CN103459513A - Water-soluble azo dye, dye composition containing same, and dyeing method using same - Google Patents
Water-soluble azo dye, dye composition containing same, and dyeing method using same Download PDFInfo
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- CN103459513A CN103459513A CN2012800172717A CN201280017271A CN103459513A CN 103459513 A CN103459513 A CN 103459513A CN 2012800172717 A CN2012800172717 A CN 2012800172717A CN 201280017271 A CN201280017271 A CN 201280017271A CN 103459513 A CN103459513 A CN 103459513A
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- ANHHLENDHAHFPE-VPHDGDOJSA-N Cc(cc(c(OC)c1)/N=N/c(c(O)c(ccc(Nc2ccccc2)c2)c2c2)c2S(O)(=O)=O)c1/N=N/c(cc1)ccc1S Chemical compound Cc(cc(c(OC)c1)/N=N/c(c(O)c(ccc(Nc2ccccc2)c2)c2c2)c2S(O)(=O)=O)c1/N=N/c(cc1)ccc1S ANHHLENDHAHFPE-VPHDGDOJSA-N 0.000 description 1
- KMSLYIOOIPTKRA-CDJCAARLSA-N Cc1cc2cc(Nc(ccc3c4O)cc3cc(S(O)(=O)=O)c4N(C)Nc(cc(cc3)C(O)=O)c3OC)ccc2c(O)c1/N=N/c(cc(cc1)C(O)=O)c1OC Chemical compound Cc1cc2cc(Nc(ccc3c4O)cc3cc(S(O)(=O)=O)c4N(C)Nc(cc(cc3)C(O)=O)c3OC)ccc2c(O)c1/N=N/c(cc(cc1)C(O)=O)c1OC KMSLYIOOIPTKRA-CDJCAARLSA-N 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/62—Natural or regenerated cellulose using direct dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
- C09B33/02—Disazo dyes
- C09B33/04—Disazo dyes in which the coupling component is a dihydroxy or polyhydroxy compound
- C09B33/052—Disazo dyes in which the coupling component is a dihydroxy or polyhydroxy compound the coupling component being a bis-(naphthol-amine)
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/24—Disazo or polyazo compounds
- C09B45/28—Disazo or polyazo compounds containing copper
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/41—Organic pigments; Organic dyes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Coloring (AREA)
- Paper (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The present invention relates to a disazo compound or salt thereof, expressed by the following formula (1) (in the formula, Ar1 represents a phenyl group that is substituted with a hydroxy group or a methoxy group at the ortho position with regards to the azo group, and then substituted with a carboxyl group; and Ar2 represents a phenyl group that is substituted with a hydroxy group or a methoxy group at the ortho position with regards to the azo group, and which may then be substituted with a sulfonate group, sulfonamide group, or carboxyl group).
Description
Technical field
The dye composite that the present invention relates to soluble azo dyes and contain it.More particularly, the present invention relates to tetrazo compound, as the salt of the copper complex formazan copper tetrazo compound of tetrazo compound or these compounds and contain the copper tetrazo compound or the dye composite of its salt and other dye compositions or its salt.The invention still further relates to the dyeing process that uses described soluble azo dyes or described dye composite.
Background technology
So far, as the cellulosic fibre material that will comprise papermaking material, dye securely the dyestuff of blueness to purple, known the direct indigo plant 15 of C.I., the direct indigo plant 200 of C.I., C.I. directly indigo plant 202, the direct indigo plant 203 of C.I. etc.These dyestuffs, as the dyestuff of the cotton for cloth dyeing or artificial silk or as the dyestuff for paper pulp or paper dyeing, by continually for paper industry.These dyestuffs are generally used dianisidine as the main raw material manufacture.
Especially, in papermaking material dyeing field, exist and with micro-blue dyes or purple dye, the scraps of paper are dyeed, thereby make the scraps of paper seem than the pure white whiter technology of optics.This dyeing process, be called as blueing (bluing), the general substantive dyestuff of blueness to purple that adopt.This blueing is for example needing between the shelf lives dyestuff self or dye solution stable with dyestuff aspect characteristic, and produces afterwards the high bright colors of fastness to light etc. in dyeing.Use dianisidine to be used as continually conventional blueing dyestuff as the blue dyes of raw material manufacture due to its bright colour.
Yet, FAQs in these dyestuffs is that the dianisidine that is used as main raw material belongs to the specified I class particular chemicals (that is, may cause to the staff the harmful chemical substance of height of serious Health cost) of Japanese industry safety and health method (Japanese Industrial Safety and Health Act).Therefore, in the manufacturing processed of every kind of dyestuff, use dianisidine to be subject to the strict supervision of rules.This is the management of safety and Health and the restriction essential factor of raising as operated under the protection equipment very harsh of manufacturing efficiency.
Blueness by the raw material manufacture except dianisidine comprises the direct indigo plant 67 of C.I., the direct indigo plant 78 of C.I., the direct indigo plant 106 of C.I., the direct indigo plant 108 of C.I., the direct purple 9 of C.I., the direct purple 35 of C.I. and the direct purple 51 of C.I. to the dyestuff of purple or the example of substantive dyestuff.Yet any in these dyestuffs all obviously is inferior to the dyestuff containing dianisidine in dyeing behavior aspect vividness, dyeability, fastness or thermotolerance.Therefore, these dyestuffs equally both had been not suitable for use in the cellulosic fibre material that comprises papermaking material is dyed to the firmly blue dyestuff to purple, also were not suitable for use in the blueing dyestuff.
Therefore, strongly need for a long time to produce bright-coloured and blueness firmly color and replace these the existing dyestuffs in dyestuff manufacture, papermaking and dyeing industry to dyestuff or the substantive dyestuff of purple.However, not yet obtain the excellent dyestuff that meets all these demands.
For instance, Japanese Patent Publication 64-5623 communique (patent documentation 1) and each self-described of Japanese kokai publication hei 7-18192 communique (patent documentation 2) dye composition that meaned by formula (5) as not containing the blue dyes of dianisidine:
Use this dyestuff papermaking material can be dyed to the bright-coloured blueness with good level-dyeing property.Yet the color and luster band of this dyestuff is green and therefore can't produce moderate reddish blue, thereby causes applying limited.In addition, this dyestuff adversely has poor dyeing property and colouring intensity and low for the suitability of blueing separately.
Viewpoint from the dyeing behavior of expectation color and actual dyeing processibility, dye composite as substantive dyestuff generally need to be highly stable with the form of dye solution,, even still almost there is no crystallize out through after a certain amount of time between the shelf lives, and needing tone not change.However, not yet need to produce moderate reddish blue that blueing uses and the dye composite containing substantive dyestuff of the excellent in stability between the shelf lives.
Under this background, Japanese kokai publication sho 59-140263 communique (patent documentation 3) has been described the compound that meaned by formula shown below (6) as the tetrazo compound for dye composite.Yet this document is not described the tetrazo compound had through the phenyl of carboxyl substituted.
Prior art
Patent documentation
Patent documentation 1: Japanese Patent Publication 64-5623 communique
Patent documentation 2: Japanese kokai publication hei 7-18192 communique
Patent documentation 3: Japanese kokai publication sho 59-140263 communique
Summary of the invention
The problem that invention will solve
One object of the present invention is for providing the dyeing process of a kind of dyestuff and the described dyestuff of use, and described dyestuff is not in the situation that used the dianisidine that belongs to the specified I class particular chemicals of Japanese industry safety and health method to meet dyeability, fastness, thermotolerance, vividness etc.
Another object of the present invention is for providing the dyeing process of a kind of dyestuff and the described dyestuff of use, described dyestuff by cellulosic fibre material, particularly papermaking material as paper pulp dye there is fastness and high density more medium blue look to purple, and aspect safety and health, resources conservation and environmental pollution to the mankind or earth close friend.
Another object of the present invention is for a kind of dye composite being provided and using the dyeing process of described dye composite, and described dye composite does not produce and is applicable to the bright-coloured reddish blue with good dyeing property of blueing with dyestuff containing the blue substantive dyestuff of raw material dianisidine and purple substantive dyestuff by combination.
The means of dealing with problems
Inventor's discovery, these purposes can be separately by being used the tetrazo compound or its salt that are meaned by formula shown below (1) realize.
The inventor also finds, generation is specially adapted to blueing and obtains by being used in combination two kinds of substantive dyestuff with the dye composite of the bright-coloured reddish blue with good dyeing characteristic of dyestuff, and these two kinds of substantive dyestuff are the compound (copper complex formazan a kind of form of the tetrazo compound meaned by formula shown below (1)) that meaned by formula shown below (4) or its salt and compound (also being described in " background technology " paragraph) or its salt of by formula shown below (5), being meaned.
Specifically, each aspect of the present invention is as follows:
[1] a kind of tetrazo compound or its salt meaned by following formula (1),
Wherein, Ar1 is illustrated in respect to the ortho position of azo-group by hydroxyl or methoxy substitution and further by the phenyl of carboxyl substituted, and Ar2 is illustrated in respect to the ortho position of azo-group by hydroxyl or methoxy substitution and optionally further by the phenyl of sulfonic group, sulfoamido or carboxyl substituted.
[2] copper complex or its salt of the described tetrazo compound meaned by formula (1) of basis [1].
[3], according to [2] described copper complex or its salt, wherein said copper complex is the copper tetrazo compound meaned by following formula (2):
Wherein, X means sulfonic group, sulfoamido or carboxyl.
[4], according to [2] or [3] described copper complex or its salt, wherein said copper complex is the copper tetrazo compound meaned by following formula (3):
Wherein, X means sulfonic group, sulfoamido or carboxyl.
[5] according to [3] or [4] described copper complex or its salt, wherein, X means sulfoamido or carboxyl.
[6] a kind of dye composite, it comprises two kinds of substantive dyestuff, and described two kinds of substantive dyestuff are respectively the compound or its salt meaned by following formula (4) and the compound or its salt meaned by following formula (5):
[7], according to [6] described dye composite, wherein, the compound or its salt meaned by formula (4) is 5:95～90:10 with the ratio of components (in mass) between compound or its salt by formula (5) expression.
[8] a kind of by the method for cellulose dyeing, it comprises and using according to described compound or its salt of any one in [1] to [5] or according to the solution of [6] or [7] described dye composite.
[9] a kind of dyed material, it is by obtaining according to [8] described dyeing process.
[10] a kind of ink composite, it comprises according to the described compound or its salt of any one in [1] to [5] as tinting material.
[11] according to [10] described ink composite, wherein, described ink composite further comprises water-miscible organic solvent.
[12] a kind of color-tinted product, it is with painted according to [10] or [11] described ink composite.
The advantageous effects of invention
The tetrazo compound meaned by formula (1) of the present invention, as the copper complex formazan copper tetrazo compound of tetrazo compound or the salt of these compounds, do not correspond to the dianisidine that belongs to I class particular chemicals, and can obtain by the manufacture method of not using dianisidine.These compound or its salts can be used as the cellulosic fibre material that comprises papermaking material is dyed to medium blue look with high vividness, high density and fastness soluble azo dyes to purple.In addition, the salt of tetrazo compound of the present invention, copper tetrazo compound or these compounds also has the following advantages: its due to high dyeability less by color white, be subject to that water hardness affects hardly, less variable color and there is high stability of solution.These compound or its salts with the dyestuff described in Japanese kokai publication sho 59-140263 communique, compare in dyeability, vividness, stability of solution and the stability while mixing with other existing dyestuffs aspect excellent especially, and compare in excellence aspect dyeing property and colouring intensity with the dyestuff described in Japanese kokai publication hei 7-18192 communique with Japanese Patent Publication 64-5623 communique.
Especially, comprise two kinds of substantive dyestuff according to dye composite of the present invention crystallize out and there is high stability of solution not, compound (copper complex of tetrazo compound) or its salt that described two kinds of substantive dyestuff are respectively the compound (copper complex of tetrazo compound) that meaned by formula (4) or its salt and are meaned by formula (5).In addition, with this dye composite, cellulosic fibre material dyeing can be produced to the material of the reddish blue dyeing of the balanced dyeing property with vividness and strong fastness (photostabilization, water tolerance etc.).
Embodiment
The tetrazo compound meaned by formula (1) according to of the present invention will be described.
In formula, Ar1 is illustrated in respect to the ortho position of azo-group by hydroxyl or methoxy substitution and further by the phenyl of carboxyl substituted, and Ar2 is illustrated in respect to the ortho position of azo-group by hydroxyl or methoxy substitution and optionally further by the phenyl of sulfonic group, sulfoamido or carboxyl substituted.
Be not particularly limited by the position of carboxyl substituted in Ar1, replace as long as can realize.Contraposition with respect to hydroxyl or methoxyl group is preferred.
Ar2 is preferably by the phenyl of the sulfoamido in sulfonic group, sulfoamido and carboxyl or carboxyl substituted.These substituting groups are further given compound water soluble.Be not particularly limited by the position of sulfonic group, sulfoamido or carboxyl substituted in Ar2, replace as long as can realize.Can adopt the optional position in ortho position, a position and the contraposition with respect to hydroxyl or methoxyl group.
The example of the method for manufacturing the tetrazo compound meaned by formula (1) will be described hereinafter.The method of manufacturing this compound is not limited to method shown below.
Known or the aromatic amines compound meaned by formula shown below (7) and formula (8) that obtain by the method for applying manufacture similar compound as known in the art own can pass through ordinary method diazotization in the art, under for example 5 ℃～40 ℃, preferably 10 ℃～25 ℃, utilize subsequently the commercially available dinaphthylamine derivative meaned by formula shown below (9) to carry out alkaline diazonium coupling reaction, thereby obtain the tetrazo compound meaned by formula (1).
Ar1-NH
2 (7)
Wherein Ar1 is as defined in above-mentioned Ar1.
Ar2-NH
2 (8)
Wherein Ar2 is as defined in above-mentioned Ar2.
Copper complex or its salt of the tetrazo compound meaned by formula (1) is also contained in the present invention.This copper complex formazan example comprises single copper complex and two copper complexs.Its preferred embodiment comprises that wherein X means sulfonic group, sulfoamido or carboxyl as the two copper complex formazan copper tetrazo compounds that meaned by formula (2).In this copper complex, the preferred the position of substitution of carboxyl in Ar1, in the preferred group in sulfonic group, sulfoamido and carboxyl in Ar2 etc. with identical in the tetrazo compound meaned by formula (1).
This copper complex can be used the tetrazo compound manufacture meaned by formula (1) according to procedures known in the art.For instance, this copper complex can be by following acquisition: the copper complex compound that will consist of copper sulfate and ammoniacal liquor and/or alkanolamine and/or vulkacit H etc. joins in the tetrazo compound meaned by formula (1), carries out the copper reaction afterwards under for example 50 ℃～100 ℃, preferably 90 ℃～100 ℃.In this reaction, methoxyl group experiences demethylating reaction and causes copper.
The tetrazo compound or its copper complex that by formula (1), are meaned can be obtained by reaction soln by common salting-out process or acid-precipitation method.In addition, the tetrazo compound meaned by formula (1) or its copper complex can obtain by the Direct spraying of reaction soln is dry.Perhaps, can directly or in desalination and after concentrating in reaction soln, add solubilizing agent or stablizer as urea, alkanolamine, alkylamine, ε-caprolactam, and use with the solution form.
The thus obtained tetrazo compound meaned by formula (1) or its copper complex exist with the form of free acid or its salt.Especially, salt form is preferred.The example of salt comprises an alkali metal salt, alkaline earth salt, alkylamine salt and alkanolamine salt.Especially, an alkali metal salt is preferred as sodium salt, sylvite and lithium salts.These salt obtain via salt-forming reaction usually.
The compound (copper complex of tetrazo compound) meaned by formula (4) of copper complex formazan a kind of form of the tetrazo compound as being meaned by formula (1) or its salt can be combined with the compound (copper complex of tetrazo compound) meaned by formula (5) or its salt, and use with the dye composite form that comprises these two kinds of substantive dyestuff.This dye composite is for producing the dye composite that has the bright-coloured reddish blue of good dyeing property and be preferred for the blueing purpose.
The compound meaned by formula (4) can obtain by the method for application manufacture related compound as known in the art.This copper complex can be by for example manufacturing as follows: 3-amino-4-methoxyl phenylformic acid is carried out to diazotization reaction; This reaction product is joined in the solution of 7,7'-imino-two (4-hydroxyl naphthalene-2-sulfonic acids) and form tetrazo compound; Afterwards this compound is joined in copper complex solution and carries out the copper reaction, described copper complex solution is by joining diethanolamine and 2-methylamino ethanol in copper sulfate solution and prepare.
The example of the salt of the compound meaned by formula (4) comprises an alkali metal salt, alkaline earth salt, alkylamine salt and alkanolamine salt.Especially, an alkali metal salt is preferred as sodium salt, sylvite and lithium salts or low-grade alkane alcohol amine salt as diethanolamine salt.These salt obtain via salt-forming reaction usually.
The compound or its salt meaned by formula (5) is for being called as in the art directly blue 273 compound of C.I..This copper complex used or its salt can be manufactured based on document as known in the art.Perhaps, can use commercially available dyestuff.
In comprising the dye composite that is respectively the compound or its salt meaned by formula (4) and two kinds of substantive dyestuff of the compound or its salt meaned by formula (5), the compound or its salt meaned by formula (4) is preferably 5:95 to 90:10 with the ratio of components (in mass) between compound or its salt by formula (5) expression.
Comprise the dye composite that is respectively the compound or its salt meaned by formula (4) and two kinds of substantive dyestuff of the compound or its salt meaned by formula (5), can contain other dyestuffs except compound (4) or its salt and compound (5) or its salt, to regulate tone or to regulate fastness, dyeing property etc.In addition, for similar purpose, this dye composite can further contain pigment, staining agent etc.This dye composite can further comprise solvent as water; Salt is as sodium-chlor; Oiliness becomes to grade.
Can be for cellulosic fibre material be dyeed according to the salt of tetrazo compound of the present invention, copper tetrazo compound or these compounds.These compound or its salts can be for for example: for the dyeing process under the common dyeing condition of paper or dye of pulp, the top sizing dyeing process that comprises size press and coating process, or there is the beater dyeing method of the more medium blue look of high vividness and excellent photostabilization and water tolerance to the material of purple dyeing for acquisition.In addition, these compound or its salts can be for the dyeing process under common dyeing condition as dip-dye, continuous dyeing or printing so that cellulosic fibre material is dyed to the blueness that daylight and washing is had to fastness as the fiber of natural or man-made cellulose fibers and cellulose as cotton or artificial silk.Under this background, dyed material also comprises dyed cellulosic fibre material that the processing by filamentary material obtains and film, building board, non-woven fabrics etc.
Especially, dyed material can use the solution of the dye composite that contains two kinds of substantive dyestuff to obtain by dyeing process, and described two kinds of substantive dyestuff are respectively the compound or its salt meaned by formula (4) and the compound or its salt meaned by formula (5).Use this dye composite to make and can dye reddish blue.Described solution is preferably the aqueous solution.Solution obtains by dissolving or dilute dye composite.
The salt of tetrazo compound of the present invention, copper tetrazo compound or these compounds can be as the tinting material in paper use or fiber use ink composite to obtain color-tinted product.This ink composite can further comprise water-miscible organic solvent as methyl alcohol, ethanol, Virahol, hydroxyethyl methylamine, thanomin, diethanolamine or trolamine.As the tinting material of the ink composite for fiber, the salt of tetrazo compound of the present invention, copper tetrazo compound or these compounds is preferred.In this case, ink composite can further comprise dispersion agent as polymerization sulfonic acid, preferably the formalin condenses of the formalin condenses of aromatic sulphonic acid or lignosulfonic acid.
Embodiment
Hereinafter, with reference to embodiment, the present invention is described in more detail.Yet the present invention is not limited by these embodiment should.
In an embodiment, " part " and " % " refers to respectively mass parts and quality %.In addition, the sulfonic group in various means with free form.
Embodiment 1
Add 11 part of 35% hydrochloric acid in the water of 70 parts 18 ℃～22 ℃, then add 7.25 parts of 3-amino-4-methoxyl phenylformic acid.Gained solution is cooled to 5 ℃.Add wherein 3.14 parts of Sodium Nitrites, and mixture is carried out to diazotization reaction 30 minutes, thereby obtain reaction soln.Add 10 part 7 in the water of 150 parts 18 ℃～22 ℃, 7'-imino-two (4-hydroxyl naphthalene-2-sulfonic acid) and 5.8 parts of sodium carbonate.By adding sodium carbonate, pH is being remained in 8.5～9.5, with 1 hour, in gained solution, adding above-mentioned reaction soln.Mixture is further stirred 3 hours.Then, add wherein 25 portions of salt, and mixture is stirred and spends the night.By adding 17 part of 35% hydrochloric acid, solution is carried out to the acid out processing, and collect precipitate (that is the compound, meaned by formula shown below (10)) by filtration.
Embodiment 2
Add 3.41 parts of 3-amino-4-methoxyl phenylformic acid and 4.71 part of 35% hydrochloric acid in the water of 100 parts 18 ℃～22 ℃.Gained solution is cooled to 5 ℃.Add wherein 1.46 parts of Sodium Nitrites, and mixture is carried out to diazotization reaction 2 hours, thereby obtain reaction soln.Add 12.22 part 7 in the water of 160 parts 18 ℃～22 ℃, 7'-imino-two (4-hydroxyl naphthalene-2-sulfonic acids), and with sodium carbonate the pH regulator to 7.0 by mixture, and mixture is cooled to 5 ℃.By adding sodium carbonate, pH is being remained in 7.0～7.5, with 2 hours, in gained solution, adding above-mentioned reaction soln.Then, mixture is further stirred 5 hours.Add 3.76 parts of 3-amino-4-hydroxy benzsulfamides and 4.88 part of 35% hydrochloric acid in 80 parts of water, and solution is cooled to 0 ℃.Add wherein 1.46 parts of Sodium Nitrites, and mixture is carried out to diazotization reaction 2 hours, thereby the acquisition reaction soln, then, by adding sodium carbonate that pH is remained in 7.0～8.0, joined it in the above-mentioned reaction soln of stirring after 5 hours with 2 hours.By adding sodium carbonate that pH is remained in 8.0～9.0, this solution is further stirred 2 hours.To the processing of being saltoutd of this reaction soln, and collect precipitate (that is the compound, meaned by formula shown below (11)) by filtration by adding 100 portions of salt.
Embodiment 3
Add 17.16 parts of diethanolamine and 6.09 parts of 2-methylamino ethanol in the aqueous solution that contains 10.08 parts of copper sulfate and 20 parts of water, thereby prepare copper complex solution.Add wherein 15 parts of tetrazo compounds (10) that obtain in embodiment 1.Carry out the copper reaction under 95 ℃～100 ℃, until be completely consumed raw material (approximately 9 hours).The salt that is 10% by the amount that adds with respect to solution is saltoutd to solution, and collects precipitate by filtration, and the dry dyestuff (that is the compound, meaned by formula shown below (4)) to obtain free acid form.The maximum absorption wavelength λ max (hereinafter, λ max means the observed value in the aqueous solution) of this aqueous dye solutions is 556nm.
Embodiment 4
Add 17.16 parts of diethanolamine and 6.09 parts of 2-methylamino ethanol in the aqueous solution that contains 10.08 parts of copper sulfate and 20 parts of water, thereby prepare copper complex solution.Add wherein 16.05 parts of tetrazo compounds (11) that obtain in embodiment 2.Carry out the copper reaction under 95 ℃～100 ℃, until be completely consumed raw material (approximately 9 hours).The salt that is 10% by the amount that adds with respect to solution is saltoutd to solution, and collects precipitate by filtration, and the dry dyestuff (that is the compound, meaned by formula shown below (13)) to obtain free acid form.The λ max of this aqueous dye solutions is 559nm.
Embodiment 5
By 1 part in the copper tetrazo compound meaned by formula (4) obtained in embodiment 3 is dissolved in 1000 parts of water to prepare dye bath.Add 300 parts of kraft pulps through making beating (30 parts of absolute dry pulps, beating degree: 35SR), and at room temperature mixture is stirred 15 minutes in this dye bath.Then, add wherein 1 part of gum rosin (30% aqueous solution), and mixture is further stirred 10 minutes.Then, add wherein 3 parts of crystalline sulfuric acid aluminium, and mixture is stirred 20 minutes.Dyed paper pulp is carried out to papermaking, thereby obtain moderate bright-coloured purple paper.
Comparative example 1
Except the copper tetrazo compound meaned by formula (4) that uses following dyestuff A as known in the art, B or C to replace obtaining in embodiment 3, in mode in the same manner as in Example 5 by dye of pulp and carry out papermaking to obtain dyed material.
Dyestuff A as known in the art: the purple dye of current frequent use (C.I. is purple 51 directly) is as follows.
Dyestuff B as known in the art: the purple dye of current frequent use (C.I. is purple 35 directly) is as follows.
Dyestuff C as known in the art: the purple dye of current frequent use (C.I. is purple 9 directly) is as follows.
Test example 1
Compare color and luster, vividness, thermochromism and light fastness between the material of the dyeing obtained in embodiment 5 and comparative example 1.The results are shown in table 1.
By use cylinder drying machine will dyed material heat treatment 10 minutes under 80 ℃～100 ℃ and the aberration that uses colorimeter (Color Eye3000, by GretagMacbeth AG manufacture) to measure itself and untreated dyed material estimate the thermochromism of each dyed material.
Test the light fastness of each dyed material according to JIS L0842 " to the test method (Test methods for color fastness to enclosed carbon arc lamp light) of the colour fastness of closed carbon arc light ", and use the specified blue standard of JIS L0841 " to the test method (Test methods for color fastness to daylight) of the colour fastness of daylight " to be estimated it.The larger expression light fastness of the number of test-results is higher.
Table 1
| Dye type | Color and luster | Vividness | Thermochromism | Light fastness |
| Known dye A | Moderate purple | Dim | Variable color is large | 1 grade |
| Known dye B | Bluish voilet | Dim | Variable color is large | 1 grade |
| Known dye C | Bluish voilet | Dim | Variable color is little | 1 grade |
| The dyestuff of formula (4) | Moderate purple | Bright-coloured | Variable color is little | The 3-4 level |
The color and luster of the known purple dye A of current frequent use is moderate purple, but shows strong dimness and lack vividness.The thermochromism of this dyestuff is large and light fastness is poor (1 grade).
The color and luster of the known purple dye B of current frequent use significantly with blueness, there is strong dimness and lack vividness.The thermochromism of this dyestuff is large and light fastness is poor (1 grade).
The color and luster of the known purple dye C of current frequent use slightly with blueness, there is strong dimness and lack vividness.Although this dyestuff its thermochromism little aspect excellence, the light fastness of this dyestuff poor (1 grade).
By contrast, the color and luster of dyestuff of the present invention (dyestuff of formula (4)) be moderate purple and its thermochromism little aspect excellence.This dyestuff also has good light fastness (3-4 level) and high vividness.The metal ion that this dyestuff also is subject to for example to dye in water hardly affects and therefore is being better than known purple dye A, B or C aspect this characteristic.
Embodiment 6
During 10 parts of copper tetrazo compounds that meaned by formula (13) in acquisition in embodiment 4 are dissolved in to 1000 parts of water.Add 2 parts of anionic property Surface Size in this solution, then by the pH regulator to 8.0 of solution, thereby prepare the size press coating fluid.This solution is delivered in size presser, is then that the weak sized paper of 7 seconds is painted by the Stockigt degree of sizing in size presser, thereby obtains bright-coloured, the slightly reddish purple paper with good level-dyeing property.
Comparative example 2
Except the copper tetrazo compound meaned by formula (13) that uses dyestuff A as known in the art, B or C to replace obtaining, by the mode with in the same manner as in Example 6, dye to obtain dyed material in embodiment 4.
Test example 2
Compare color and luster, vividness and thermochromism between the dyed material obtained in embodiment 6 and comparative example 2.The results are shown in table 2.
Table 2
| Dye type | Color and luster | Vividness | Thermochromism |
| Known dye A | Moderate purple | Dim | Variable color is large |
| Known dye B | Bluish voilet | Dim | Variable color is large |
| Known dye C | Bluish voilet | Dim | Variable color is little |
| The dyestuff of formula (13) | Moderate purple | Bright-coloured | Variable color is little |
Although the color and luster of the known purple dye A of current frequent use is moderate purple, thermochromism is large and have a low vividness.
The color and luster of the known purple dye B of current frequent use significantly is with blueness, and thermochromism is large and have a low vividness.
Although the known purple dye C of current frequent use its thermochromism little aspect excellence, the color and luster of this dyestuff slightly is with blueness and is had low vividness.
By contrast, the color and luster of dyestuff of the present invention (dyestuff of formula (13)) be moderate purple and its thermochromism little aspect excellence.The vividness of this dyestuff is higher than the vividness of known purple dye A, B or C.
Embodiment 7
The diethanolamine salt of the compound meaned by formula (4) that will obtain in embodiment 3 mixes with each ratio hereinafter with the diethanolamine salt of the compound meaned by formula (5).Prepare to adding water take in mixture the water soluble dyestuffs composition that dye strength is 10%.Each water soluble dyestuffs composition is at room temperature stored to 1 week.As a result, all these water soluble dyestuffs compositions all keep stable and do not have crystal to separate out.
<ratio of mixture >
5% compound (4): 95% compound (5)
10% compound (4): 90% compound (5)
20% compound (4): 80% compound (5)
40% compound (4): 60% compound (5)
60% compound (4): 40% compound (5)
90% compound (4): 10% compound (5)
Comparative example 3
The diethanolamine salt of the compound that will be meaned by formula shown below (14) mixes with each ratio hereinafter with the diethanolamine salt of the compound meaned by formula (5).Prepare to adding water take in mixture the water soluble dyestuffs composition that dye strength is 10%.Each water soluble dyestuffs composition is at room temperature stored to 1 week.As a result, all these water soluble dyestuffs compositions crystallize out all.
<ratio of mixture >
5% compound (14): 95% compound (5)
10% compound (14): 90% compound (5)
20% compound (14): 80% compound (5)
40% compound (14): 60% compound (5)
60% compound (14): 40% compound (5)
90% compound (14): 10% compound (5)
Comparative example 4
The diethanolamine salt of the compound that will be meaned by formula (6) mixes with each ratio hereinafter with the diethanolamine salt of the compound meaned by formula (5).Prepare to adding water take in mixture the water soluble dyestuffs composition that dye strength is 10%.All these water soluble dyestuffs compositions crystallize out immediately all after mixing.
<ratio of mixture >
5% compound (6): 95% compound (5)
10% compound (6): 90% compound (5)
20% compound (6): 80% compound (5)
40% compound (6): 60% compound (5)
60% compound (6): 40% compound (5)
90% compound (6): 10% compound (5)
Comparative example 5
The diethanolamine salt of the compound that will be meaned by formula shown below (15) (C.I. is purple 51 directly) mixes with each ratio hereinafter with the diethanolamine salt of the compound meaned by formula (5).Prepare to adding water take in mixture the water soluble dyestuffs composition that dye strength is 10%.Each water soluble dyestuffs composition is at room temperature stored to 1 week.As a result, all these water soluble dyestuffs compositions crystallize out all.
<ratio of mixture >
5% compound (15): 95% compound (5)
10% compound (15): 90% compound (5)
20% compound (15): 80% compound (5)
40% compound (15): 60% compound (5)
60% compound (15): 40% compound (5)
90% compound (15): 10% compound (5)
Embodiment 8
The diethanolamine salt of 25 parts of compounds that meaned by formula (4) is mixed with the diethanolamine salt of 75 parts of compounds that meaned by formula (5).Prepare to adding water take in mixture the water soluble dyestuffs composition that dye strength is 10%.
Comparative example 6
Preparation is containing direct blue 201 the aqueous solution (dye strength: 10%) of the blue substantive dyestuff C.I. of dianisidine.
Comparative example 7
Preparation is not containing direct blue 67 the aqueous solution (dye strength: 10%) of the blue substantive dyestuff C.I. of the tetrazo of dianisidine.
Manufacture the material of dyeing
The aqueous dye solutions of 0.05 part of embodiment 8, comparative example 6 or comparative example 7 is dissolved in 1000 parts of water to prepare dye bath.Add 300 parts of kraft pulps through making beating (30 parts of absolute dry pulps, beating degree: 35SR), and at room temperature mixture is stirred 15 minutes in this dye bath.Then, add wherein 1 part of gum rosin (30% aqueous solution), and mixture is further stirred 10 minutes.Then, add wherein 3 parts of crystalline sulfuric acid aluminium, and mixture is stirred 20 minutes.Dyed paper pulp is carried out to papermaking, thereby obtain bright-coloured reddish blue paper.
Test example 3
Test stability of solution, the color harmony light fastness of each aqueous dye solutions and their dyed material.Evaluation result is as follows.
By aqueous dye solutions being stored at room temperature and the visual observation crystal separates out the stability of solution of estimating each aqueous dye solutions.
Estimate in the same manner as described above the light fastness of each dyed material.
Table 3
| Dyestuff | Tone | Light fastness | Stability of solution |
| Embodiment 8 | Bright-coloured reddish blue | Excellent | Stable |
| Comparative example 6 | Bright-coloured reddish blue | Excellent | Stable |
| Comparative example 7 | Dim reddish blue | Poor | Slightly unstable |
Apparent from the result of the dyestuff of evaluation comparison example 7, that uses at present does not have poor light fastness or stability of solution as the blueing in field of papermaking with dyestuff containing the blue substantive dyestuff of raw material dianisidine.By contrast, the result of the dyestuff of embodiment 8 shows, although be mixed, the dye composite of the present invention of two kinds of substantive dyestuff does not contain dianisidine as raw material, but with the same in the dyestuff of use dianisidine as the comparative example 6 of raw material, for thering is the reddish blue dyestuff of good light fastness and stability of solution; Therefore, prove that the blueing dyestuff that dye composite of the present invention is used as paper is excellent.
Industrial applicibility
According to tetrazo compound of the present invention, can be used as the cellulosic fibre material that comprises papermaking material is dyed to medium blue look with high vividness, high density and fastness soluble azo dyes to purple as the salt of the copper complex formazan copper tetrazo compound of tetrazo compound or these compounds.Described copper tetrazo compound or its salt obtain producing the dye composite of the bright-coloured reddish blue with good dyeing property, and are preferably used as thus the blueing dyestuff.
Claims (12)
1. tetrazo compound or its salt meaned by formula (1),
Wherein, Ar1 is illustrated in respect to the ortho position of azo-group by hydroxyl or methoxy substitution and further by the phenyl of carboxyl substituted, and Ar2 is illustrated in respect to the ortho position of azo-group by hydroxyl or methoxy substitution and optionally further by the phenyl of sulfonic group, sulfoamido or carboxyl substituted.
2. copper complex or its salt of the tetrazo compound meaned by formula (1) according to claim 1.
3. copper complex according to claim 2 or its salt, wherein, described copper complex is the copper tetrazo compound meaned by formula (2):
Wherein, X means sulfonic group, sulfoamido or carboxyl.
4. according to the described copper complex of claim 2 or 3 or its salt, wherein, described copper complex is the copper tetrazo compound meaned by formula (3):
Wherein, X means sulfonic group, sulfoamido or carboxyl.
5. according to the described copper complex of claim 3 or 4 or its salt, wherein, X means sulfoamido or carboxyl.
6. a dye composite, it comprises two kinds of substantive dyestuff, and described two kinds of substantive dyestuff are respectively the compound or its salt meaned by formula (4) and the compound or its salt meaned by formula (5):
7. dye composite according to claim 6, wherein, the compound or its salt meaned by formula (4) is 5:95～90:10 with the ratio of components (in mass) between compound or its salt by formula (5) expression.
8. one kind by the method for cellulose dyeing, and it comprises and using according to the described compound or its salt of any one in claim 1 to 5 or according to the solution of claim 6 or 7 described dye composites.
9. a dyed material, it obtains by dyeing process according to claim 8.
10. an ink composite, it comprises according to the described compound or its salt of any one in claim 1 to 5 as tinting material.
11. ink composite according to claim 10, further comprise water-miscible organic solvent.
12. a color-tinted product, its be use according to the described ink composite of claim 10 or 11 painted.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011085037 | 2011-04-07 | ||
| JP2011-085037 | 2011-04-07 | ||
| JP2011097760 | 2011-04-26 | ||
| JP2011-097760 | 2011-04-26 | ||
| PCT/JP2012/058963 WO2012137736A1 (en) | 2011-04-07 | 2012-04-02 | Water-soluble azo dye, dye composition containing same, and dyeing method using same |
Publications (2)
| Publication Number | Publication Date |
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| CN103459513A true CN103459513A (en) | 2013-12-18 |
| CN103459513B CN103459513B (en) | 2016-04-20 |
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| CN201280017271.7A Active CN103459513B (en) | 2011-04-07 | 2012-04-02 | Soluble azo dyes, containing its dye composite and use its dyeing process |
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| Country | Link |
|---|---|
| JP (1) | JP5913291B2 (en) |
| CN (1) | CN103459513B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2013129170A1 (en) * | 2012-02-28 | 2013-09-06 | 日本化薬株式会社 | Dye-based polarizing element, and polarizing plate |
| CN104105988B (en) * | 2012-02-28 | 2016-05-18 | 日本化药株式会社 | Dyestuff is polarization element and polarizer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58174461A (en) * | 1982-04-06 | 1983-10-13 | Canon Inc | Recording solution |
| GB2134915A (en) * | 1983-02-01 | 1984-08-22 | Nippon Kayaku Kk | Disazo compounds for use in dyeing |
| JPH09235482A (en) * | 1996-02-28 | 1997-09-09 | Nippon Kayaku Co Ltd | Aqueous liquid composition and method for dyeing therewith |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH364061A (en) * | 1957-11-06 | 1962-08-31 | Durand & Huguenin Ag | Process for the production of new, metallizable azo dyes |
| GB1527602A (en) * | 1974-12-23 | 1978-10-04 | Clayton Aniline Co Ltd | Preparation of concentrated aqueous solutions of tertiary amine salts of disazo dyestuffs |
| JPS58176277A (en) * | 1982-04-09 | 1983-10-15 | Canon Inc | Recording liquid |
| JP2534908B2 (en) * | 1989-05-29 | 1996-09-18 | 日本化薬株式会社 | Azo compound and dyeing method using the same |
| JP2986614B2 (en) * | 1992-06-09 | 1999-12-06 | オリヱント化学工業株式会社 | Alcohol-soluble dye and ink composition containing the same |
| MY139010A (en) * | 2005-01-21 | 2009-08-28 | Ciba Holding Inc | 6-azo-5, 5'-dihydroxy -7,7'-disulfo-2-2'-dinaphthylamine derivatives |
-
2012
- 2012-04-02 JP JP2013508862A patent/JP5913291B2/en active Active
- 2012-04-02 CN CN201280017271.7A patent/CN103459513B/en active Active
- 2012-04-02 WO PCT/JP2012/058963 patent/WO2012137736A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58174461A (en) * | 1982-04-06 | 1983-10-13 | Canon Inc | Recording solution |
| GB2134915A (en) * | 1983-02-01 | 1984-08-22 | Nippon Kayaku Kk | Disazo compounds for use in dyeing |
| JPH09235482A (en) * | 1996-02-28 | 1997-09-09 | Nippon Kayaku Co Ltd | Aqueous liquid composition and method for dyeing therewith |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5913291B2 (en) | 2016-04-27 |
| WO2012137736A1 (en) | 2012-10-11 |
| JPWO2012137736A1 (en) | 2014-07-28 |
| CN103459513B (en) | 2016-04-20 |
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