.For color preferably, maximum absorption wavelength is preferably at 520nm-580nm, more preferably at 520nm-570nm.Half breadth is 110nm or narrower preferably, is more preferably 90nm or narrower.

Compound with above-mentioned physicals is selected arbitrarily from azoic dyestuff, quinone dyestuff, cyanine dyes, cationic dyestuff, phthalocyanine pigment, indigoide colors, fulgide dyestuff, intermolecular charge transfer dyestuff etc.Although the dyestuff of these types can be used for the present invention arbitrarily, select and be easy to synthetic the satisfy compound that oxidizing potential and color require, preferred especially azo-compound from the width of its tone.Can be used for compound of the present invention although also will describe, should describe being suitable for other different dye structure suitably, be not construed as limiting the invention with particular reference to azo-compound.

Not only, can obtain to satisfy compound about the condition of oxidizing potential by above-mentioned actual oxidation potential measurement but also by molecular designing based on chemical structure.The oxidizing potential of known compound is relevant with the energy level of compound H OMO, as (editors) such as Manabu Seno-o, Daigakuin Buturikagaku (Chu), the 534-536 page or leaf, KodanshaScientific (1992) and Yasuhiko Saawaki, instruct in the Kisokagaku CourseButuriyukikagaku 187-189 page or leaf, Maruzen (1999).Therefore, can make the oxidizing potential of compound near desired level by adjusting the HOMO level.

Before the HOMO level of adjusting compound, need obtain this HOMO level by any known technology.The HOMO level of compound can be by its oxidizing potential or by the molecular orbital method backwards calculation.Up-to-date molecular orbital method and details thereof are described in The ChemicalSociaty of Japan (editor), kikan Kagaku Sousetu No.46 Koseido BunshiSekkei to Shinsozai Kaihatsu-Kinokagaku no Shintenkai wo Mezashite-, the 65-96 page or leaf, Japan Scientific Societies Press (2000) and Sumio Tokita, Electronics Kanren Shikiso-Genjo to Shorai Tenbo-20-25 page or leaf, CMC (1988).Although wish to obtain suitable calculation result, can use simpler calculating easily according to required tolerance range by accurate as far as possible Molecular Orbital Calculation.

With reference to substituting group influence and colour developing structure the structure of azo-compound and the relation of HOMO level thereof are discussed.Makoto Ohkawara etc., Kinousei Shikiso, the 39-42 page or leaf, Kodansha Scientific (1992), Makoto Ohkawara etc., Kinousei Shikiso noKagaku, 43-45 page or leaf, CMC (1981) and Sumio Tokita, Kinousei Shikiso noBunshi Sekkei-PPP Bunshikidoho to sono katuyo, 89-108 page or leaf, Maruzen (1989) have described the relation of substituting group influence with absorbing wavelength skew and orbital energies level.Be understood that this HOMO level can adjust by any substituting group is joined the position with big HOMO coefficient.That is, add electron-withdrawing substituent and make the HOMO level reduce, adding increases the HOMO level to electron substituent group.

When the oxidizing potential of a certain compound does not reach the scope of the present invention's definition, can improve desired level by adding substituting group according to the molecular designing guide of being instructed.In this case, by using aforementioned Hammett substituent constant σ p value can select suitable substituents.In order to understand molecular orbital(MO), be important to understanding the HOMO coefficient by molecular orbital method.Yet, certain restriction is arranged by substituting group influence raising.Easily expect, add many substituting groups and will be difficult to synthetic dyestuff.And replacement is accompanied by color change, makes it be difficult to satisfy the requirement of oxidizing potential and color.Only by in known compound, add substituting group may, still can be very difficult to realize purpose of the present invention.Owing to, therefore recognize and to start with from colour developing structure itself by simply utilizing the free difficulty of also adjusting the HOMO level of compound widely of substituent influence.

The colour developing structure is discussed then.Colour developing structure or can use nitrogen benzide structure (it is a basic structure) perhaps can be one to have heterocyclic heterocycle azo structure.Think and not only answer the controlled oxidation current potential, and should control absorption characteristic, therefore colour developing structure optimizing Billy is fallen in the specified range with the easier physicals that makes of substituent effect.Promptly, expect easily, when select to have minimize the HOMO level and with the colour developing structure of the approaching color of required color when adding substituting group with the basic structure of the color of oxidizing potential with adjustment and adjustment, compare with the adjustment that only depends on above-mentioned substituting group influence, the degree of freedom of molecular designing will be widened.From this angle, assert preferred heterocycle azo type compound.

Makoto Ohkawara etc., Kinousei Shikiso, the 42nd page, KodanshaScientific (1992) has especially shown the use heterocycle, particularly sulfur heterocyclic ring makes the example of absorbing wavelength to longer wavelength side skew.Think that utilizing this color development system to widen selects available substituent degree of freedom, makes its easier design can realize the compound of the object of the invention then.

Except the one-piece construction and substituting group influence of color development system, the other factors that influences the color development system of dyestuff comprises intermolecular and intramolecularly effect, solvent effect, tautomerism, acid-alkali balance, three-dimensional influence etc., as Kinousei Shikiso no Kagaku, the 58-63 page or leaf is described in the CMC (1981).

Design has an above-mentioned half breadth in its absorption spectrum compound is given the color picture of satisfactory color., instruct among the Maruzen (1982) at Chemical Seminar 9 ColorChemistry 150-161 pages or leaves as Sumio Tokita, color always not only is subjected to the influence of electron energy level, and is subjected to the influence of molecular vibration or rotation.Therefore wish that the influence that reduces because of molecular vibration or rotation will make absorption band narrower and sharper, and half breadth is narrower.The method that reduces molecular vibration or rotate influence of color comprises to the three-dimensional big substituting group of correct position adding, thus the rotation of inhibition any key.

Confirm that by above-mentioned test and observation the present invention obtains specific oxidizing potential and half breadth combination the color picture of anti-ozone gas and color excellence.The compound that can be used for the combination with specific oxidizing potential and half breadth of the present invention is the azo-compound of formula (7) representative preferably:

A ⁶-N＝N-B ⁶ (7)

A wherein ⁶And B ⁶Representative replaces or unsubstituted aryl or replacement or unsubstituted 5-or 6-unit heterocyclic radical separately.

As A ⁶Or B ⁶Replacement or the unsubstituted aryl aryl that preferably has 6-30 carbon atom, for example phenyl, naphthyl or anthryl, they can have substituting group separately.Small intestine one fused rings that can be connected with each other of two substituting groups on this aryl.

As A ⁶Or B ⁶Replacement or unsubstituted 5-or the 6-unit heterocyclic radical heterocyclic radical that preferably has 3-30 carbon atom, for example thienyl, furyl, pyrryl, indyl, imidazolyl, pyrazolyl, indazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, thiadiazolyl group, oxadiazole base, triazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, quinolyl, isoquinolyl, phthalazinyl, quinoxalinyl and quinazolyl, each heterocyclic radical can have substituting group.The fused rings that can be connected with each other of two substituting groups on this heterocyclic radical.When this heterocyclic radical contained nitrogen-atoms, this nitrogen-atoms can be a seasonization.Preferred A ⁶And B ⁶In at least one is to replace or unsubstituted 5-or 6-unit heterocyclic radical.More preferably A ⁶And B ⁶All be to replace or unsubstituted 5-or 6-unit heterocyclic radical.

In the above-mentioned azo-compound, those with heterocyclic radical azo-type colour developing structure are especially successfully realized purpose of the present invention.Based on this knowledge, the inventor has obtained the compound that oxidizing potential, maximum absorption wavelength and half breadth all fall into above-mentioned scope and realize the object of the invention.

Following table is to be included in oxidizing potential to be higher than and to show that maximum absorption and half breadth are the specific examples of the azo-compound in 150nm or the narrower compound scope relatively under 1.0V (SCE) and the wavelength between 500nm-480nm.Only purpose provides these examples in order to describe, and never is used for restriction.

By the useful compound of listing above as can be known, can not estimate the oxidizing potential of azo-compound by its chemical structure.In other words, the compound by above-mentioned various factors optimizing can be obtained to have required physical properties.

The method that the present invention improves ozone resistants can be used for various image recording materials, particularly the color image recording material.Specifically, present method can be used for ink jet recording materials, thermo-sensitivity recording materials, pressure-sensitive recording materials, electrophotographic recording material, transfer printing type photographic silver halide material, marking ink, stylus etc.Effective especially to ink jet recording materials, thermo-sensitivity recording materials and electrophotographic recording material.Most preferably using is ink-vapor recording.

Present method also finds to can be used for the colour filter that solid-state image pickup such as CCD and CMOS, display plotter such as LCD and PDP use, and the dye bath of fabric.

Method of the present invention is to specialize by following: prepare and a kind ofly has the substituent compound of selection according to the molecule outward appearance, so that present the physical properties that is applicable to the application of wanting, and for example solubleness, dispersiveness and hot movability.The selection form that this compound goes for wanting to use is used, for example solution or dispersion liquid (for example emulsion or suspension).

[composition for ink jet recording]

Inkjet ink composition of the present invention prepares by above-mentioned azoic dyestuff is dissolved and/or is distributed in oleophylic or the water-bearing media.Preferably use the aqueous ink composition of water-bearing media.Other must additive be to add in the scope of not damaging effect of the present invention.Useful additive comprises antidesiccant (wetting agent), emulsion stabilizer, permeate agent, UV light absorber, anti-enzymatic regent, anti-mycotic agent, pH regulator agent, surface tension improving agent, defoamer, sterilant, viscosity improving agent, dispersion agent, dispersion stabilizer, rust-preventive agent and chelating.These additives are directly joined in the water-based inks goods.Place in that oil-soluble colourant use with the form of dispersion liquid joins these additives in the dye dispersion liquid that makes usually, perhaps can join the oil phase or the aqueous phase of printing ink goods.

In order to prevent preferably to use antidesiccant because of the purpose of ink setting plug nozzle.Having the water-miscible organic solvent that the steam than water forces down is preferred antidesiccant.The example of these water-miscible organic solvents comprises polyvalent alcohol, for example ethylene glycol, propylene glycol, Diethylene Glycol, polyoxyethylene glycol, thiodiglycol, two thiodiglycols, 2-methyl isophthalic acid, ammediol, 1,2,6-hexanetriol, acetylenediol derivative, glycerine and TriMethylolPropane(TMP); The lower alkyl ether of polyvalent alcohol, for example glycol monomethyl methyl (or single ethyl) ether, Diethylene Glycol monomethyl (or single ethyl) ether and triethylene glycol list ethyl (or monobutyl) ether; Heterogeneous ring compound, for example 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, 1,3-dimethyl-2-imidazolone and N-ethylmorpholine; Sulfocompound, for example tetramethylene sulfone, methyl-sulphoxide and 3-cyclobufene sultone; Polyfunctional compound, for example Pyranton and diethanolamine; And urea derivatives.The polyvalent alcohol of preference such as glycerine and Diethylene Glycol wherein.These antidesiccants can use separately or use with its two or more mixture.The preferred content of antidesiccant in ink composite is 10-50% weight.

In order to help the purpose of ink penetration in the paper, preferably add permeate agent.Useful permeate agent comprises alcohols, for example ethanol, Virahol, butanols, two (or three) ethylene glycol monobutyl ether and 1,2-hexylene glycol; Sodium lauryl sulphate, sodium oleate and nonionogenic tenside.Not cause the content of burr or strikethrough decision permeate agent.The permeate agent content of 5-30% weight will enough obtain gratifying effect in the ink composite.

UV light absorber is used to improve the stability of image.Useful UV light absorber for example comprises disclosed benzotriazole cpd among JP-A-58-185677, JP-A-61-190537, JP-A-2-782, JP-A-5-197075 and the JP-A-9-34057; For example JP-A-46-2784, JP-A-5-194483 and U.S. Pat 3,214, the benzophenone compound described in 463; The styracin compound described in JP-B-48-30492, JP-B-56-21141 and the JP-A-10-88106 for example; Disclosed triaizine compounds among JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621 and the JP-W-8-501291 (term used herein " JP-W " is meant and examines disclosed international patent application) for example; And the compound that provides among the Research DisclosureNo.24239.Also can use the compound that absorbs UV-light and send fluorescence, i.e. white dyes, for example diphenyl ethylene derivatives and benzoxazole derivative.

Anti-enzymatic regent is used to improve the stability of image.Can use various organic or metal complex anti-enzymatic regents.Organic anti-enzymatic regent comprises hydroquinones, alkoxy benzene phenols, dialkoxy phenol, phenol, phenyl amines, amine, indane class, chroman class, alkoxy benzene amine and heterogeneous ring compound.The metal complex anti-enzymatic regent comprises nickel complex and zinc complex.The specific examples of anti-enzymatic regent is shown in Research Disclosure, the patent of quoting as proof in No.17643 (VII-I to VII-J), 15162,18716 (the 650th page of left hurdle), 36544 (the 527th pages), 307105 (the 872nd pages) and 15162.Also can use the compound and the specific examples thereof of the general formula representative described in the JP-A-62-215272 (127-137 page or leaf).

Useful mycocide comprises dehydration sodium acetate, Sodium Benzoate, pyrithione-1-sodium oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazole-3-ketone and salt thereof.The preferred content of mycocide in ink composite is 0.02-1.00% weight.

Can use neutralizing agent, for example organic bases and mineral alkali are as the pH regulator agent.In order to improve the printing ink storage stability, take all factors into consideration, preferably add the pH regulator agent ink composite is adjusted to pH 6-10, particularly pH 7-10.

Surface tension modifier comprises nonionic, positively charged ion or anion surfactant.The surface tension of inkjet ink composition of the present invention is 20-60mN/m, particularly 25-45mN/m preferably.Preferred ink composite of the present invention has 30mPa.s or lower, particularly 20mPa.s or lower viscosity.

Useful anion surfactant comprises soap, alkyl-sulphate, alkylbenzene sulfonate, sulfonated alkyl naphathalene, dialkyl sulfosuccinates, alkyl phosphate salt, naphthene sulfonic acid-formalin condenses and polyalkylene glycol alkyl vitriol.Useful ionic surfactant pack is drawn together polyethylene glycol alkyl ether, polyalkylene glycol alkyl allyl ethers, cithrol, sorbitan aliphatic ester, polyoxyethylene sorbitan aliphatic ester, polyoxyethylene alkyl amine, glycerol fatty acid ester, ethylene oxide-oxypropylene block copolymer and is derived from Air Products ﹠amp with trade name Surfynol; The acetylenediol based surfactants of Chemicals.Also can use the amine oxide type amphoterics, N for example, N-dimethyl-N-alkyl amine oxide.Also can use JP-A-59-157636 (37-38 page or leaf) and Research Disclosure, the tensio-active agent described in the No.308119 (1989).

The defoamer that can add comprises fluorochemicals, silicon compound and sequestrant, for example EDTA if necessary.

When azoic dyestuff of the present invention is scattered in water-bearing media, the preferred technical description that adopts is at JP-A-11-286637 and Japanese patent application No. 2000-78491,2000-80259 and 2000-62370, the colored particles that wherein contains dyestuff and oil-soluble polymers is scattered in the water-bearing media, perhaps be described in Japanese patent application No. 2000-78454,2000-78491,2000-203856 and 2000-203857, wherein the dyestuff that will be dissolved in the high boiling organic solvent is scattered in the water-bearing media.Dyestuff is scattered in the specific examples of method of water-bearing media and the kind and the quantity (oil-soluble polymers, high boiling organic solvent and additive) of used material thereof, can suitably select with reference to the document of quoting as proof above.Also can this azoic dyestuff is directly finely divided in water-bearing media.Dispersion agent and tensio-active agent can help to disperse.Suitable dispersing apparatus comprises simple agitator, impeller agitator, online agitator, shredder (for example colloidal mill, ball mill, sand mill, attritor, roll mill and stirring kneader), ultrasonic stirring device and high-pressure emulsification device or clarifixator (for example Gaulin clarifixator, microfluidization device and DeBEE 2000).

Except above-mentioned document, following document also provides the information of jetted ink goods: JP-A-5-148436, JP-A-5-295312, JP-A-7-97541, JP-A-7-82515, JP-A-7-118584, JP-A-11-286637 and Japanese patent application 2000-87539.

The water-bearing media that can be used for ink composite of the present invention is the water that contains the water-miscible organic solvent usually.Useful water-miscible organic solvent comprises alcohols, for example methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, hexanol, hexalin and phenylcarbinol; Polyvalent alcohol, for example ethylene glycol, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butyleneglycol, hexylene glycol, pentanediol, glycerine, hexanetriol and thiodiglycol; Diol, derivatives, for example glycol monomethyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, Diethylene Glycol single-butyl ether, propylene glycol monomethyl ether, propylene glycol single-butyl ether, DPGME, glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol list ethyl ether and glycol monomethyl phenyl ether; Amine, for example thanomin, diethanolamine, trolamine, N methyldiethanol amine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, quadrol, Diethylenetriamine, three second tetramines, polymine and 4-methyl-diaminopropane; With other polar solvent, for example methane amide, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, methyl-sulphoxide, tetramethylene sulfone, 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, N-vinyl-2-Pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidone, acetonitrile and acetone.These solvents can use separately, perhaps with two kinds or its multiple mixing use.

Inkjet ink composition preferably contains the azo-compound of the present invention that concentration is 0.2-10 weight %.Except azo-compound of the present invention, this inkjet ink composition can contain known tinting material.In this case, the total concn of preferred tinting material is in above-mentioned scope.

Inkjet ink composition of the present invention not only can be used to form monochrome image, and can be used to form full-colour image.In order to form full-colour image, can use magenta ink, cyan ink and Yellow ink.In order to adjust tone, can mix the use black ink.

Mixing the yellow dyes that uses selects through any.Useful yellow dyes comprise have phenol, naphthols, aniline, heterogeneous ring compound (for example pyrazolone or pyridone), open chain activity methene compound etc. be as the aryl or the heterocyclic radical azoic dyestuff of quality component; Has the azomethine dyes as the quality component such as open chain activity methene compound; Methine dyes such as Ben Yajiaji dyestuff and single methyl carbonyl alcohol dyestuff; Quinone dyestuff such as naphthoquinone dyestuff and anthraquinone dye; Quinone phthalein ketone dyes, nitro-dye, nitroso-dye, acridine dye and dihydroketoacridine dyestuff.

Mixing the cyan dye that uses can be any cyan dye.Useful cyan dye comprise have phenol, naphthols or aniline is as the aryl or the heterocyclic radical azoic dyestuff of quality component; Has the azomethine dyes as the quality component such as phenol, naphthols or heterogeneous ring compound (for example Pyrazolotriazole); The polymethine dyestuff is cyanine dyes, carbonyl alcohol dyestuff and merocyanine dye for example; Carbonium dye is diphenylmethane dye, triphenhlmethane dye and xanthene dye for example; Phthalocyanine pigment; Anthraquinone dye; Indigoide colors and thioindigo class dyestuff.

The yellow or the cyan dye that also can use a part of color base to dissociate and just develop the color.Counter cation in this class dyestuff comprises inorganic cation such as basic metal or ammonium, and organic cation such as pyridine and quaternary ammonium salt perhaps have the polymer cation of this positively charged ion as part-structure.

The black dyes that can mix use comprises two azoic dyestuffs, trisazo dye, Tetrakisazo dyes and carbon black dispersion.

[ink jet recording method]

By applying an energy to jetted ink, fly to tiny ink droplet on the known visual receiver media with formation, carry out ink-vapor recording thereby form image.Known medium comprises paper (for example, disclosed ink jetting paper in JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238783, JP-A-10-153989, JP-A-10-217473, JP-A-10-235995, JP-A-10-337947, JP-A-10-217597 and JP-A-10-337947), film, electrophotography paper, cloth, glass, metal and the pottery of common paper, coating resin.

In order to give the weather patience of visual gloss, water-repellancy or raising, the polymer latex compound can be used for imaging.Can be before imaging, afterwards or simultaneously, latex compounds is applied on the visual receiver media.In other words, latex compounds may reside in this medium or in the ink composite, perhaps can apply separately by liquid form.Its details can be referring to Japanese patent application No. 2000-363090,2000-315231,2000-354380,2000-343944,2000-268952,2000-299465 and 2000-297365.

The recording paper and the recording sheet that can be used as with the image-recording medium of ink composite spray ink Printing of the present invention generally include substrate and ink receiving layer and reverse side coating if necessary.Substrate comprises paper, synthetic paper and plastics film.Paper as substrate is by dissolving pulp (as LBKP or NBKP), mechanical pulp is (as ground wood pulp (GP), the ground wood pulp (PGW) of compression, refiner mechanical pulp (RMP), heat-mechanical pulp (TMP), chemical heat-mechanical pulp (CTMP), chemimechanical pulp (CMP) or chemiground wood pulp (CGP)), perhaps paper waste is as (for example, the paper pulp of de-oiling China ink (DIP)), (if necessary, it can contain known additives such as pigment, tackiness agent, sizing agent, fixing agent, cationoid reagent and paper reinforcer), make with copper mesh paper machine or mould machine etc. by paper-making technique.This substrate preferably has thickness and the 10-250g/m of 10-250 μ m ²Ground mass.

Can directly provide ink receiving layer and reverse side coating, provide ink receiving layer and reverse side coating to carrier after perhaps can or forming the anchor coating with starching such as starch, polyvinyl alcohol to this substrate.If necessary, this substrate is flattened on calender, thermograde rolling press, soft press-polishing machine etc.Preferred substrate be on the two sides all lamination the paper of polyolefine (for example polyethylene), polystyrene, polyethylene terephthalate, polybutene or its copolymer film and plastics film is arranged.In this laminating resin, add white pigment (for example titanium dioxide or zinc oxide) or the toning material (for example cobalt blue, ultramarine and Neodymium trioxide) be preferred.

The ink receiving layer that provides on substrate comprises pigment (preferred white pigment) and aqueous binders.Useful white pigment comprises mineral dye, for example lime carbonate, kaolin, talcum, clay, diatomite, synthetic soft silica, pure aluminium silicate, Magnesium Silicate q-agent, Calucium Silicate powder, aluminium hydroxide, alumina, lithopone, zeolite, barium sulfate, calcium sulfate, titanium dioxide, zinc sulphide and zinc carbonate; And pigment dyestuff, for example styrene plastic(s) pigment, acrylplastics pigment, urea resin and melamine resin.Preferred porous inorganic pigment.More preferably surface-area is bigger, for example synthetic soft silica.Can use silicic anhydride that obtains by dry method or the moisture silicic acid that obtains by wet method.Preferred especially moisture silicic acid.

The useful aqueous binders that can be used for forming ink receiving layer comprises water-soluble polymers such as polyvinyl alcohol, silanol modified polyethylene alcohol, starch, cationic starch, casein, gelatin, carboxymethyl cellulose, Natvosol, Polyvinylpyrolidone (PVP), polyalkylene oxide and polyalkylene oxide derivative; With aqueous dispersion polymers such as styrene-butadiene latex and vinylformic acid emulsion.These aqueous binders can use or mix use separately.For ability bonding with granules of pigments and the anti-release coating of formation, the pure and mild silanol modified polyethylene of preferably polyethylene alcohol in the above-mentioned tackiness agent.

Except these pigment and aqueous binders, ink receiving layer can contain mordant, water-resisting agent, photostabilization improving agent, tensio-active agent and other additive.

The mordant that joins ink receiving layer is preferably through fixing.For this reason, preferably use polymer mordant.The details of useful polymer mordant is shown in JP-A-48-28325, JP-A-54-74430, JP-A-54-124726, JP-A-55-22766, JP-A-55-142339, JP-A-60-23850, JP-A-60-23851, JP-A-60-23852, JP-A-60-23853, JP-A-60-57836, JP-A-60-60643, JP-A-60-118834, JP-A-60-122940, JP-A-60-122941, JP-A-60-122942, JP-A-60-235134, JP-A-1-161236 and U.S. Pat 2,484,430,2,548,564,3,148,061,3,309,690,4,115,124,4,124,386,4,193,800,4,273,853,4,282,305 and 4,450,224.Specifically, for high image quality and have the sunproof image of raising, the polymer mordant described in the preferred JP-A-1-161236 (212-215 page or leaf).

Make the water-resisting agent of visual waterproof preferably include resin cation (R.C.) effectively, for example polymeric amide-polyamine epichlorohydrin, polymine, polyamine sulfone, chlorination dimethyldiallylammonium polymkeric substance, cationic polyacrylamide and colloid silica.Special preferred polyamide-polyamine epichlorohydrin.Content preferably the 1-15% weight, particularly 3-10% weight of resin cation (R.C.) in the image receiving layer.

The photostabilization improving agent comprises zinc sulfate, zinc oxide, hindered amine antioxidant and benzophenone or benzotriazole UV absorbers.Zinc sulfate is suitable especially.

Tensio-active agent plays the coating auxiliary agent, peels off patience improving agent, slip improving agent or static inhibitor in visual receiving layer.Useful tensio-active agent is described in JP-A-62-173463 and JP-A-62-183457.Can use organic fluoride substitution list surface-active agent.Preferred hydrophobic organic fluoride, for example fluorine surfactant, oiliness fluorine cpd (for example fluorocarbon oil) and solid fluoride (for example tetrafluoroethylene resin).The details of organic fluoride is described in JP-B-57-9053 (8-17 hurdle), JP-A-61-20994 and JP-A-62-135826.Other additive that can join ink receiving layer comprises pigment dispersing agent, thickening material, defoamer, dyestuff, white dyes, sterilant, pH regulator agent, matting agent and stiffening agent.Ink receiving layer can have one deck or two-layer structure.

Reverse side coating (can provide if necessary) comprises white pigment, aqueous binders and additive.White pigment comprises white inorganic pigment, for example light sedimentary lime carbonate, water-ground limestone, kaolin, talcum, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulphide, zinc carbonate, stain white, pure aluminium silicate, diatomite, Calucium Silicate powder, Magnesium Silicate q-agent, synthetic soft silica, colloid silica, colloid alumina, pseudobochmite, aluminium hydroxide, alumina, lithopone, zeolite, hydrated halloysite, magnesiumcarbonate and magnesium hydroxide; With pigment dyestuff such as styrene plastic(s) pigment, acrylplastics pigment, polyethylene, hollow particle, urea resin and melamine resin.

The aqueous binders that can be used in the reverse side coating comprises water-soluble polymers such as vinylbenzene/maleate copolymer, styrene/acrylic salt copolymer, polyvinyl alcohol, silanol modified polyethylene alcohol, starch, cationic starch, casein, gelatin, carboxymethyl cellulose, Natvosol and Polyvinylpyrolidone (PVP); With aqueous dispersion polymers such as styrene-butadiene latex and vinylformic acid emulsion.The additive that can be used in the reverse side coating comprises defoamer, suds suppressor, dyestuff, white dyes, sterilant and water-resisting agent.

Polymer latex can be joined in any layer (comprising the reverse side coating) that constitutes ink jet recording paper or film so that improve film performance, for example dimensional stability, prevent to roll, anti-clogging plug and anti-splitting.Its details is referring to JP-A-62-245258, JP-A-62-136648 and JP-A-62-110066.The polymer latex that will have low Tg (40 ℃ or lower) joins in the layer that contains mordant and will prevent to split or roll.The polymer latex that will have high glass transition temperature joins the reverse side coating and also prevents from effectively to roll.

Inkjet ink composition of the present invention can be used for any known ink-jet recording system, for example sprays the electrostatic system of ink droplet by electrostatic attraction; Utilize the piezoelectric system (pressure pulse system) of the oscillation pressure of piezoelectric element; Electrical signal is converted into acoustic beam, is applied to this bundle on the printing ink and utilizes radiation pressure to spray the sound system of ink droplet.And, ink-vapor recording comprise spray the low droplet printing ink (so-called photograph printing ink) of many concentration but system, use the different printing ink goods of the substantially the same concentration of many colors to improve the system of image quality and use the system of water white transparency printing ink.

[color toner]

Color toner of the present invention comprises that azo-compound of the present invention is scattered in wherein adhesive resin as tinting material.Can use the adhesive resin that is usually used in any kind in the toning agent, for example styrene resin, acrylic resin, styrene/acrylic resin and vibrin.

In order to improve flowability or control electric charge, toner-particle can mix with the inorganic or organic granular as external additive.The preferred use with containing the coupler of alkyl through surface-treated silicon-dioxide or titanium dioxide particulate.These particles preferably have the average initial particle diameter of 10-500nm.The desired contents of these particles in color toner is 0.1-20% weight.

Toning agent can contain releasing agent.Can use the releasing agent of any kind that is usually used in toning agent.The example of useful releasing agent comprises alkene, for example low-molecular-weight polypropylene, low molecular weight polyethylene and ethylene-propylene copolymer, Microcrystalline Wax, carnauba wax, Fischer-Tropsh wax and paraffin.The appropriate level of releasing agent in toning agent is 1-5% weight.

If necessary, toning agent can contain charge control agent.In order to develop the color, charge control agent is preferably colourless.For example, can use the charge control agent that has quaternary ammonium salt structure and have the calixarene structure.

Carrier can mix with toning agent and use to constitute two-component developing agent, only comprises non-coating carrier that is made of magnetic-particle such as iron and ferrite and the coating carrier that is made of magnetic-particle and resin coating.Carrier granule preferably has the volume average particle size of 30-150 μ m.

Can use the color picture formation system of color toner of the present invention to have no particular limits.For example, color toner can be applied to one will be on the full-colour image that forms by continuous formation monochrome image on the sight sensor be transferred to system on the medium; Perhaps be applied to one with the monochrome image continuously transfer printing that forms on the sight sensor to the intermediate image holding element to form full-colour image, then it is transferred in the system on the medium.

[hot tranfer recording material]

Hot tranfer recording material of the present invention is made of printing ink sheet and visual receiving sheet.The printing ink sheet comprises substrate and is dispersed in the ink lay of the azoic dyestuff of the present invention in the tackiness agent.The printing ink receiving sheet receives and secures the dyestuff that shifts from the printing ink sheet according to the picture record signal through the heat of heating head.The ink lay of printing ink sheet is to be applied on the substrate in solvent and tackiness agent or with the finely divided ink composite that makes in the tackiness agent of azoic dyestuff with azoic dyestuff dissolving, and this coating drying is made.Be used to prepare adhesive resin, printing ink solvent and the substrate of printing ink sheet and visual receiving sheet to be made up and be preferably selected from described in the JP-A-7-137466 those.

In order to form full-colour image, preparation have the ink lay that contains the thermal diffusivity cyan dye the cyan ink sheet, have the magenta ink sheet of the ink lay that contains the thermal diffusivity magenta dye and have the yellow oil ink sheet of the ink lay that contains the thermal diffusivity yellow dyes.If necessary, can mix the black oil ink sheet that uses ink lay with the material that contains formation black image.

[colour filter]

Colour filter is to form pattern by a kind of use photo-resist that comprises, this method of patterning then dyes; And a kind ofly comprise that the method for patterning that forms the photo-resist contain tinting material makes.Back one method is disclosed in JP-A-4-163552, JP-A-4-128703 and JP-A-4-175753.Anyly in these methods all can be used for producing colour filter of the present invention.Colour filter of the present invention is preferably by disclosed method production among JP-A-4-175753 and the JP-A-6-35182, they comprise: be applied on the substrate with a kind of positive corrosion-resistant composition that contains thermosetting resin, quinone diazide, linking agent, tinting material and solvent, with this coating (photo-resist) exposure, the exposure region development is formed the positive resist pattern case by shielding; Should expose by whole corrosion-resisting patterns; And corrosion-resisting pattern solidified.Form black matix to obtain RGB or YMC colour filter according to usual manner.Used thermosetting resin, quinone diazide, linking agent and solvent types and amount thereof are preferably selected from those disclosed in the patent of quoting as proof above.

The invention provides a kind of method that on visual receiver media, improves the ozone resistants of color picture during ink-vapor recording, described visual receiver media has a substrate and contain inorganic white pigment particulate ink receiving layer with one of inkjet ink composition formation on this substrate, and this method comprises uses above-mentioned ink composite of the present invention to carry out ink-vapor recording.

The used visual receiver media of this respect of the present invention is with described identical with regard to ink jet recording method.

Embodiment

Describe the present invention in more detail referring now to embodiment, what it should be understood that is that the present invention does not think and is limited to this.Except as otherwise noted, all per-cents and part are all by weight.

Embodiment 1

The preparation of water-based inks

Following component is mixed, and the adding deionized water is made 1 liter.This mixture heated 1 hour down at 30-40 ℃, stirred simultaneously.If necessary, the pH of this mixture is adjusted to 9, and under pressure, is that the micro-strainer of 0.25 μ m filters by mean pore size, make ink composite A this mixture with the 10mol/L potassium hydroxide aqueous solution.

The prescription of ink composite A

Azo-compound a-26 8.5g/l

Diethylene Glycol 150g/l

Urea 37g/l

Glycerine 130g/l

Triethylene glycol single-butyl ether 130g/l

Trolamine 6.9g/l

Benzotriazole 0.08g/l

Surfynol 465 (derives from Air Products﹠amp; Chemicals company) 10g/l

Proxel XL 3.5g/l

Prepare ink composite B-L with same way as, just replace compound a-26 with the azoic dyestuff shown in the following table 10 with ink composite A.

Picture record and evaluation

Go up each ink composite A-L of use at ink-jet printer (PM-700C derives from Seiko Epson Corporation of Cisco) and go up record one image at waxy luster printing paper (super developing out paper level derives from Fujiphoto company limited).Color, photostabilization and the ozone resistants of following evaluation gained image.Gained the results are shown in table 10.

1) color

Its color that detects by an unaided eye, and press the graduation of A-C rank.A is meant " excellence ", and B is meant " good ", and C is meant " poor ".

2) photostabilization

Use reflection densitometer X-Rite 310TR to measure after the record at once density of image (initial density: C _i).In the burn-in test meter (Atlas Ci65 derives from Atlas electrical equipment company) with image with xenon light (85000lux) exposure 7 days after, once more at initial density C _iBe that 3 points of 1,1.5 and 2.0 are measured density of image (C _f).Calculate dyestuff retention rate (%) by following equation:

Dyestuff retention rate (%)=[(C _i-C _f)/C _i] * 100

With the dyestuff retention rate of each measuring point be 80% or higher image be decided to be A.There is 1 or 2 s' dyestuff retention rate to be lower than 80% image in 3 points and is decided to be B.The dyestuff retention rate of each point is lower than 80% image and is decided to be C.

3) ozone resistants

At once image after the record in being the chamber of 0.5ppm, concentration of ozone gas was left standstill 24 hours.To estimate the dyestuff retention rate of identical mode after 3 measuring points obtain to be exposed in the ozone with photostabilization.Concentration of ozone gas in the chamber is to adjust with ozone gas detector (OZG-EM-01 derives from Applics company limited).With the dyestuff retention rate of each measuring point be 70% or higher image be decided to be A.There is 1 or 2 s' dyestuff retention rate to be lower than 70% image in 3 points and is decided to be B.The dyestuff retention rate of each point is lower than 70% image and is decided to be C.

Table 10

Printing ink	Dyestuff	Color	Photostabilization	Ozone resistants	Remarks
						A	a-26	A	A	A	Invention
B	a-27	A	A	A	Invention
						C	a-28	A	A	A	Invention
D	a-29	A	A	A	Invention
						E	b-5	A	A	A	Invention
F	b-8	A	A	A	Invention
						G	c-2	A	A	A	Invention
H	c-3	A	A	A	Invention
						I	(a)	A-B	C	C	Contrast
J	(b)	B-C	B	C	Contrast
						K	(c)	B	B	C	Contrast
L	(d)	A	B	C	Contrast

Comparative dye (a):

Comparative dye (b):

Comparative dye (c):

Comparative dye (d):

As seen from Table 10, the magenta of printing with ink composite A-H of the present invention is visual clearer than what print with comparative ink composition I-L.And the image of printing with ink composite A-H is in excellence aspect photostabilization and the ozone resistants.

And, go up use ink composite A-H at identical ink-jet printer (PM-700C) and print ultra-fine waxy luster printing paper (MJA4S3P derives from Cisco's Epson).Estimate color, photostabilization and the ozone resistants of gained image, obtain showing similar gratifying result to table 10.

Embodiment 2

The preparation of ink sample 201

Under 70 ℃ azoic dyestuff b-1 (oil-soluble colourant) (4.83g) is dissolved in 4.22g high boiling organic solvent S-2 (showing below), 5.63g high boiling organic solvent S-11 (showing below) and the 50ml ethyl acetate with the 7.04g dioctyl sodium sulphosuccinate.In this solution, add the 500ml deionized water, stir with magnetic stirrer simultaneously, prepare the thick dispersion liquid of a kind of oil-in-water-type, with this thick dispersion liquid in the pressure of 600bar down by microfluidization device (deriving from Microfluidics company) 5 times.Gained emulsion desolventizing on rotatory evaporator is up to the smell that can't smell ethyl acetate.The thin emulsion of gained hydrophobic dye is mixed with 140g Diethylene Glycol, 50g glycerine, 7g Surfynol 465 (deriving from air products and chemical company) and 900ml deionized water, make ink sample 201.

S-2：

S-11：

(preparation of ink sample 202-210)

Prepare ink sample 202-210 in the mode identical, just replace oil soluble azo-compound b-1 with the oil soluble azo-compound shown in the following table 11 with ink sample 201.Table 11 has also shown the volume average particle size with the gained emulsion ink goods 201-210 of the particle size analyzer Micro Track UPA mensuration of Nikkiso company limited supply.

Picture record and evaluation

Waxy luster printing paper (ink-jet developing out paper level derives from Fujiphoto) ink-jet printer (PM-700C derives from Cisco's Epson) writes down an image with each ink sample 201-210.Estimate color, paper dependency, water-based, photostabilization and the ozone resistants of the image of record in accordance with the following methods.Also estimate the comparative ink composition I-L that makes among the embodiment 1 in the same manner.Gained the results are shown in table 11.

1) color

With the reflection spectrum of 10nm wavelength interval at the area test image of 390-730nm, and with CIE 1976L ^*a ^*b ^*The color space system is basic calculation a ^*And b ^*Value.Preferred magenta tone is defined as follows, and color that should image is divided into the A-C level according to following standard.

Preferred a ^*Value: 76 or bigger

Preferred b ^*Value :-30 to 0

A:a ^*And b ^*Value is in preferable range separately.

B:a ^*And b ^*One of value is in its preferable range.

C:a ^*And b ^*Value is not in preferable range separately.

2) paper dependency

The tone of the image that forms separately on the paper with the tone of the image that forms on the waxy luster printing paper and plain paper copier is compared.Difference between two is little, illustrates that the paper dependency is little, is decided to be A (satisfactory), and difference is big is decided to be B (poor).

3) water-repellancy

With the waxy luster printing paper that is formed with image thereon under room temperature dry 1 hour, in water, soaked for 30 seconds then, and seasoning under room temperature.Observe the printing ink image thorn that becomes mildewed, and the water-repellancy of printing ink is decided to be A (not having burr), B (slightly jagged) or C (sizable burr).

4) photostabilization

The image that forms on waxy luster printing paper in the burn-in test meter (Ci65 derives from Atlas) xenon light (85,000lux) expose 3 days down.Obtain dyestuff retention rate in the mode identical at 3 measuring points with embodiment 1.The dyestuff retention rate of each measuring point be 70% or higher image be decided to be A.There is the dyestuff retention rate of 1 or 2 point to be lower than 70% image in 3 points and is decided to be B.Be lower than 70% image at the dyestuff retention rate of every bit and be decided to be C.

5) ozone resistants

According to embodiment 1 used identical measuring method and staging hierarchy.

Table 11

Sample	Dyestuff	Median size (nm)	Color	The paper dependency	Water-repellancy	Photostabilization	Ozone resistants
								201	a-21	55	A	A	A	A	A
202	a-22	48	A	A	A	A	A
								203	a-23	63	A	A	A	A	A
204	a-24	58	A	A	A	A	A
								205	a-25	70	A	A	A	A	A
206	b-1	73	A	A	A	A	A
								207	b-3	72	A	A	A	A	A
208	c-4	53	A	A	A	A	A
								209	c-5	52	A	A	A	A	A
210	e-1	68	A	A	A	A	A
								I	(a)	-	B	B	B	B	C
J	(b)	-	B	B	B	A-B	C
								K	(c)	-	B	B	B	B	C
L	(d)	-	A-B	B	B	A-B	C

As seen from Table 11, inkjet ink composition coupling development of the present invention, paper dependency, color, water-repellancy and ozone resistants excellence.

Embodiment 3

Use the ink-jet printer BJ-F850 (deriving from Canon Inc.) that loads print cartridge (filling each ink composite of preparation among the embodiment 2) on waxy luster printing paper GP-301 (deriving from Canon Inc.), to carry out spray ink Printing.What obtain among these visual evaluation results and the embodiment 2 is identical.

Embodiment 4

The preparation of color toner

The copolymer in cinnamic acrylic ester HIMRTB-1000F (deriving from Sanyo chemical industry company limited) of 3 parts of azoic dyestuff a-16 and 100 parts is pulverized in ball mill, mediate down at 150 ℃, and cooling.With the coarse reduction in hammer mill of this solid, pulverize at jet-propelled pulverizer, and classification prepares the toning agent that particle diameter is the 1-20 micron.This toning agent is mixed with 10: 90 weight ratio with iron powder carrier EFV250/400 (deriving from Powdertech company), make a two-component developing agent.

Prepare photographic developer in the same manner, only be to use the pigment shown in 3 parts of dyestuffs shown in the table 12 or the 6 parts of tables 12 to replace 3 parts of azoic dyestuff a-16.

Imaging and evaluation

Use each photographic developer of gained to duplicate test at dry type electrophotographic duplicating machine NP-5000 (by Canon Inc.'s supply).Use paper and OHP thin slice to form reflection image and transmission image respectively as visual receiver media.The amount of adherent toning agent is set in 0.7 ± 0.05mg/cm on the medium ²Estimate color, photostabilization and the transparency (the OHP image) of gained image in accordance with the following methods.Gained the results are shown in table 12.

1) color

With with embodiment 1 in identical mode observe color and classification.

2) photostabilization

In burn-in test meter (Ci65 derives from Atlas) with toner image xenon light (85,000lux) down expose 5 days, with the dyestuff retention rate after the mode calculation exposure identical with embodiment 1.The dyestuff retention rate be 90% or higher image be decided to be A.The dyestuff retention rate is that the image of 80-90% is decided to be B.The dyestuff retention rate is lower than 80% image and is decided to be C.

3) transparency

Measure the visible transmission ratio of OHP image with the 330 type automatic recording spectrophotometers that derive from Hitachi company limited at 650nm.Use the spectral transmittance (650nm) of the OHP thin slice that is not formed with image to be used for proofreading and correct.With spectral transmittance be 80% or higher image be decided to be A.Spectral transmittance is that the image of 70-80% is decided to be B.Spectral transmittance is lower than 70% image and is decided to be C.

Table 12

	Tinting material	Color	Photostabilization	Transparency
					The present invention	a-16	A	A	A
The present invention	a-17	A	A	A
					The present invention	a-1	A	A	A
The present invention	b-2	A	A	A
					Contrast	(e)	A	C	A
Contrast	(f)	B	B	B
					Contrast	C.I. Pigment red 57:1	C	A	C
Contrast	C.I. pigment red 122	C	A	C

Comparative dye (e):

Comparative dye (f) (compound of JP-A-7-209912, embodiment 1):

As seen from Table 12, color toner of the present invention presents excellent color rendition and high transparency (being fit to OHP).Therefore, they are applicable to panchromatic reproduction.Owing to have gratifying photostabilization, therefore toning agent of the present invention can provide the image that can preserve for a long time.

Embodiment 5

The preparation of hot transfer ink sheet

With metal thread bar be coated with coating composition that device will have the ink lay of following prescription be coated to the 6 μ m thick pet films (deriving from Teijin company limited) that a heat-resisting sliding coating is arranged on the reverse side go up to its dry thickness be 1.5 μ m, make a hot transfer ink sheet 501.The prescription of the coating composition of ink lay:

Azoic dyestuff b-2 10mmol

Polyvinyl butyral resin (Denka Butyral 5000-A, 3g

Derive from Denki Kagaku Kogyo K.K.)

Toluene 40ml

Methyl ethyl ketone 40ml

(Takenate D110N derives from Takedaization 0.2ml to polymeric polyisocyanate

Learn Industrial Co., Ltd)

Prepare hot transfer ink sheet 502-505 in the mode identical, just replace compound b-2 with the dye composition shown in the following table 13 with printing ink sheet 501.

Heat transfer resembles the reception preparation of sections

With metal thread bar be coated with coating composition that device will have following prescription be coated to the thick synthetic paper YUPO-FPG-150 of 150 μ m (deriving from YUPO company) go up to its dry thickness be 8 μ m, with its in 100 ℃ stove dry 30 minutes, make a heat transfer and resemble the reception thin slice.

The prescription of the coating composition of image receiving layer:

Vibrin (Vylon 280, derive from Toyobo company limited) 22g

Polymeric polyisocyanate (KP-90 derives from Dainippon ink chemistry company) 4g

(KF-857 derives from Shin-Etsu polysiloxane 0.5g to amino modified silicone oil

Company limited)

Methyl ethyl ketone 85ml

Toluene 85ml

Pimelinketone 15ml

Each printing ink sheet 501-505 and image are received thin slice to be overlapped each other and makes ink lay face visual receiving layer.Is that 0.15-15msec and dot density are to carry out hot tranfer recording under the condition of 6 point/mm by applying heat energy from printing ink sheet side with heating head being output as 0.25W/ point, pulse width.The magenta image that forms on visual receiving layer is clear, does not have the transfer printing inhomogeneity.

Measure the maximum density of gained image.And, the image on the visual receiving layer is exposed 5 days down at xenon light (17000lux).Measure initial conditions A reflection density (before the exposure) and be the state A reflection density of 1.0 area of image, calculate the dyestuff percent retention, thereby estimate the photostabilization of dyestuff.Gained the results are shown in table 13.

Table 13

The dyestuff supply sheet	Dyestuff	Maximum density	Photostabilization (%)	Remarks
					501	b-2	1.8	91	The present invention
502	b-6	1.7	89	The present invention
					503	a-16	1.6	92	The present invention
504	a-19	1.6	90	The present invention
					505	(g)	1.8	52	Contrast

Comparative dye (g):

As can be seen from Table 13, the hot tranfer recording material that contains azoic dyestuff of the present invention provides the transferred image that comparison is more clear than the color of material and photostabilization is high.

Embodiment 6

The preparation of positive corrosion-resistant composition

By the positive corrosion-resistant composition of following preparation of compositions.

Thermosetting resin: by-cresols/p-Cresol/formaldehyde (3.4 parts of mol ratios

=5/5/7.5) cresol novolac resin of Huo Deing; With polystyrene conversion

Molecular-weight average: 4300

Quinone diazide: 1.8 parts of the 5-that makes by the oxybenzene compound of following formula

The adjacent naphthoquinone two azide (average 2 hydroxyls are esterified) of sulfonic acid

Linking agent: 0.8 part of hexa methoxy methoxylation melamine

Solvent: 20 parts of ethyl lactates

1 part of magenta dye of the present invention (referring to table 14)

The preparation of colour filter

With positive corrosion-resistant composition by spin-applied to the wafer and the heating evaporation solvent.The photo-resist layer of Xing Chenging uses online stepper LD-5010-i (NA=0.40) (by the supply of Hitachi company limited) by a shielding exposure thus, thereby the quinone diazide of exposure region is decomposed.The photo-resist of exposure is heated to 100 ℃, uses alkaline developer SOPD or SOPD-B (deriving from Sumitomo chemistry company limited) to develop to remove these exposure regions then, obtaining resolving power is 0.8 μ m dot matrix multi color pattern.With the whole regional exposure of this pattern, and 150 ℃ of down heating 15 minutes, the magenta color filter that the reproducibility that obtains losing lustre is used.

The preparation of contrast colour filter

Prepare positive corrosion-resistant composition in identical as mentioned above mode, just replace magenta dye of the present invention with contrast magenta dye Orasol Pink (deriving from Ciba-Geigy company limited).With the positive corrosion-resistant composition of gained by spin-applied to wafer, then heating is with solvent evaporation.Wafer through scheming decent exposure, is developed to form resolving power with alkaline developer and is the positive colored pattern of 1 μ m, it is exposed fully, and heated 10 minutes down, obtain contrasting magenta color filter at 150 ℃.

Estimate

The absorption characteristic and the photostabilization of following evaluation gained colour filter.Gained the results are shown in table 14.

1) absorption characteristic

Measure the transmitted spectrum of each magenta color filter, and compare the acutance of these spectrum at the slope of short or longer wavelength side.The colour filter that has steep slope on the two sides is decided to be A.The colour filter that has one side to have steep slope in the two sides is decided to be B.The two sides does not all have the colour filter of steep slope to be decided to be C.

2) photostabilization

In burn-in test meter (Ci65 derives from Atlas), colour filter is exposed 7 days down at xenon light (85000lux).Estimate photostabilization with the dyestuff retention rate (%) after the exposure.Gained the results are shown in table 14.

Table 14

	Dyestuff	Absorption characteristic	Photostabilization (%)
				The present invention	a-16	A	92
The present invention	b-2	A	88
				The present invention	e-3	A	87
The present invention	e-5	A	85
				Contrast	Orasol Pink	B	67

As seen from Table 14, compare with the contrast colour filter, the colour filter that uses azoic dyestuff of the present invention to make all shows steep slope in short and longer wavelength side, has guaranteed excellent color rendition and excellent photostabilization.

Because coloured composition of the present invention contains a kind of new dye, this dyestuff presents excellent absorption characteristic to one of 3 kinds of primary colours and has the performance of the reactive gas in enough anti-light, heat, the wet and environment, so this coloured composition can provide the color picture or the coloured material of color and patience excellence.This coloured composition be particularly useful for making printing ink sheet, the electrophotography of marking ink such as jetted ink, hot tranfer recording material color toner, be used for indicating meter such as the colour filter of LCD and PDP and solid-state image pickup such as CCD and the dye bath that fabric is used.

Comprise the inkjet ink composition of this coloured composition and use the ink jet recording method of this inkjet ink composition that the image of the performance of reactive gas, particularly ozone gas in satisfactory color and anti-light and the environment is provided.

Use the hot tranfer recording material of this coloured composition preparation that the colour transfer that color is clear and photostabilization is excellent image is provided.Use the color toner of this coloured composition preparation that the toner image that presents high-light-fastness, excellent color rendition and high-clarity (to OHP) is provided.

Use the colour filter of this coloured composition preparation to have excellent color rendition and photostabilization.

Embodiment 7

The preparation of water-based inks

Following component is mixed,, stir simultaneously, and under pressure, be that 0.8 μ m and diameter are that the micro-strainer of 47mm filters, make ink composite 2-A by mean pore size 30-40 ℃ of heating 1 hour down.

The prescription of ink composite 2-A

5 parts of azo-compound 2-a-6

9 parts of Diethylene Glycols

9 parts of TEG monos

7 parts of glycerine

2 parts of diethanolamine

70 parts in water

Prepare ink composite 2-B to 2-L with same way as, just replace compound 2-a-6 with the azoic dyestuff shown in the following table 2-6 with ink composite 2-A.

Picture record and evaluation

Go up each ink composite 2-A to 2-L of use at ink-jet printer (PM-700C derives from Seiko Epson Corporation of Cisco) and go up record one image at waxy luster printing paper (super developing out paper level derives from Fujiphoto company limited).Color, photostabilization and the ozone resistants of following evaluation gained image.

Gained the results are shown in table 2-6.

1) color

Its color that detects by an unaided eye, and press the graduation of A-C rank.A is meant " excellence ", and B is meant " good ", and C is meant " poor ".

2) photostabilization

Use reflection densitometer X-Rite 310TR to measure after the record at once density of image (initial density: C _i).In burn-in test meter (Atlas Ci65 derives from Atlas electrical equipment company) with image with xenon light (85,000lux) after the exposure 7 days, be that 3 points of 1,1.5 and 2.0 are measured density of image (C in initial density once more _f).Calculate dyestuff retention rate (%) by following equation:

Dyestuff retention rate (%)=[(C _i-C _f)/C _i] * 100

With the dyestuff retention rate of each measuring point be 80% or higher image be decided to be A.There is 1 or 2 s' dyestuff retention rate to be lower than 80% image in 3 points and is decided to be B.The dyestuff retention rate of each point is lower than 80% image and is decided to be C.

3) ozone resistants

At once image after the record in being the chamber of 0.5ppm, concentration of ozone gas was left standstill 24 hours.With with photostabilization estimate identical mode with X-Rite 310TR initial density be 1,1.5 with 2.0 3 somes mensuration and dyestuff retention rate after ozone contacts.Ozone concn in the chamber is to adjust with ozone gas detector (OZG-EM-01 derives from Applics company limited).With the dyestuff retention rate of each measuring point be 70% or higher image be decided to be A.There is 1 or 2 s' dyestuff retention rate to be lower than 70% image in 3 points and is decided to be B.The dyestuff retention rate of each point is lower than 70% image and is decided to be C.

Table 2-6

Printing ink	Dyestuff	Color	Photostabilization	Ozone resistants	Remarks
						2-A	2-a-6	A	A	A	The present invention
2-B	2-a-7	A	A	A	The present invention
						2-C	2-a-8	A	A	A	The present invention
2-D	2-a-9	A	A	A	The present invention
						2-E	2-b-1	A	A	A	The present invention
2-F	2-b-4	A	A	A	The present invention
						2-G	2-c-1	A	A	A	The present invention
2-H	2-c-3	A	A	A	The present invention
						2-I	(2-a)	A-B	C	C	Contrast
2-J	(2-b)	B-C	B	C	Contrast
						2-K	(2-c)	B	B	C	Contrast
2-L	(2-d)	A	B	C	Contrast

Comparative dye (2-a):

Comparative dye (2-b):

Comparative dye (2-c):

Comparative dye (2-d):

2-6 finds out from table, and is clearer than what print with comparative ink composition 2-I to 2-L with the magenta image that ink composite 2-A to 2-H of the present invention prints.And the image of printing with ink composite 2-A to 2-H is in excellence aspect photostabilization and the ozone resistants.

And, go up use ink composite 2-A to 2-H at identical ink-jet printer (PM-700C) and print ultra-fine waxy luster printing paper (MJA4S3P derives from Cisco's Epson).Color, photostabilization and the ozone resistants of evaluation gained image obtain and show 2-6 and show similar gratifying result.

Because coloured composition of the present invention contains a kind of new dye, this dyestuff presents excellent absorption characteristic to one of 3 kinds of primary colours with regard to color and color rendition and has the performance of the reactive gas in enough anti-light, heat, the wet and environment, so this coloured composition can provide the color picture or the coloured material of color and patience excellence.This coloured composition is particularly useful for making the dye bath that marking ink such as jetted ink and fabric are used.

Comprise the inkjet ink composition of this coloured composition and use the ink jet recording method of this inkjet ink composition that the image of the performance of reactive gas, particularly ozone gas in satisfactory color and anti-light and the environment is provided.

Embodiment 8

Compound 3-12's is synthetic

With 0.13g (0.6mmol) 2-amino-4; the mixture of 5-dicyano-1-ethoxy carbonyl Methylimidazole, 0.8ml acetate and 1.2ml propionic acid stirs under 0 ℃ or lower internal temperature, and to 45% nitrosyl sulphuric acid that wherein adds 0.19g (0.66mmol).This mixture was stirred 30 minutes under this temperature, form a diazonium salt.

In another flask, with 0.26g (0.5mmol) 2,6-two (4-octyl group phenylamino)-3-cyano group-4-picoline, 0.8g sodium acetate, 4.5ml dimethyl formamide (DMF) and 2ml ethyl acetate stir and are cooled to 0 ℃ or lower internal temperature.Above-mentioned diazonium salt is joined in this mixture.After the adding, reaction mixture was reacted 1 hour under this uniform temp.In this reaction mixture, add the 30ml saturated sodium-chloride water solution.Suction filtration is collected the throw out (comprising compound 3-5) that forms thus.This coarse crystallization obtains compound 3-12 by column chromatography (hexane-ethyl acetate) purifying.

λ _Max=510nm (DMF solution)

M/z (FAB-MS, positive ion model)=755

Embodiment 9

Compound 3-15's is synthetic

With 0.13g (0.6mmol) 2-amino-4; the mixture of 5-dicyano-1-ethoxy carbonyl Methylimidazole, 0.8ml acetate and 1.2ml propionic acid stirs under 0 ℃ or lower internal temperature, and to 45% nitrosyl sulphuric acid that wherein adds 0.19g (0.66mmol).This mixture was stirred 30 minutes under this temperature, form a diazonium salt.

In another flask, with 0.25g (0.5mmol) 2,6-two (4-octyl group phenylamino)-4-picoline, 0.8g sodium acetate, 4.5ml DMF and 2ml ethyl acetate stir and are cooled to 0 ℃ or lower internal temperature.Above-mentioned diazonium salt is joined in this mixture, reaction mixture was reacted 1 hour under this uniform temp.In this reaction mixture, add the 30ml saturated sodium-chloride water solution.Suction filtration is collected the throw out that forms thus.This coarse crystallization obtains compound 3-15 by column chromatography (hexane-ethyl acetate) purifying.

λ _Max=528nm (DMF solution)

M/z (FAB-MS, positive ion model)=730

Embodiment 10

Compound 3-35's is synthetic

The mixture of 0.16g (0.6mmol) 5-amino-1-tert-butoxycarbonyl methyl-3-Phenyltriazole, 0.6ml acetate and 0.9ml propionic acid is stirred under 0 ℃ or lower internal temperature, and to 45% nitrosyl sulphuric acid that wherein adds 0.19g (0.66mmol).This mixture was stirred 30 minutes under this temperature, form a diazonium salt.

In another flask, with 0.26g (0.5mmol) 2,6-two (4-octyl group phenylamino)-3-cyano group-4-picoline, 0.8g sodium acetate, 4.5ml DMF and 2ml ethyl acetate stir and are cooled to 0 ℃ or lower internal temperature.Above-mentioned diazonium salt is joined in this mixture, and after adding, reaction mixture was reacted 1 hour under this uniform temp.In this reaction mixture, add the 30ml saturated sodium-chloride water solution.Suction filtration is collected the throw out that forms thus.Obtain the compound 3-35 of 0.15g (37%) by the acetonitrile recrystallize.

λ _Max=493nm (DMF solution)

M/z (FAB-MS, positive ion model)=810

Embodiment 11

Compound 3-37's is synthetic

The mixture of 0.16g (0.6mmol) 5-amino-1-tert-butoxycarbonyl methyl-3-Phenyltriazole, 0.6ml acetate and 0.9ml propionic acid is stirred under 0 ℃ or lower internal temperature, and to 45% nitrosyl sulphuric acid that wherein adds 0.19g (0.66mmol).This mixture was stirred 30 minutes under this temperature, form a diazonium salt.

In another flask, with 0.25g (0.5mmol) 2,6-two (4-octyl group phenylamino)-3-formamyl-4-picoline, 0.8g sodium acetate, 4.5ml DMF and 2ml ethyl acetate stir and are cooled to 0 ℃ or lower internal temperature.Above-mentioned diazonium salt is joined in this mixture.After the adding, reaction mixture was reacted 1 hour under this uniform temp.In this reaction mixture, add the 30ml saturated sodium-chloride water solution, and use the ethyl acetate extraction organism.The gained coarse crystallization obtains compound 3-37 by column chromatography (hexane-ethyl acetate) purifying.

λ _Max=507nm (DMF solution)

M/z (FAB-MS, positive ion model)=828

Embodiment 12

Compound 3-38's is synthetic

The mixture of 0.16g (0.6mmol) 5-amino-1-tert-butoxycarbonyl methyl-3-Phenyltriazole, 0.6ml acetate and 0.9ml propionic acid is stirred under 0 ℃ or lower internal temperature, and to 45% nitrosyl sulphuric acid that wherein adds 0.19g (0.66mmol).This mixture was stirred 30 minutes under this temperature, form a diazonium salt.

In another flask, with 0.27g (0.5mmol) 2,6-two (4-octyl group phenylamino)-4-picoline, 0.8g sodium acetate, 4.5ml DMF and 2ml ethyl acetate stir and are cooled to 0 ℃ or lower internal temperature.Above-mentioned diazonium salt is joined in this mixture.After the adding, reaction mixture was reacted 1 hour under this uniform temp.In this reaction mixture, add the 30ml saturated sodium-chloride water solution, and use the ethyl acetate extraction organism.The gained coarse crystallization obtains compound 3-38 by column chromatography (hexane-ethyl acetate) purifying.

λ _Max=511nm (DMF solution)

M/z (FAB-MS, positive ion model)=785

Embodiment 13

The preparation of jetted ink

Following component is mixed,, stir simultaneously, and under pressure, be that 0.8 μ m and diameter are that the micro-strainer of 47mm filters, make ink composite 3-A by mean pore size 30-40 ℃ of heating 1 hour down.

The prescription of ink composite 3-A

5 parts of compound 3-21

9 parts of Diethylene Glycols

9 parts of TEG monos

7 parts of glycerine

1 part of diethanolamine

70 parts in water

Prepare ink composite 3-B to 3-D with same way as, just replace compound 3-21 with the azo-compound shown in the following table 3-5 with ink composite 3-A.Also prepare comparative ink composition 3-E to 3-H in the same manner, but be to use following comparative dye (3-a) to (3-d):

Comparative dye (3-a):

Comparative dye (3-b):

Comparative dye (3-c):

Comparative dye (3-d):

Picture record and evaluation

Go up each ink composite 3-A to 3-H of use at ink-jet printer (PM-700C derives from Seiko Epson Corporation of Cisco) and go up record one image at waxy luster printing paper (super developing out paper level derives from Fujiphoto company limited).The photostabilization and the ozone resistants of following evaluation gained image.Gained the results are shown in table 3-5.

1) photostabilization

Use reflection densitometer X-Rite 310TR to measure after the record at once density of image (initial density: C _i).In burn-in test meter (Atlas Ci65 derives from Atlas electrical equipment company) with image with xenon light (85,000lux) after the exposure 7 days, be that 3 points of 1,1.5 and 2.0 are measured density of image (C in initial density once more _f).Calculate dyestuff retention rate (%) by following equation:

Dyestuff retention rate (%)=[(C _i-C _f)/C _i] * 100

With the dyestuff retention rate of each measuring point be 80% or higher image be decided to be A.There is 1 or 2 s' dyestuff retention rate to be lower than 80% image in 3 points and is decided to be B.The dyestuff retention rate of each point is lower than 80% image and is decided to be C.

2) ozone resistants

At once image after the record in being the chamber of 0.5ppm, concentration of ozone gas was left standstill 24 hours.Obtain contact dyestuff retention rate afterwards to estimate identical mode with ozone with photostabilization.Ozone concn in the chamber is to adjust with ozone gas detector (OZG-EM-01 derives from Applics company limited).With the dyestuff retention rate of each measuring point be 70% or higher image be decided to be A.There is 1 or 2 s' dyestuff retention rate to be lower than 70% image in 3 points and is decided to be B.The dyestuff retention rate of each point is lower than 70% image and is decided to be C.

Table 3-5

Printing ink	Dyestuff	Photostabilization	Ozone resistants	Remarks
					3-A	3-21	A	A	The present invention
3-B	3-23	A	A	The present invention
					3-C	3-44	A	A	The present invention
3-D	3-46	A	A	The present invention
					3-E	3-a	C	C	Contrast
3-F	3-b	B	C	Contrast
					3-G	3-c	B	C	Contrast
3-H	3-d	A-B	B	Contrast

3-5 finds out from table, the magenta image of printing with ink composite 3-A to 3-D than the image of printing with comparative ink composition 3-E to 3-H more excellent aspect photostabilization and the ozone resistants.In addition, compare with comparative dye, dyestuff of the present invention presents excellent color rendition at the absorption spectrum that has steep slope than short and longer wavelength side.

And, go up use ink composite 3-A to 3-D at identical ink-jet printer (PM-700C) and print ultra-fine waxy luster printing paper (MJA4S3P derives from Cisco's Epson).The photostabilization and the ozone resistants of evaluation gained image obtain and show 3-5 and show similar gratifying result.

Embodiment 14

The preparation of ink sample 3-101 (emulsion ink)

Under 70 ℃ azoic dyestuff 3-12 (oil-soluble colourant) (5.63g) is dissolved in 4.22g high boiling organic solvent 3-S-2 (showing below), 5.63g high boiling organic solvent 3-S-11 (showing below) and the 50ml ethyl acetate with the 7.04g dioctyl sodium sulphosuccinate.In this solution, add the 500ml deionized water, stir with magnetic stirrer simultaneously, prepare the thick dispersion liquid of a kind of oil-in-water-type, with this thick dispersion liquid in the pressure of 600bar down by microfluidization device (deriving from Microfluidics company) 5 times.Gained emulsion desolventizing on rotatory evaporator is up to the smell that can't smell ethyl acetate.The thin emulsion of gained hydrophobic dye is mixed with 140g Diethylene Glycol, 50g glycerine, 7g Surfynol 465 (deriving from air products and chemical company) and 900ml deionized water, make ink sample 3-101.

The preparation of ink sample 3-102 to 3-105

Prepare ink sample 3-102 to 3-105 in the mode identical, just replace oil-soluble compounds 3-12 with the oil-soluble compounds shown in the following table 3-6 with ink sample 3-101.Prepare comparative ink sample 3-106 to 3-107 in the same manner, only be to use following comparative dye (3-e) and (3-f).

Comparative dye (3-e):

Comparative dye (3-f):

3-3-2：

3-S-11：

Picture record and evaluation

Waxy luster printing paper (ink-jet developing out paper level derives from Fujiphoto) ink-jet printer (PM-700C derives from Cisco's Epson) writes down an image with each ink sample 3-101 to 3-107.Estimate paper dependency, water-repellancy, photostabilization and the ozone resistants of the image of record in accordance with the following methods.Gained the results are shown in table 3-6.

1) paper dependency

The tone of the image that forms separately on the paper with the tone of the image that forms on the waxy luster printing paper and plain paper copier (PPC) is compared.Difference between two is little, illustrates that the paper dependency is little, is decided to be A (satisfactory), and difference is big is decided to be B (poor).

2) water-repellancy

With the waxy luster printing paper that is formed with image thereon under room temperature dry 1 hour, in water, soaked for 30 seconds then, and seasoning under room temperature.Observe the printing ink image thorn that becomes mildewed, and the water-repellancy of printing ink is decided to be A (not having burr), B (slightly jagged) or C (sizable burr).

3) photostabilization

The image that forms on waxy luster printing paper in the burn-in test meter (Ci65 derives from Atlas) xenon light (85,000lux) expose 3 days down.Obtain the dyestuff retention rate in the mode identical with embodiment 8.The dyestuff retention rate of each measuring point be 70% or higher image be decided to be A.There is the dyestuff retention rate of 1 or 2 point to be lower than 70% image in 3 points and is decided to be B.Be lower than 70% image at the dyestuff retention rate of every bit and be decided to be C.

4) ozone resistants

According to used identical measuring method of embodiment 13 (water-based inks) and staging hierarchy.

Table 3-6

Sample	Dyestuff	The paper dependency	Water-repellancy	Photostabilization	Ozone resistants
						3-101	3-12	A	A	A	A
3-102	3-17	A	A	A	A
						3-103	3-36	A	A	A	A
3-104	3-43	A	A	A	A
						3-105	3-45	A	A	A	A
3-106	3-e	B	B	B	C
						3-107	3-f	B	B	B	B

Result from table 3-6 finds out that inkjet ink composition of the present invention presents excellent paper dependency, water-repellancy, photostabilization and ozone resistants.And, to compare with comparative dye, dyestuff of the present invention presents excellent color rendition at the absorption spectrum that has steep slope than short and longer wavelength side.

Embodiment 15

Use the ink-jet printer BJ-F850 (deriving from Canon Inc.) that loads print cartridge (filling each ink composite of preparation among the embodiment 14) on waxy luster printing paper GP-301 (deriving from Canon Inc.), to carry out spray ink Printing, and estimate the image of these printings in mode identical among the embodiment 13.What obtain among these visual evaluation results and the embodiment 13 is identical.

New dye compound of the present invention presents excellent absorption characteristic.The image forming material that contains The compounds of this invention has the performance of the oxidizing gas in enough anti-light, heat, the wet and environment.

Embodiment 16

Compound 4-5's is synthetic

With 0.1g (0.6mmol) 5-amino-2-ethylmercapto group-1,3, the mixture of 4-thiadiazoles, 0.4ml acetate and 0.6ml propionic acid stirs under 0 ℃ or lower internal temperature, and to 45% nitrosyl sulphuric acid that wherein adds 0.19g (0.66mmol).This mixture was stirred 30 minutes under this temperature, form a diazonium salt.

In another flask, with 0.26g (0.5mmol) 2,6-two (4-octyl group phenylamino)-3-cyano group-4-picoline, 0.8g sodium acetate, 4.5ml dimethyl formamide (DMF) and 2ml ethyl acetate stir and are cooled to 0 ℃ or lower internal temperature.Above-mentioned diazonium salt is joined in this mixture.After the adding, reaction mixture was reacted 1 hour under this uniform temp.In this reaction mixture, add the 30ml saturated sodium-chloride water solution.Suction filtration is collected the throw out that forms thus.This coarse crystallization obtains 0.2g (57%) compound 4-5 by the acetonitrile recrystallize.

λ _Max=517nm (DMF solution)

ε＝41300

M/z (FAB-MS, positive ion model)=697

Embodiment 17

Compound 4-8's is synthetic

The mixture of 0.084g (0.6mmol) 5-amino-4-cyano group-3-methyl isothiazole, 0.4ml acetate and 0.6ml propionic acid is stirred under 0 ℃ or lower internal temperature, and to 45% nitrosyl sulphuric acid that wherein adds 0.19g (0.66mmol).This mixture was stirred 30 minutes under this temperature, form a diazonium salt.

In another flask, with 0.27g (0.5mmol) 2,6-two (4-octyl group phenylamino)-3-formamyl-4-picoline, 0.8g sodium acetate, 4.5ml DMF and 2ml ethyl acetate stir and are cooled to 0 ℃ or lower internal temperature.Above-mentioned diazonium salt is joined in this mixture, and reaction mixture was reacted 1 hour under this uniform temp.In this reaction mixture, add the 30ml saturated sodium-chloride water solution.Suction filtration is collected the throw out that forms thus.This coarse crystallization obtains 0.19g (55%) compound 4-8 by the methyl alcohol recrystallize.

λ _Max=563nm (DMF solution)

ε＝47700

M/z (FAB-MS, positive ion model)=693

Embodiment 18

Compound 4-13's is synthetic

The mixture of 0.44g (2.1mmol) 2-amino-5-carbonyl oxyethyl group-3-cyano group-4-thiotolene, 2.8ml acetate and 4.2ml propionic acid is stirred under 0 ℃ or lower internal temperature, and to 45% nitrosyl sulphuric acid that wherein adds 0.64g (2.3mmol).This mixture was stirred 30 minutes under this temperature, form a diazonium salt.

In another flask, with 1g (2mmol) 2,6-two (4-octyl group phenylamino)-4-picoline, 4ml N,N-dimethylacetamide and 2ml picoline stir and are cooled to 0 ℃ or lower internal temperature.Above-mentioned diazonium salt is joined in this mixture, and reaction mixture was reacted 1 hour under this uniform temp.In this reaction mixture, add saturated sodium-chloride water solution, and suction filtration is collected the throw out that forms thus.By the acetonitrile recrystallize, obtain 1.4g (97%) compound 4-13.

λ _Max=592nm (DMF solution)

ε＝40000

M/z (FAB-MS, positive ion model)=722

Embodiment 19

Compound 4-14's is synthetic

The mixture of 0.25g (1.8mmol) 5-amino-4-cyano group-3-methyl isothiazole, 1.2ml acetate and 1.8ml propionic acid is stirred under 0 ℃ or lower internal temperature, and to 45% nitrosyl sulphuric acid that wherein adds 0.6g (1.98mmol).This mixture was stirred 30 minutes under this temperature, form a diazonium salt.

In another flask, with 0.54g (1.5mmol) 2,6-two (2 ', 4 ', 6 '-trimethylanilino)-3-cyano group-4-picoline, 2.4g sodium acetate, 13.5ml DMF and 6ml ethyl acetate stir and be cooled to 0 ℃ or lower internal temperature.Above-mentioned diazonium salt is joined in this mixture.After the adding, reaction mixture was reacted 2 hours under this uniform temp.In this reaction mixture, add the 30ml saturated sodium-chloride water solution, and suction filtration is collected the throw out that forms thus.The gained coarse crystallization obtains 0.05g (55%) compound 4-14 through silica gel column chromatography (hexane-ethyl acetate) purifying.

λ _Max=529nm (DMF solution)

M/z (FAB-MS, positive ion model)=509

Embodiment 20

The preparation of inkjet ink composition

Following component is mixed,, stir simultaneously, and under pressure, be that 0.8 μ m and diameter are that the micro-strainer of 47mm filters, make ink composite 4-A by mean pore size 30-40 ℃ of heating 1 hour down.

The prescription of ink composite 4-A

5 parts of compound 4-2

9 parts of Diethylene Glycols

9 parts of TEG monos

7 parts of glycerine

1 part of diethanolamine

70 parts in water

Prepare ink composite 4-B to 4-D with same way as, just replace compound 4-2 with the azo-compound shown in the following table 4-6 with ink composite 4-A.Also prepare comparative ink composition 4-E to 4-H in the same manner, but be to use following comparative dye (4-a) to (4-d):

Comparative dye (4-a):

Comparative dye (4-b):

Comparative dye (4-c):

Comparative dye 4-d (being disclosed in EP1066341)

Picture record and evaluation

Go up each ink composite 4-A to 4-H of use at ink-jet printer (PM-700C derives from Seiko Epson Corporation of Cisco) and go up record one image at waxy luster printing paper (super developing out paper level derives from Fujiphoto company limited).Color, photostabilization and the ozone resistants of following evaluation gained image.Gained the results are shown in table 4-6.

1) color

Its color that detects by an unaided eye, and press the graduation of A-C rank.A is meant " excellence ", and B is meant " good ", and C is meant " poor ".

2) photostabilization

Use reflection densitometer X-Rite 310TR to measure after the record at once density of image (initial density: C _i).In burn-in test meter (Atlas Ci65 derives from Atlas electrical equipment company) with image with xenon light (85,000lux) after the exposure 7 days, be that 3 points of 1,1.5 and 2.0 are measured density of image (C in initial density once more _f).Calculate dyestuff retention rate (%) by following equation:

Dyestuff retention rate (%)=[(C _i-C _f)/C _i] * 100

With the dyestuff retention rate of each measuring point be 80% or higher image be decided to be A.There is 1 or 2 s' dyestuff retention rate to be lower than 80% image in 3 points and is decided to be B.The dyestuff retention rate of each point is lower than 80% image and is decided to be C.

3) ozone resistants

At once image after the record in being the chamber of 0.5ppm, concentration of ozone gas was left standstill 24 hours.Obtain contact dyestuff retention rate afterwards to estimate identical mode with ozone with photostabilization.Ozone concn in the chamber is to adjust with ozone gas detector (OZG-EM-01 derives from Applics company limited).With the dyestuff retention rate of each measuring point be 70% or higher image be decided to be A.There is 1 or 2 s' dyestuff retention rate to be lower than 70% image in 3 points and is decided to be B.The dyestuff retention rate of each point is lower than 70% image and is decided to be C.

Table 4-6

Printing ink	Dyestuff	Color	Photostabilization	Ozone resistants	Remarks
						4-A	4-2	A	A	A	The present invention
4-B	4-3	A	A	A	The present invention
						4-C	4-10	A	A	A	The present invention
4-D	4-18	A	A	A	The present invention
						4-E	4-a	A-B	C	C	Contrast
4-F	4-b	B-C	B	C	Contrast
						4-G	4-c	B	B	B	Contrast
4-H	4-d	A-B	B	C	Contrast

4-6 finds out from table, the magenta image of printing with ink composite 4-A to 4-D than the image of printing with ink composite 4-E to 4-H more excellent aspect color, photostabilization and the ozone resistants.

And, go up use ink composite 4-A to 4-D at identical ink-jet printer (PM-700C) and print ultra-fine waxy luster printing paper (MJA4S3P derives from Cisco's Epson).Estimate the color and the photostabilization of gained image in the mode identical with embodiment 20.Identical shown in the 4-6 of gained result and table.

Embodiment 21

The preparation of emulsion ink (sample 4-101)

Under 70 ℃ azo-compound 4-5 (oil-soluble colourant) (5.63g) is dissolved in 4.22g high boiling organic solvent 4-S-2 (showing below), 5.63g high boiling organic solvent 4-S-11 (showing below) and the 50ml ethyl acetate with the 7.04g dioctyl sodium sulphosuccinate.In this solution, add the 500ml deionized water, stir with magnetic stirrer simultaneously, prepare the thick dispersion liquid of a kind of oil-in-water-type, with this thick dispersion liquid in the pressure of 600bar down by microfluidization device (deriving from Microfluidics company) 5 times.Gained emulsion desolventizing on rotatory evaporator is up to the smell that can't smell ethyl acetate.The thin emulsion of gained hydrophobic dye is mixed with 140g Diethylene Glycol, 50g glycerine, 7g Surfynol 465 (deriving from air products and chemical company) and 900ml deionized water, make ink sample 4-101.

The preparation of ink sample 4-102 to 4-105

Prepare ink sample 4-102 to 4-105 in the mode identical, just replace compound 4-5 with the compound shown in the following table 4-7 with ink sample 4-101.Prepare comparative ink sample 4-106 to 4-107 in the same manner, only be to use following comparative dye (4-e) and (4-f).

Comparative dye (4-e):

Comparative dye (2-f):

4-S-2：

4-S-11：

Picture record and evaluation

Waxy luster printing paper (ink-jet developing out paper level derives from Fujiphoto) ink-jet printer (PM-700C derives from Cisco's Epson) writes down an image with each ink sample 4-101 to 4-107.Estimate color, paper dependency, water-repellancy, photostabilization and the ozone resistants of the image of record in accordance with the following methods.Gained the results are shown in table 4-7.

1) color

With the reflection spectrum of 10nm wavelength interval at the area test image of 390-730nm, and with CIE 1976L ^*a ^*b ^*The color space system is basic calculation a ^*And b ^*Value.Preferred magenta tone is defined as follows, and color that should image is divided into the A-C level according to following standard.

Preferred a ^*Value: 76 or bigger

Preferred b ^*Value :-30 to 0

A:a ^*And b ^*Value is all in preferable range separately.

B:a ^*And b ^*One of value is in its preferable range.

C:a ^*And b ^*Value is not all in preferable range separately.

2) paper dependency

The tone of the image that forms separately on the paper with the tone of the image that forms on the waxy luster printing paper and plain paper copier (PPC) is compared.Difference between two is little, illustrates that the paper dependency is little, is decided to be A (satisfactory), and difference is big is decided to be B (poor).

3) water-repellancy

With the waxy luster printing paper that is formed with image thereon under room temperature dry 1 hour, in water, soaked for 30 seconds then, and seasoning under room temperature.Observe the printing ink image thorn that becomes mildewed, and the water-repellancy of printing ink is decided to be A (not having burr), B (slightly jagged) or C (sizable burr).

4) photostabilization

The image that forms on waxy luster printing paper in the burn-in test meter (Ci65 derives from Atlas) xenon light (85,000lux) expose 3 days down.Obtain in 3 points (original reflection density: dyestuff retention rate 1,1.5 or 2.0) in the mode identical with embodiment 20.The dyestuff retention rate of each measuring point be 70% or higher image be decided to be A.There is the dyestuff retention rate of 1 or 2 point to be lower than 70% image in 3 points and is decided to be B.Be lower than 70% image at the dyestuff retention rate of every bit and be decided to be C.

5) ozone resistants

According to used identical measuring method of embodiment 20 (water-based inks) and staging hierarchy.

Table 4-7

Sample	Dyestuff	Color	The paper dependency	Water-repellancy	Photostabilization	Ozone resistants
							4-101	4-5	A	A	A	A	A
4-102	4-6	A	A	A	A	A
							4-103	4-8	A	A	A	A	A
4-104	4-13	A	A	A	A	A
							4-105	4-17	A	A	A	A	A
4-106	4-e	B	B	B	B	C
							4-107	4-f	C	C	B	B	C

Result from table 4-7 finds out that inkjet ink composition of the present invention presents excellent color, paper dependency, water-repellancy, photostabilization and ozone resistants.

Embodiment 22

Use the ink-jet printer BJ-F850 (deriving from Canon Inc.) that loads print cartridge (filling each ink composite of preparation among the embodiment 21) on waxy luster printing paper GP-301 (deriving from Canon Inc.), to carry out spray ink Printing, and estimate the image of these printings in mode identical among the embodiment 20.What obtain among these visual evaluation results and the embodiment 20 is identical.

New dye compound of the present invention just presents excellent absorption characteristic with regard to the color of one of 3 primary colours and color rendition.The image forming material that contains The compounds of this invention has the performance of the oxidizing gas in enough anti-light, heat, the wet and environment.

Embodiment 23

The preparation of water-based inks

Following component is mixed,, stir simultaneously, and under pressure, be that 0.8 μ m and diameter are that the micro-strainer of 47mm filters, make ink composite 5-A by mean pore size 30-40 ℃ of heating 1 hour down.

The prescription of ink composite 5-A

4 parts of compound 5-137 (dyestuff)

9 parts of Diethylene Glycols

9 parts of TEG monos

7 parts of glycerine

1 part of diethanolamine

70 parts in water

Prepare ink composite 5-B to 5-H with same way as, just replace compound 5-137 with the azo-compound shown in the following table 5-6 with ink composite 5-A.

Picture record and evaluation

Go up each ink composite 5-A to 5-H of use at ink-jet printer (PM-700C derives from Seiko Epson Corporation of Cisco) and go up record one image at waxy luster printing paper (super developing out paper level derives from Fujiphoto company limited).Color, photostabilization, ozone resistants and the water-repellancy of following evaluation gained image.Gained the results are shown in table 5-6.

1) color

Its color that detects by an unaided eye, and press the graduation of A-C rank.A is meant " excellence ", and B is meant " good ", and C is meant " poor ".

2) photostabilization

Use reflection densitometer X-Rite 310TR to measure after the record at once density of image (initial density: C _i).In burn-in test meter (Atlas Ci65 derives from Atlas electrical equipment company) with image with xenon light (85,000lux) after exposure 1O days, be that 3 points of 1,1.5 and 2.0 are measured density of image (C in initial density once more _f).Calculate dyestuff retention rate (%) by following equation:

Dyestuff retention rate (%)=[(C _i-C _f)/C _i] * 100

With the dyestuff retention rate of each measuring point be 80% or higher image be decided to be A.There is 1 or 2 s' dyestuff retention rate to be lower than 80% image in 3 points and is decided to be B.The dyestuff retention rate of each point is lower than 80% image and is decided to be C.

3) ozone resistants

At once image after the record in being the chamber of 0.5ppm, concentration of ozone gas was left standstill 7 days.Obtain contact dyestuff retention rate afterwards to estimate identical mode with ozone with photostabilization.At initial density (C _i) be to measure on 3 points of 1,1.5 or 2.0.Ozone concn in the chamber is to adjust with ozone gas detector (OZG-EM-01 derives from Applics company limited).With the dyestuff retention rate of each measuring point be 70% or higher image be decided to be A.There is 1 or 2 s' dyestuff retention rate to be lower than 70% image in 3 points and is decided to be B.The dyestuff retention rate of each point is lower than 70% image and is decided to be C.

4) water-repellancy

With the waxy luster printing paper that is formed with image thereon under room temperature dry 1 hour, in 20 ℃ water, soaked for 10 seconds then, and seasoning.Use reflection densitometer X-Rite 310TR at 3 density points (C _i=1,1.5 or 2.0) measure before the immersion treatment and density of image afterwards.Obtain to soak dyestuff retention rate afterwards to estimate identical mode with photostabilization.To each C _iMeasure at 20 points, obtain each C _iMean value, and calculate the average dyestuff retention rate of these 3 initial density.Average dyestuff retention rate be 80% or higher image be decided to be A.The dyestuff retention rate is for more than or equal to 70% and be decided to be B less than 80% image.Retention rate is lower than 70% image and is decided to be C.

Use contains 0.1mol.dm ^-3The N of perchloric acid tetrapropyl ammonium, dinethylformamide solution is as supporting electrode and 1x 10 ^-3Mol.dm ^-3Dye composition and Graphite Electrodes are measured the oxidizing potential of dye composition with DC polarographic analyze P-100 as working electrode.The gained result also is shown in table 5-6.

Table 5-6

Printing ink	Dyestuff	Color	Photostabilization	Ozone resistants	Oxidizing potential	Remarks
							5-A	5-137	A	A	A-B	+1.44	The present invention
5-B	5-143	A	A	A	+1.40	The present invention
							5-C	5-145	A	A	A	+1.36	The present invention
5-D	5-148	A	A	A	+1.46	The present invention
							5-E	5-107	A	A	A-B	*1.25	The present invention
5-F	5-a	A	A	B	+1.33	Contrast
							5-G	5-b	A-B	C	C	+0.65	Contrast
5-H	5-c	B-C	B	C	+0.70	Contrast

Comparative dye 5-a:

Comparative dye 5-b:

Comparative dye 5-c:

5-6 finds out from table, the magenta image of printing with ink composite 5-A to 5-F than the image of printing with ink composite 5-G and 5-H more excellent aspect photostabilization and the ozone resistants.

The image of printing with ink composite 5-A to 5-E of the present invention, prove and preferably uses that to contain at least two pKa values be-10 to 5 specific azo-compound substituent of the present invention in excellence aspect the ozone resistants than the image of printing with ink composite 5-F.The image that obtains with ink composite 5-E slightly poor aspect the ozone resistants, prove that preferably it is-10 to 5 substituent azo-compound that each side at azo group has at least one pKa value than the image that obtains with ink composite 5-A to 5-D.Relatively to confirm preferably to have three or more pKa value be-10 to 5 substituent azo-compound to the ozone resistants of image that obtains with ink composite 5-B to 5-D and the image that obtains with ink composite 5-A and 5-E.

The water-repellancy and the ozone resistants that compare ink composite 5-A to 5-F, see that the image with higher water-repellancy presents higher ozone resistants, confirmation is securely fixed in the place of the desired location on the medium by the mordant dyeing effect with dye composition, and ozone resistants improves.

And, go up use ink composite 5-A to 5-H at identical ink-jet printer (PM-700C) and print ultra-fine waxy luster printing paper (MJA4S3P derives from Cisco's Epson).Estimate color, photostabilization, ozone resistants and the water-repellancy of gained image, obtain with show 5-6 in identical result.

The invention provides various coloured compositions, inkjet ink composition for example, use a kind of novel azo compound like this, color picture or coloured material in color, water-repellancy and colour fastness excellence are provided with performance of the reactive gas in absorption characteristic to the color rendition excellence of one of 3 kinds of primary colours, excellent water-repellancy and enough anti-light, heat, the wet and environment.The invention provides a kind of inkjet ink composition and a kind of can form have satisfactory color, the method for the image of excellent water-repellancy and high patience to the reactive gas in light and the environment (particularly ozone gas).The present invention also provides a kind of method that improves the ozone resistants of color picture in the ink-vapor recording.

Embodiment 24

The preparation of water-based inks

Following component is mixed,, stir simultaneously, and under pressure, be that 0.8 μ m and diameter are that the micro-strainer of 47mm filters, make ink composite 6-A by mean pore size 30-40 ℃ of heating 1 hour down.

The prescription of ink composite 6-A

(38) 4 parts of compound 6-

9 parts of Diethylene Glycols

9 parts of TEG monos

7 parts of glycerine

1 part of diethanolamine

70 parts in water

Prepare ink composite 6-B to 6-F with same way as, just replace compound 6-(38) with the azo-compound shown in the following table 6-1 with ink composite 6-A.

Picture record and evaluation

Go up each ink composite 6-A to 6-F of use at ink-jet printer (PM-700C derives from Seiko Epson Corporation of Cisco) and go up record one image at waxy luster printing paper (super developing out paper level derives from Fujiphoto company limited).Color, photostabilization and the ozone resistants of following evaluation gained image.Gained the results are shown in table 6-1.

1) color

Its color that detects by an unaided eye, and press the graduation of A-C rank.A is meant " excellence ", and B is meant " good ", and C is meant " poor ".

2) photostabilization

Use reflection densitometer X-Rite 310TR to measure after the record at once density of image (initial density: C _i).In burn-in test meter (Atlas Ci65 derives from Atlas electrical equipment company) with image with xenon light (85,000lux) after the exposure 7 days, be that 3 points of 1,1.5 and 2.0 are measured density of image (C in initial density once more _f).Calculate dyestuff retention rate (%) by following equation:

Dyestuff retention rate (%)=[(C _i-C _f)/C _i] * 100

With the dyestuff retention rate of each measuring point be 80% or higher image be decided to be A.There is 1 or 2 s' dyestuff retention rate to be lower than 80% image in 3 points and is decided to be B.The dyestuff retention rate of each point is lower than 80% image and is decided to be C.

3) ozone resistants

At once image after the record in being the chamber of 0.5ppm, concentration of ozone gas was left standstill 24 hours.To estimate identical mode at initial density (C with photostabilization _i) be to obtain to contact dyestuff retention rate afterwards on 1,1.5 or 2.0 the measuring point with ozone.Ozone concn in the chamber is to adjust with ozone gas detector (OZG-EM-01 derives from Applics company limited).With the dyestuff retention rate of each measuring point be 70% or higher image be decided to be A.There is 1 or 2 s' dyestuff retention rate to be lower than 70% image in 3 points and is decided to be B.The dyestuff retention rate of each point is lower than 70% image and is decided to be C.

The half breadth of the oxidizing potential of following mensuration dyestuff, maximum absorption wavelength and absorption spectrum.The gained result also is shown in table 6-1.

4) oxidizing potential (E _Ox)

Use contains 0.1mol.dm ^-3The DMF solution of perchloric acid tetrapropyl ammonium is as supporting electrode and 1x10 ^-3Mol.dm ^-3Dye composition and Graphite Electrodes are as working electrode and use SCE as reference electrode, measure oxidizing potential with polarographic analyze P-100.

5) maximum absorption wavelength and half breadth

Preparation concentration is about 5x10 ^-5Mol.dm ^-3The DMF solution of dye composition.Use path length to measure the interior absorption spectrum of wavelength region of 200nm-900nm with UV-VIS recording spectrophotometer UV-260 (by the supply of Shimadzu company) as the quartzy unit of 1cm.

Table 6-1

Printing ink	Dyestuff	Color	Photostabilization	Ozone resistants	E ox(SCE relatively)	λ max (nm)	Half breadth (nm)	Remarks
									6-A	6-(38)	A	A	A	+1.36	557	73	The present invention
6-B	6-(20)	A	A	A	+1.15	538	86	The present invention
									6-C	6-(11)	B	A	A	+1.12	541	97	The present invention
6-D	6-(39)	A	A	A	+1.37	560	76	The present invention
									6-E	6-a	B	C	C	+0.65	549	86	Contrast
6-F	6-b	B	B	C	+0.70	528	96	Contrast

Comparative dye 6-a:

Comparative dye 6-b:

6-1 finds out from table, contain oxidizing potential be higher than 1.0V (relatively SCE) and its maximum absorption wavelength between 500nm and 580nm and half breadth for the ink composite 6-A to 6-D of 150nm or narrower compound provide aspect color, photostabilization and the ozone resistants than the excellent magenta image of printing with ink composite 6-E or 6-F of image.

And, go up use ink composite 6-A to 6-D at identical ink-jet printer (PM-700C) and print ultra-fine waxy luster printing paper (MJA4S3P derives from Cisco's Epson).Estimate color, photostabilization and the ozone resistants of gained image, obtain and show similar gratifying result shown in the 6-1.

Embodiment 25

The preparation of ink sample 6-201

Under 70 ℃ azoic dyestuff 6-(33) (oil-soluble colourant) (5.63g) is dissolved in 4.22g high boiling organic solvent 6-S-2 (showing below), 5.63g high boiling organic solvent 6-S-11 (showing below) and the 50ml ethyl acetate with the 7.04g dioctyl sodium sulphosuccinate.In this solution, add the 500ml deionized water, stir with magnetic stirrer simultaneously, prepare the thick dispersion liquid of a kind of oil-in-water-type, with this thick dispersion liquid in the pressure of 600bar down by microfluidization device (deriving from Microfluidics company) 5 times.Gained emulsion desolventizing on rotatory evaporator is up to the smell that can't smell ethyl acetate.The thin emulsion of gained hydrophobic dye is mixed with 140g Diethylene Glycol, 50g glycerine, 7g Surfynol 465 (deriving from air products and chemical company) and 900ml deionized water, make ink sample 6-101.

6-S-2：

6-S-11：

The preparation of ink sample 6-202 to 6-208

Prepare ink sample 6-202 to 6-208 in the mode identical, just replace oil-soluble compounds 6-(33) with the oil-soluble compounds shown in the following table 6-2 with ink sample 6-201.

Picture record and evaluation

Waxy luster printing paper (ink-jet developing out paper level derives from Fujiphoto) ink-jet printer (PM-700C derives from Cisco's Epson) writes down an image with each ink sample 6-201 to 6-208.Estimate color, paper dependency, water-repellancy, photostabilization and the ozone resistants of the image of record in accordance with the following methods.Gained the results are shown in table 6-2.

1) color

With the reflection spectrum of 10nm wavelength interval at the area test image of 390-730nm, and with CIE 1976L ^*a ^*b ^*The color space system is basic calculation a ^*And b ^*Value.Preferred magenta tone is defined as follows, and color that should image is divided into the A-C level according to following standard.

Preferred a ^*Value: 76 or bigger

Preferred b ^*Value :-30 to 0

A:a ^*And b ^*Value is all in preferable range separately.

B:a ^*And b ^*One of value is in its preferable range.

C:a ^*And b ^*Value is not all in preferable range separately.

2) paper dependency

The tone of the image that forms separately on the paper with the tone of the image that forms on the waxy luster printing paper and plain paper copier (PPC) is compared.Difference between two is little, illustrates that the paper dependency is little, is decided to be A (satisfactory), and difference is big is decided to be B (poor).

3) water-repellancy

With the waxy luster printing paper that is formed with image thereon under room temperature dry 1 hour, in water, soaked for 30 seconds then, and seasoning under room temperature.Observe the printing ink image thorn that becomes mildewed, and the water-repellancy of printing ink is decided to be A (not having burr), B (slightly jagged) or C (sizable burr).

4) photostabilization

The image that forms on waxy luster printing paper in the burn-in test meter (Ci65 derives from Atlas) xenon light (85,000lux) expose 3 days down.Obtain the dyestuff retention rate in the mode identical with embodiment 24.The dyestuff retention rate of each measuring point be 70% or higher image be decided to be A.There is the dyestuff retention rate of 1 or 2 point to be lower than 70% image in 3 points and is decided to be B.Be lower than 70% image at the dyestuff retention rate of every bit and be decided to be C.

4) ozone resistants

According to embodiment 24 used identical measuring method and staging hierarchies.

Measure the oxidizing potential and the λ of used dye composition in the mode identical with embodiment 24 _MaxAnd the half breadth of absorption spectrum.The result also is shown in table 6-2.

Table 6-2

Printing ink	Dyestuff	Color	The paper dependency	Water-repellancy	Photostabilization	Ozone resistants	E ox(SCE relatively)	λ max (nm)	Half breadth (nm)
										6-201	6-(33)	A	A	A	A	A	+1.47	565	81
6-202	6-(34)	A	A	A	A	A	+1.38	558	77
										6-203	6-(35)	A	A	A	A	A	+1.42	562	81
6-204	6-(1)	A	A	A	A	A	+1.37	544	88
										6-205	6-(15)	A	A	A	A	A	+1.36	556	75
6-206	6-(23)	B	A	B	B	A	+1.15	547	99
										6-207	6-a	B	B	B	B	C	+0.65	549	86
6-208	6-b	B	B	B	B	C	+0.70	528	96

Result the 6-2 finds out from table, contain oxidizing potential be higher than 1.0V (SCE relatively) and its maximum absorption wavelength between 500nm and 580nm and half breadth for the sample 6-201 to 6-206 of 150nm or narrower compound provide aspect color, paper dependency, water-repellancy, photostabilization and the ozone resistants than the excellent magenta image of printing with sample 6-207 or 6-208 of image.

Embodiment 26

Use the ink-jet printer BJ-F850 (deriving from Canon Inc.) that loads print cartridge (filling each ink composite of preparation among the embodiment 25) on waxy luster printing paper GP-301 (deriving from Canon Inc.), to carry out spray ink Printing, and estimate the image of these printings in mode identical among the embodiment 25.What obtain among these visual evaluation results and the embodiment 25 is identical.

By using a kind of coloured composition, for example a kind of ink composite or a kind of inkjet ink composition, it contains oxidizing potential and is higher than 1.0V (SCE relatively) and shows that under the wavelength between 500nm and the 580nm maximum absorption and half breadth are 150nm or narrower compound, the present invention has set up a kind of color and the weather resistance of being provided at, the particularly method of the color picture of ozone gas aspect excellence or coloured material.

To require the full content of each foreign patent of foreign priority to add this paper by reference among the application, as statement in full.

Claims (7)

1. imaging coloured composition comprises and has the nitrogenous 6-of aromatics unit heterocyclic azoic dyestuff as the quality component, and wherein said azoic dyestuff is represented by formula (1):

Wherein the A representative comprises the diazo component A-NH of pyrazoles ring, imidazole ring or benzoxazole ring ₂Residue;

B ¹And B ²Representative-CR respectively ¹=and-CR ²=, perhaps B ¹And B ²In any one represents nitrogen-atoms, another representative-CR ¹=or-CR ²=;

R ⁵And R ⁶Represent hydrogen atom independently of one another, have the aliphatic group of 1-20 carbon atom, the aromatic group with 6-20 carbon atom, 5-or 6-unit heterocyclic group, acyl group, alkoxy carbonyl, the aryloxycarbonyl with 7-12 carbon atom, formamyl, alkyl sulphonyl, aryl sulfonyl or sulfamyl with 6-20 carbon atom with 1-20 carbon atom with 2-12 carbon atom with 2-12 carbon atom, condition is R ⁵And R ⁶Different times table hydrogen atom;

G and R ¹Represent hydrogen atom independently of one another, halogen atom, aliphatic group with 1-20 carbon atom, aromatic group with 6-20 carbon atom, 5-or 6-unit heterocyclic group, cyano group, carboxyl, formamyl, alkoxy carbonyl with 2-12 carbon atom, aryloxycarbonyl with 7-12 carbon atom, acyl group with 2-12 carbon atom, hydroxyl, alkoxyl group with 1-12 carbon atom, aryloxy with 6-12 carbon atom, siloxy-, acyloxy with 2-12 carbon atom, formamyl oxygen base, 5-or 6-unit heterocyclic oxy group, alkoxy-carbonyl oxy with 2-12 carbon atom, aryloxycarbonyl oxygen base with 7-12 carbon atom, with alkyl with 1-6 carbon atom, has the aryl of 6-12 carbon atom or the amino of 5-or the heterocyclic radical replacement of 6-unit, acyl amino with 2-12 carbon atom, urea groups with 1-12 carbon atom, sulfamyl amino, alkoxycarbonyl amino with 2-12 carbon atom, aryloxycarbonyl amino with 7-12 carbon atom, alkyl sulfonyl-amino with 1-12 carbon atom, arlysulfonylamino with 6-12 carbon atom, alkylthio with 1-12 carbon atom, arylthio with 6-12 carbon atom, alkyl sulphonyl with 1-20 carbon atom, aryl sulfonyl with 6-20 carbon atom, alkyl sulphinyl with 1-20 carbon atom, aryl sulfonyl kia with 6-20 carbon atom, sulfamyl, sulfo group or 5-or 6-unit heterocycle sulfenyl;

R ²Represent hydrogen atom, halogen atom, aliphatic group with 1-20 carbon atom, aromatic group with 6-20 carbon atom, 5-or 6-unit heterocyclic group, cyano group, carboxyl, formamyl, alkoxy carbonyl with 2-12 carbon atom, aryloxycarbonyl with 7-12 carbon atom, acyl group with 2-12 carbon atom, acyloxy with 2-12 carbon atom, formamyl oxygen base, alkoxy-carbonyl oxy with 2-12 carbon atom, aryloxycarbonyl oxygen base with 7-12 carbon atom, acyl amino with 2-12 carbon atom, urea groups with 1-12 carbon atom, sulfamyl amino, alkoxycarbonyl amino with 2-12 carbon atom, aryloxycarbonyl amino with 7-12 carbon atom, alkyl sulfonyl-amino with 1-12 carbon atom, arlysulfonylamino with 6-12 carbon atom, nitro, alkyl sulphonyl with 1-20 carbon atom, aryl sulfonyl with 6-20 carbon atom, alkyl sulphinyl with 1-20 carbon atom, aryl sulfonyl kia with 6-20 carbon atom, sulfamyl or sulfo group;

Perhaps R ⁵Can with R ¹Or R ⁶Link to each other and form a 5-or 6-unit ring; And

Above-mentioned by G,, R ¹, R ², R ⁵And R ⁶Each group of representative can have and is selected from following substituting group: halogen atom; aliphatic group with 1-20 carbon atom; aromatic group with 6-20 carbon atom; 5-or 6-unit heterocyclic group; cyano group; carboxyl; formamyl; alkoxy carbonyl with 2-12 carbon atom; aryloxycarbonyl with 7-12 carbon atom; acyl group with 2-12 carbon atom; hydroxyl; alkoxyl group with 1-12 carbon atom; aryloxy with 6-12 carbon atom; siloxy-; acyloxy with 2-12 carbon atom; formamyl oxygen base; 5-or 6-unit heterocyclic oxy group; alkoxy-carbonyl oxy with 2-12 carbon atom; aryloxycarbonyl oxygen base with 7-12 carbon atom; with a alkyl with 1-6 carbon atom; has the aryl of 6-12 carbon atom or the amino of 5-or the heterocyclic radical replacement of 6-unit; acyl amino with 2-12 carbon atom; urea groups with 1-12 carbon atom; sulfamyl amino; alkoxycarbonyl amino with 2-12 carbon atom; aryloxycarbonyl amino with 7-12 carbon atom; alkyl sulfonyl-amino with 1-12 carbon atom; arlysulfonylamino with 6-12 carbon atom; nitro; alkylthio with 1-12 carbon atom; arylthio with 6-12 carbon atom; 5-or 6-unit heterocycle sulfenyl; alkyl sulphonyl with 1-20 carbon atom; aryl sulfonyl with 6-20 carbon atom; alkyl sulphinyl with 1-20 carbon atom; aryl sulfonyl kia with 6-20 carbon atom; sulfamyl and sulfo group.

2. imaging coloured composition as claimed in claim 1 is in its Chinese style (1)

The A representative comprises the diazo component A-NH of pyrazoles ring or imidazole ring ₂Residue;

B ¹And B ²Representative-CR respectively ¹=and-CR ²=, perhaps B ¹And B ²In any one represents nitrogen-atoms, another representative-CR ¹=or-CR ²=;

R ⁵And R ⁶Represent hydrogen atom independently of one another, have the alkyl of 1-20 carbon atom, the aromatic group with 6-20 carbon atom, 5-or 6-unit heterocyclic group, acyl group or sulfamyl with 2-12 carbon atom, condition is R ⁵And R ⁶Different times table hydrogen atom;

G represents hydrogen atom, halogen atom, carboxyl, formamyl, hydroxyl, alkoxyl group with 1-12 carbon atom, aryloxy with 6-12 carbon atom, acyloxy with 2-12 carbon atom, 5-or 6-unit heterocyclic oxy group, with alkyl with 1-6 carbon atom, has the aryl of 6-12 carbon atom or the amino of 5-or the heterocyclic radical replacement of 6-unit, acyl amino with 2-12 carbon atom, urea groups with 1-12 carbon atom, sulfamyl amino, alkoxycarbonyl amino with 2-12 carbon atom, aryloxycarbonyl amino with 7-12 carbon atom, alkyl sulfonyl-amino with 1-12 carbon atom, arlysulfonylamino with 6-12 carbon atom, alkyl sulphonyl with 1-20 carbon atom, aryl sulfonyl with 6-20 carbon atom, alkyl sulphinyl with 1-20 carbon atom, aryl sulfonyl kia with 6-20 carbon atom, sulfamyl or sulfo group;

R ¹Represent hydrogen atom, halogen atom, 5-or 6-unit heterocyclic group, cyano group, carboxyl, formamyl, alkoxy carbonyl, aryloxycarbonyl, acyl group, alkyl sulphonyl, aryl sulfonyl, alkyl sulphinyl, aryl sulfonyl kia, sulfamyl or sulfo group with 6-20 carbon atom with 1-20 carbon atom with 6-20 carbon atom with 1-20 carbon atom with 2-12 carbon atom with 7-12 carbon atom with 2-12 carbon atom;

R ²Represent hydrogen atom, halogen atom, have the aliphatic group of 1-20 carbon atom, the alkoxy carbonyl with 2-12 carbon atom, aromatic group, 5-or 6-unit heterocyclic group, carboxyl, formamyl, sulfamyl or sulfo group with 6-20 carbon atom;

Perhaps R ⁵Can with R ¹Or R ⁶Link to each other and form a 5-or 6-unit ring; And

Above-mentioned by G,, R ¹, R ², R ⁵And R ⁶Each group of representative can have substituting group as defined in claim 1.

3. imaging coloured composition as claimed in claim 1, wherein said azoic dyestuff is represented by formula (2):

Z wherein ¹Representative has the acyl group of 2-12 carbon atom, the alkoxy carbonyl with 2-12 carbon atom, nitro, cyano group, has the alkyl sulphonyl of 1-12 carbon atom, the aryl sulfonyl with 6-18 carbon atom, the formamyl with 1-12 carbon atom, the alkyl sulphinyl with 1-20 carbon atom, the aryl sulfonyl kia with 6-20 carbon atom, sulfamyl, the haloalkyl with 1-12 carbon atom or halogen atom;

Z ²Represent hydrogen atom, have the aliphatic group of 1-20 carbon atom, aromatic group or 5-or 6-unit heterocyclic group with 6-20 carbon atom;

R ¹, R ², R ⁵And R ⁶Definition and formula (1) in identical;

R ³And R ⁴Represent hydrogen atom independently of one another, have the aliphatic group of 1-20 carbon atom, the aromatic group with 6-20 carbon atom, 5-or 6-unit heterocyclic group, acyl group, alkoxy carbonyl, aryloxycarbonyl, formamyl, alkylsulfonyl or sulfamyl with 7-12 carbon atom with 2-12 carbon atom with 2-12 carbon atom;

Q represents hydrogen atom, has the aliphatic group of 1-20 carbon atom, forms the required nonmetal aromatic group of 5-to 8-unit ring or forms the required nonmetal heterocyclic group of 5-to 8-unit ring;

Z wherein ¹, Z ², R ¹, R ², R ³, R ⁴, R ⁵, R ⁶Can have as defined in claim 1 substituting group with each group of Q representative.

4. imaging coloured composition as claimed in claim 3, wherein in formula (2),

R ¹Represent hydrogen atom, halogen atom, 5-or 6-unit heterocyclic group, cyano group, carboxyl, formamyl, alkoxy carbonyl, aryloxycarbonyl, acyl group, alkyl sulphonyl, aryl sulfonyl, alkyl sulphinyl, aryl sulfonyl kia, sulfamyl or sulfo group with 6-20 carbon atom with 1-20 carbon atom with 6-20 carbon atom with 1-20 carbon atom with 2-12 carbon atom with 7-12 carbon atom with 2-12 carbon atom;

R ²Represent hydrogen atom, halogen atom, have the aliphatic group of 1-20 carbon atom, the alkoxy carbonyl with 2-12 carbon atom, aromatic group, 5-or 6-unit heterocyclic group, carboxyl, formamyl, sulfamyl or sulfo group with 6-20 carbon atom;

R ³And R ⁴Represent hydrogen atom independently of one another, have the aliphatic group of 1-20 carbon atom, the aromatic group with 6-20 carbon atom, 5-or 6-unit heterocyclic group, acyl group, alkoxy carbonyl, aryloxycarbonyl, alkyl sulphonyl, formamyl, alkylsulfonyl or sulfamyl with 1-20 carbon atom with 7-12 carbon atom with 2-12 carbon atom with 2-12 carbon atom;

R ⁵And R ⁶Represent hydrogen atom independently of one another, have the alkyl of 1-20 carbon atom, the aromatic group with 6-20 carbon atom, 5-or 6-unit heterocyclic group, acyl group, alkyl sulphonyl or sulfamyl with 1-20 carbon atom with 2-12 carbon atom, condition is R ⁵And R ⁶Different times table hydrogen atom;

Q represents hydrogen atom, has the aliphatic group of 1-20 carbon atom, forms the required nonmetal aromatic group of 5-to 8-unit ring or forms the required nonmetal heterocyclic group of 5-to 8-unit ring;

Z wherein ¹, Z ², R ¹, R ², R ³, R ⁴, R ⁵, R ⁶Can have as defined in claim 1 substituting group with each group of Q representative.

5. imaging coloured composition as claimed in claim 4, wherein in formula (2),

Z ¹Represent cyano group, have the alkyl sulphinyl or the halogen atom of 1-20 carbon atom;

Z ²Representative has alkyl, phenyl or the pyridyl of 1-20 carbon atom, and Z ²Can have and be selected from following substituting group: alkyl, halogen atom and sulfo group with 1-20 carbon atom;

R ¹Represent hydrogen atom, cyano group or formamyl;

R ²Represent hydrogen atom, have the alkyl of 1-20 carbon atom, alkoxy carbonyl or formamyl with 2-12 carbon atom;

R ³Representative have 1-20 carbon atom alkyl, have 6-20 carbon atom aromatic group, have the acyl group of 2-12 carbon atom or have the alkyl sulphonyl of 1-20 carbon atom, and R ³Can have and be selected from following substituting group: have the alkyl of 1-20 carbon atom, alkoxyl group and sulfo group with 1-12 carbon atom;

R ⁴Represent hydrogen atom;

R ⁵And R ⁶Represent hydrogen atom independently of one another, have the alkyl of 1-20 carbon atom, the aromatic group with 6-20 carbon atom, the acyl group with 2-12 carbon atom, benzothiazolyl, have the alkyl sulphonyl of 1-20 carbon atom, condition is R ⁵And R ⁶Different times table hydrogen atom, and by R ⁵And R ⁶Each group of representative can have and is selected from following substituting group: have the alkyl of 1-20 carbon atom, the alkoxyl group with 1-12 carbon atom, carboxyl, sulfamyl, halogen atom and sulfo group; And

Q representative is selected from the heterocyclic radical of pyridyl, pyrimidyl and benzothiazolyl, and Q can have and is selected from following substituting group: halogen atom, nitro, sulfamyl, cyano group, with amino, carboxyl and the sulfo group of the alkyl replacement with 1-6 carbon atom.

6. inkjet ink composition comprises the coloured composition of claim 1.

7. ink jet recording method is included in and has a substrate and and contain on the visual receiver media of inorganic white pigment particulate ink receiving layer, sprays inkjet ink composition as claimed in claim 6, forms an image.

Images