CN103459513B - Soluble azo dyes, containing its dye composite and use its dyeing process - Google Patents
Soluble azo dyes, containing its dye composite and use its dyeing process Download PDFInfo
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- CN103459513B CN103459513B CN201280017271.7A CN201280017271A CN103459513B CN 103459513 B CN103459513 B CN 103459513B CN 201280017271 A CN201280017271 A CN 201280017271A CN 103459513 B CN103459513 B CN 103459513B
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- QMQKKGFCTCOEKD-SNAWJCMRSA-N C/C(/C=C)=C\N=O Chemical compound C/C(/C=C)=C\N=O QMQKKGFCTCOEKD-SNAWJCMRSA-N 0.000 description 1
- 0 Cc1cc(C(O)=O)cc2c1O*1Oc3c(CCC(NC4C=Cc5c6O*Cc(ccc(*)c7)c7NN(C)c6c(*)cc5C4)=C4)c4cc(S(O)(=O)=O)c3[N+]1[N-]2 Chemical compound Cc1cc(C(O)=O)cc2c1O*1Oc3c(CCC(NC4C=Cc5c6O*Cc(ccc(*)c7)c7NN(C)c6c(*)cc5C4)=C4)c4cc(S(O)(=O)=O)c3[N+]1[N-]2 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
Abstract
The present invention relates to a kind of tetrazo compound of being represented by following formula (1) or its salt (in formula, Ar1 represents at the ortho position relative to azo-group by hydroxyl or methoxy substitution and then by the phenyl of carboxyl substituted, and Ar2 to represent at the ortho position relative to azo-group by hydroxyl or methoxy substitution and then can by the phenyl of sulfonic group, sulfoamido or carboxyl substituted).
Description
Technical field
The present invention relates to soluble azo dyes and the dye composite containing it.More particularly, the present invention relates to tetrazo compound, as the copper complex formazan copper tetrazo compound of tetrazo compound or the salt of these compounds and the dye composite containing copper tetrazo compound or its salt and other dye compositions or its salt.The invention still further relates to the dyeing process using described soluble azo dyes or described dye composite.
Background technology
So far, as the cellulosic fibre material comprising papermaking material being dyed securely the dyestuff of blueness to purple, know the direct indigo plant 15 of C.I., C.I. directly indigo plant 200, C.I. directly indigo plant 202, C.I. direct blue 203 etc.These dyestuffs, as the dyestuff for the cotton in cloth dyeing or artificial silk or as the dyestuff being used for paper pulp or paper dyeing, are frequently used in paper industry.These dyestuffs generally use dianisidine as main raw material manufacture.
Especially, in papermaking material colouring art, exist and with micro-blue dyes or purple dye, the scraps of paper are dyeed, thus make the scraps of paper seem whiter technology more pure white than optics.This dyeing process, is called as blueing (bluing), and the general blueness that adopts is to the substantive dyestuff of purple.This blueing dyestuff characteristically need such as between the shelf lives dyestuff self or dye solution stablize, and produce the bright colors high to the fastness of light etc. after dyeing.Dianisidine is used to be frequently used as conventional blueing dyestuff as the blue dyes of raw material manufacture due to its bright colour.
But, FAQs in these dyestuffs is used as the dianisidine of main raw material to belong to I class particular chemicals (that is, the chemical substance that the height that serious health may be caused damage to staff is harmful to) specified by Japanese industry safety and health method (JapaneseIndustrialSafetyandHealthAct).Therefore, in the manufacturing processed of often kind of dyestuff, dianisidine is used to be subject to the strict supervision of regulation.This is the management of safety and Health and manufactures the raising of efficiency as the restriction essential factor operated under very harsh proterctive equipment.
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. is comprised to the dyestuff of purple or the example of substantive dyestuff by the blueness of the raw material manufacture except dianisidine.But, any one in these dyestuffs in dyeing behavior as being all obviously inferior to the dyestuff containing dianisidine in vividness, dyeability, fastness or thermotolerance.Therefore, these dyestuffs be equally both not suitable for use in the cellulosic fibre material comprising papermaking material to dye the firmly blue dyestuff to purple, were also not suitable for use in blueing dyestuff.
Therefore, bright-coloured and blueness that is firmly color is strongly needed to produce for a long time to the dyestuff of purple or substantive dyestuff to replace these the existing dyestuffs in dyestuff manufacture, papermaking and dyeing industry.However, the excellent dyestuff meeting all these demands is not yet obtained.
For example, Japanese Patent Publication 64-5623 publication (patent documentation 1) and Japanese Unexamined Patent Publication 7-18192 publication (patent documentation 2) describe the dye composition that represented by formula (5) separately as the blue dyes not containing dianisidine:
Use this dyestuff papermaking material can be dyed the bright-coloured blueness with good level-dyeing property.But the color and luster band of this dyestuff is green and therefore cannot produce moderate reddish blue, thus cause application limited.In addition, this dyestuff adversely has poor dyeing property and colouring intensity and low for the suitability of blueing separately.
From the viewpoint expecting the dyeing behavior of color and the Colour Difference of reality, dye composite as substantive dyestuff generally needs with the form of dye solution highly stable, namely, even if still almost there is no crystallize out after a certain amount of time between the shelf lives, and needing tone not change.However, not yet need to produce the moderate reddish blue of blueing and the excellent in stability between the shelf lives containing the dye composite of substantive dyestuff.
In this context, Japanese Laid-Open Patent Publication 59-140263 publication (patent documentation 3) describes the compound that represented by formula (6) shown below as the tetrazo compound in dye composite.But this document does not describe the tetrazo compound of the phenyl had through carboxyl substituted.
Prior art
Patent documentation
Patent documentation 1: Japanese Patent Publication 64-5623 publication
Patent documentation 2: Japanese Unexamined Patent Publication 7-18192 publication
Patent documentation 3: Japanese Laid-Open Patent Publication 59-140263 publication
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 meets dyeability, fastness, thermotolerance, vividness etc. when not using the dianisidine of the I class particular chemicals belonged to specified by Japanese industry safety and health method.
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 friendly to the mankind or the earth in safety and health, resources conservation and environmental pollution.
Another object of the present invention is for providing a kind of dye composite and using the dyeing process of described dye composite, and described dye composite does not produce containing the blue substantive dyestuff of raw material dianisidine and purple substantive dyestuff the bright-coloured reddish blue with good dyeing property being applicable to blueing dyestuff by combination.
The means of dealing with problems
The present inventor finds, the tetrazo compound that these objects can be represented by formula (1) shown below each via use or its salt realize.
The present inventor also finds, produce the dye composite with the bright-coloured reddish blue of good dyeing characteristic being specially adapted to blueing dyestuff to obtain by combinationally using two kinds of substantive dyestuff, these two kinds of substantive dyestuff are the compound (copper complex formazan a kind of form of the tetrazo compound represented by formula (1) shown below) or its salt and the compound (being also described in " background technology " paragraph) represented by formula (5) shown below or its salt that are represented by formula (4) shown below.
Specifically, each aspect of the present invention is as follows:
[1] a kind of tetrazo compound of being represented by following formula (1) or its salt,
Wherein, Ar1 represents at the ortho position relative to azo-group by hydroxyl or methoxy substitution and further by the phenyl of carboxyl substituted, and Ar2 represents at the ortho position relative to azo-group by hydroxyl or methoxy substitution and optionally further by the phenyl of sulfonic group, sulfoamido or carboxyl substituted.
The copper complex of the tetrazo compound represented by formula (1) [2] Gen Ju [1] or its salt.
[3] copper complex Gen Ju [2] or its salt, wherein said copper complex is the copper tetrazo compound represented by following formula (2):
Wherein, X represents sulfonic group, sulfoamido or carboxyl.
[4] according to [2] or the copper complex described in [3] or its salt, wherein said copper complex is the copper tetrazo compound represented by following formula (3):
Wherein, X represents sulfonic group, sulfoamido or carboxyl.
[5] according to [3] or the copper complex described in [4] or its salt, wherein, X represents sulfoamido or carboxyl.
[6] dye composite, it comprises two kinds of substantive dyestuff, and described two kinds of substantive dyestuff are respectively the compound or its salt represented by following formula (4) and the compound or its salt represented by following formula (5):
[7] dye composite Gen Ju [6], wherein, the ratio of components (in mass) between the compound or its salt represented by formula (4) and the compound or its salt represented by formula (5) is 5:95 ~ 90:10.
[8] by a method for cellulose dyeing, it comprises the solution used according to the compound or its salt according to any one of [1] to [5] or the dye composite according to [6] or [7].
[9] a dyed material, it is obtained by the dyeing process Gen Ju [8].
[10] ink composite, it comprises according to the compound or its salt according to any one of [1] to [5] as tinting material.
[11] ink composite Gen Ju [10], wherein, described ink composite comprises water-miscible organic solvent further.
[12] color-tinted product, it is that use basis [10] or the ink composite described in [11] are painted.
The advantageous effects of invention
Of the present invention represented by formula (1) tetrazo compound, do not correspond to as the copper complex formazan copper tetrazo compound of tetrazo compound or the salt of these compounds the dianisidine belonging to I class particular chemicals, and can by not using the manufacture method of dianisidine to obtain.These compound or its salts can be used as the cellulosic fibre material comprising papermaking material to dye there is high vividness, high density and fastness medium blue look to the soluble azo dyes of 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, affect by water hardness hardly, less variable color and there is high stability of solution.Excellent especially in the stability of these compound or its salts compared with the dyestuff described in Japanese Laid-Open Patent Publication 59-140263 publication in dyeability, vividness, stability of solution and when mixing with other existing dyestuffs, and compare in dyeing property and colouring intensity excellent with the dyestuff described in Japanese Unexamined Patent Publication 7-18192 publication with Japanese Patent Publication 64-5623 publication.
Especially, comprise two kinds of substantive dyestuff according to dye composite of the present invention not crystallize out and there is high stability of solution, described two kinds of substantive dyestuff are respectively the compound (copper complex of tetrazo compound) or its salt that are represented by formula (4) and the compound (copper complex of tetrazo compound) represented by formula (5) or its salt.In addition, with this dye composite, cellulosic fibre material dyeing can be produced the material of the reddish blue dyeing of the balanced dyeing property with vividness and strong fastness (photostabilization, water tolerance etc.).
Embodiment
To describe according to the tetrazo compound represented by formula (1) of the present invention.
In formula, Ar1 represents at the ortho position relative to azo-group by hydroxyl or methoxy substitution and further by the phenyl of carboxyl substituted, and Ar2 represents at the ortho position relative to 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, as long as can realize replacing.Preferred relative to the contraposition of hydroxyl or methoxyl group.
Ar2 is preferably the phenyl by the sulfoamido in sulfonic group, sulfoamido and carboxyl or carboxyl substituted.These substituting groups give compound water soluble further.Be not particularly limited by the position of sulfonic group, sulfoamido or carboxyl substituted in Ar2, as long as can realize replacing.Can adopt relative to the optional position in the ortho position of hydroxyl or methoxyl group, a position and contraposition.
Hereinafter, the example of the method manufacturing the tetrazo compound represented by formula (1) will be described.The method manufacturing this compound is not limited to method shown below.
Aromatic amines compound represented by formula shown below (7) and formula (8) that is known or that obtained by the method for application manufacture similar compound as known in the art itself can by ordinary method diazotization in the art, subsequently such as 5 DEG C ~ 40 DEG C, preferably 10 DEG C ~ 25 DEG C at utilize the commercially available dinaphthylamine derivative represented by formula shown below (9) to carry out alkaline diazo-coupling reactions, thus obtain the tetrazo compound represented by formula (1).
Ar1-NH
2(7)
Wherein Ar1 as in above-mentioned Ar1 define.
Ar2-NH
2(8)
Wherein Ar2 as in above-mentioned Ar2 define.
Copper complex or its salt of the tetrazo compound represented by formula (1) are also contained in the present invention.This copper complex formazan example comprises single copper complex and two copper complexs.Its preferred embodiment comprises as represented by formula (2) two copper complex formazan copper tetrazo compounds, and wherein X represents sulfonic group, sulfoamido or carboxyl.In this copper complex, in Ar1 carboxyl preferred the position of substitution, in Ar2, sulfonic group, sulfoamido and the preferred group in carboxyl etc. are identical with the tetrazo compound represented by formula (1).
This copper complex can use the tetrazo compound manufacture represented by formula (1) according to procedures known in the art.For example, this copper complex can by following acquisition: join in the tetrazo compound represented by formula (1) by the copper complex compound be made up of copper sulfate and ammoniacal liquor and/or alkanolamine and/or vulkacit H etc., afterwards such as 50 DEG C ~ 100 DEG C, preferably 90 DEG C ~ 100 DEG C at carry out copper reaction.In this reaction, methoxyl group experiences demethylating reaction and causes copper.
The tetrazo compound represented by formula (1) or its copper complex can be obtained by reaction soln by common salting-out process or acid-precipitation method.In addition, the tetrazo compound represented by formula (1) or its copper complex can be obtained by the Direct spraying drying of reaction soln.Or, can directly or in desalination and concentrated rear solubilizing agent or the stablizer of adding in reaction soln as urea, alkanolamine, alkylamine, ε-caprolactam, and to use in the form of a solution.
The thus obtained tetrazo compound that represented 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 such as sodium salt, sylvite and lithium salts is preferred.These salt obtain via salt-forming reaction usually.
The compound (copper complex of tetrazo compound) represented by formula (4) of the copper complex formazan a kind of form as the tetrazo compound represented by formula (1) or its salt can be combined with the compound (copper complex of tetrazo compound) represented by formula (5) or its salt, and use with the dye composite form comprising these two kinds of substantive dyestuff.This dye composite is produce the bright-coloured reddish blue and the dye composite being preferred for blueing object with good dyeing property.
The compound represented by formula (4) can be obtained by the method for application manufacture related compound as known in the art.This copper complex can by such as follows manufacture: diazotization reaction is carried out to 3-amino-4-methoxyl phenylformic acid; This reaction product joined in the solution of 7,7'-imino-two (4-hydroxyl naphthalene-2-sulfonic acid) and form tetrazo compound; Joined in copper complex solution by this compound afterwards and carry out copper reaction, described copper complex solution is prepared by diethanolamine and 2-methyl amino ethanol being joined in copper sulfate solution.
The example of the salt of the compound represented by formula (4) comprises an alkali metal salt, alkaline earth salt, alkylamine salt and alkanolamine salt.Especially, an alkali metal salt such as sodium salt, sylvite and lithium salts or low-grade alkane alcohol amine salt such as diethanolamine salt is preferred.These salt obtain via salt-forming reaction usually.
The compound or its salt represented by formula (5) is be called as the direct compound of blue 273 of C.I. in the art.This copper complex used or its salt can manufacture based on document as known in the art.Or, can commercial dyes be used.
In the dye composite of two kinds of substantive dyestuff comprising the compound or its salt being respectively and being represented by formula (4) and the compound or its salt represented by formula (5), the ratio of components (in mass) between the compound or its salt represented by formula (4) and the compound or its salt represented by formula (5) is preferably 5:95 to 90:10.
Comprise the dye composite of two kinds of substantive dyestuff of the compound or its salt being respectively and being represented by formula (4) and the compound or its salt represented by formula (5), can containing 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 object, this dye composite can contain pigment, staining agent etc. further.This dye composite can comprise solvent further as water; Salt is as sodium-chlor; Oil components etc.
May be used for cellulosic fibre material to dye according to the salt of tetrazo compound of the present invention, copper tetrazo compound or these compounds.These compound or its salts may be used for such as: for the dyeing process under the usual dyeing condition of paper or dye of pulp, comprise the top sizing dyeing process of size press and coating process, or for obtaining the beater dyeing method to the material of purple dye of the more medium blue look with high vividness and excellent light and water tolerance.In addition, these compound or its salts may be used for dyeing process under usual dyeing condition as contaminated, in continuous dyeing or printing with by cellulosic fibre material as blueness daylight and washing to fastness dyed by natural or man-made cellulose fibers and cellulose fiber such as cotton or artificial silk.In this context, dyed material also comprises the dyed cellulosic fibre material and film, building board, non-woven fabrics etc. that are obtained by the processing of filamentary material.
Especially, dyed material can use the solution of the dye composite containing two kinds of substantive dyestuff to obtain by dyeing process, and described two kinds of substantive dyestuff are respectively the compound or its salt represented by formula (4) and the compound or its salt represented by formula (5).This dye composite is used to make to 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 as the tinting material in paper use or fiber ink composite to obtain color-tinted product.This ink composite can comprise water-miscible organic solvent further as methyl alcohol, ethanol, Virahol, hydroxyethyl methylamine, thanomin, diethanolamine or trolamine.As for the tinting material in the ink composite of fiber, the salt of tetrazo compound of the present invention, copper tetrazo compound or these compounds is preferred.In this case, ink composite can comprise dispersion agent further as sulfonic acids, preferably the formaline condensates of aromatic sulphonic acid or the formaline condensates of lignosulfonic acid.
Embodiment
Hereinafter, in more detail the present invention is described with reference to embodiment.But the present invention should not limit by these embodiments.
In an embodiment, " part " and " % " refers to mass parts and quality % respectively.In addition, the sulfonic group in various represents in a free form.
Embodiment 1
In the water of 70 parts 18 DEG C ~ 22 DEG C, add 11 part of 35% hydrochloric acid, then add 7.25 parts of 3-amino-4-methoxyl phenylformic acid.Gained solution is cooled to 5 DEG C.Add 3.14 parts of Sodium Nitrites wherein, and diazotization reaction is carried out 30 minutes to mixture, thus obtain reaction soln.10 part of 7,7'-imino-two (4-hydroxyl naphthalene-2-sulfonic acid) and 5.8 parts of sodium carbonate are added in the water of 150 parts 18 DEG C ~ 22 DEG C.By adding sodium carbonate, pH being remained while 8.5 ~ 9.5, in gained solution, adding above-mentioned reaction soln with 1 hour.Mixture is stirred 3 hours further.Then, add 25 portions of salt wherein, and mixture stirring is spent the night.By adding 17 part of 35% hydrochloric acid, acid out process is carried out to solution, and by collecting by filtration precipitate (that is, the compound represented by formula (10) shown below).
Embodiment 2
3.41 parts of 3-amino-4-methoxyl phenylformic acid and 4.71 part of 35% hydrochloric acid is added in the water of 100 parts 18 DEG C ~ 22 DEG C.Gained solution is cooled to 5 DEG C.Add 1.46 parts of Sodium Nitrites wherein, and diazotization reaction is carried out 2 hours to mixture, thus obtain reaction soln.12.22 part of 7,7'-imino-two (4-hydroxyl naphthalene-2-sulfonic acid) is added in the water of 160 parts 18 DEG C ~ 22 DEG C, and with the pH regulator to 7.0 of sodium carbonate by mixture, and mixture is cooled to 5 DEG C.By adding sodium carbonate, pH being remained while 7.0 ~ 7.5, in gained solution, adding above-mentioned reaction soln with 2 hours.Then, mixture is stirred 5 hours further.In 80 parts of water, add 3.76 parts of 3-amino-4-hydroxy benzsulfamides and 4.88 part of 35% hydrochloric acid, and solution is cooled to 0 DEG C.Add 1.46 parts of Sodium Nitrites wherein, and diazotization reaction is carried out 2 hours to mixture, thus acquisition reaction soln, then by adding sodium carbonate, pH being remained while 7.0 ~ 8.0, being joined in the above-mentioned reaction soln of stirring after 5 hours with 2 hours.Remaining while 8.0 ~ 9.0 by adding sodium carbonate by pH, this solution is stirred 2 hours further.By adding 100 portions of salt, this reaction soln is saltoutd process, and by collecting by filtration precipitate (that is, the compound represented by formula (11) shown below).
Embodiment 3
In the aqueous solution containing 10.08 parts of copper sulfate and 20 parts of water, add 17.16 parts of diethanolamine and 6.09 parts of 2-methyl amino ethanol, thus prepare copper complex solution.Add 15 parts of tetrazo compounds obtained in embodiment 1 (10) wherein.Copper reaction is carried out, till being completely consumed raw material (about 9 hours) at 95 DEG C ~ 100 DEG C.By the salt that to add relative to the amount of solution be 10%, solution is saltoutd, and by collecting by filtration precipitate, and drying is to obtain the dyestuff (that is, the compound represented by formula (4) shown below) of free acid form.The maximum absorption wavelength λ max (hereinafter, λ max represents the observed value in the aqueous solution) of this aqueous dye solutions is 556nm.
Embodiment 4
In the aqueous solution containing 10.08 parts of copper sulfate and 20 parts of water, add 17.16 parts of diethanolamine and 6.09 parts of 2-methyl amino ethanol, thus prepare copper complex solution.Add 16.05 parts of tetrazo compounds obtained in example 2 (11) wherein.Copper reaction is carried out, till being completely consumed raw material (about 9 hours) at 95 DEG C ~ 100 DEG C.By the salt that to add relative to the amount of solution be 10%, solution is saltoutd, and by collecting by filtration precipitate, and drying is to obtain the dyestuff (that is, the compound represented by formula (13) shown below) of free acid form.The λ max of this aqueous dye solutions is 559nm.
Embodiment 5
The copper tetrazo compound represented by formula (4) obtained 1 part is in embodiment 3 dissolved in 1000 parts of water to prepare dye bath.In this dye bath, add 300 parts of kraft pulps (30 parts of absolute dry pulps, beating degree: 35SR) through making beating, and at room temperature mixture is stirred 15 minutes.Then, add 1 part of gum rosin (30% aqueous solution) wherein, and mixture is stirred 10 minutes further.Then, add 3 parts of crystalline sulfuric acid aluminium wherein, and mixture is stirred 20 minutes.Papermaking is carried out to dyed paper pulp, thus obtains moderate bright-coloured purple paper.
Comparative example 1
Except the copper tetrazo compound represented by formula (4) replacing obtaining in embodiment 3 except using following dyestuff A, B or C as known in the art, in mode in the same manner as in Example 5, dye of pulp is carried out papermaking to obtain dyed material.
Dyestuff A as known in the art: the purple dye (C.I. is purple 51 directly) of current frequent use is as follows.
Dyestuff B as known in the art: the purple dye (C.I. is purple 35 directly) of current frequent use is as follows.
Dyestuff C as known in the art: the purple dye (C.I. is purple 9 directly) of current frequent use is as follows.
Test example 1
Color and luster, vividness, thermochromism and light fastness is compared between the material of the dyeing obtained in embodiment 5 and comparative example 1.Result is shown in Table 1.
At 80 DEG C ~ 100 DEG C, colorimeter (ColorEye3000 is manufactured by GretagMacbethAG) is used to measure the aberration of itself and untreated dyed material to evaluate the thermochromism of each dyed material dyed material heat treatment 10 minutes by using cylinder drying machine.
Test the light fastness of each dyed material according to JISL0842 " test method (Testmethodsforcolorfastnesstoenclosedcarbonarclamplight) to the colour fastness of enclosed carbon arc light ", and use the blue standard specified by JISL0841 " test method (Testmethodsforcolorfastnesstodaylight) to the colour fastness of daylight " to evaluate it.The number larger expression light fastness 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 | 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.Large and the light fastness difference (1 grade) of the thermochromism of this dyestuff.
The color and luster of the known purple dye B of current frequent use significantly with blueness, there is strong dimness and lack vividness.Large and the light fastness difference (1 grade) of the thermochromism of this dyestuff.
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 is excellent in its thermochromism is little, the light fastness difference (1 grade) of this dyestuff.
By contrast, the color and luster of dyestuff of the present invention (dyestuff of formula (4)) is moderate purple and excellent in its thermochromism is little.This dyestuff also has good light fastness (3-4 level) and high vividness.This dyestuff is also subject to the metal ion effect in such as dyeing water hardly and therefore in this characteristic, is better than known purple dye A, B or C.
Embodiment 6
The copper tetrazo compound represented by formula (13) obtained 10 parts is in example 4 dissolved in 1000 parts of water.In this solution, add 2 parts of anionic surface's sizing agents, then by the pH regulator to 8.0 of solution, thus prepare size press coating fluid.Deliver in size presser by this solution, be then that the weak sized paper of 7 seconds is painted by Stockigt degree of sizing in size presser, thus obtain bright-coloured, the slightly reddish purple paper with good level-dyeing property.
Comparative example 2
Replace except using dyestuff A, B or C as known in the art, except the copper tetrazo compound represented by formula (13) that obtains in example 4, obtaining dyed material by dyeing in mode in the same manner as in Example 6.
Test example 2
Color and luster, vividness and thermochromism is compared between the dyed material obtained in embodiment 6 and comparative example 2.Result is 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 low vividness.
The color and luster of the known purple dye B of current frequent use is significantly with blueness, and thermochromism is large and have low vividness.
Although the known purple dye C of current frequent use is excellent in its thermochromism is little, the color and luster of this dyestuff is slightly with blueness and is had low vividness.
By contrast, the color and luster of dyestuff of the present invention (dyestuff of formula (13)) is moderate purple and excellent in its thermochromism is little.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 represented by formula (4) obtained in embodiment 3 is mixed with each ratio hereafter with the diethanolamine salt of the compound represented by formula (5).Water is added to prepare the water soluble dyestuffs composition that dye strength is 10% in mixture.Each water soluble dyestuffs composition is at room temperature stored 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 represented by formula (14) shown below is mixed with each ratio hereafter with the diethanolamine salt of the compound represented by formula (5).Water is added to prepare the water soluble dyestuffs composition that dye strength is 10% in mixture.Each water soluble dyestuffs composition is at room temperature stored 1 week.As a result, all these water soluble dyestuffs compositions all crystallize outs.
< 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 represented by formula (6) is mixed with each ratio hereafter with the diethanolamine salt of the compound represented by formula (5).Water is added to prepare the water soluble dyestuffs composition that dye strength is 10% in mixture.All these water soluble dyestuffs compositions crystallize out all immediately upon 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 represented by formula (15) shown below (C.I. is purple 51 directly) is mixed with each ratio hereafter with the diethanolamine salt of the compound represented by formula (5).Water is added to prepare the water soluble dyestuffs composition that dye strength is 10% in mixture.Each water soluble dyestuffs composition is at room temperature stored 1 week.As a result, all these water soluble dyestuffs compositions all crystallize outs.
< 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 the diethanolamine salt of 25 parts of compounds represented by formula (4) with 75 parts of compounds represented by formula (5) is mixed.Water is added to prepare the water soluble dyestuffs composition that dye strength is 10% in mixture.
Comparative example 6
Preparation is containing the direct aqueous solution (dye strength: 10%) of blue 201 of blue substantive dyestuff C.I. of dianisidine.
Comparative example 7
Preparation is not containing the direct aqueous solution (dye strength: 10%) of blue 67 of the blue substantive dyestuff C.I. of 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.In this dye bath, add 300 parts of kraft pulps (30 parts of absolute dry pulps, beating degree: 35SR) through making beating, and at room temperature mixture is stirred 15 minutes.Then, add 1 part of gum rosin (30% aqueous solution) wherein, and mixture is stirred 10 minutes further.Then, add 3 parts of crystalline sulfuric acid aluminium wherein, and mixture is stirred 20 minutes.Papermaking is carried out to dyed paper pulp, thus obtains bright-coloured reddish blue paper.
Test example 3
Test the stability of solution of each aqueous dye solutions and their dyed material, tone and light fastness.Evaluation result is as follows.
By aqueous dye solutions is stored at room temperature and visual observation crystal separates out the stability of solution evaluating each aqueous dye solutions.
Evaluate the light fastness of each dyed material in the same manner as described above.
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 | Difference | Slightly unstable |
Apparent from the result of the dyestuff of evaluation comparison example 7, what use at present does not have poor light fastness or stability of solution containing the blue substantive dyestuff of raw material dianisidine as the blueing dyestuff in field of papermaking.By contrast, the result display of the dyestuff of embodiment 8, although mixture has the dye composite of the present invention of two kinds of substantive dyestuff not contain dianisidine as raw material, but the same with the dyestuff using dianisidine as the comparative example 6 of raw material, for having the reddish blue dyestuff of good light fastness and stability of solution; Therefore, prove that dye composite of the present invention is excellent as the blueing dyestuff of paper.
Industrial applicibility
According to tetrazo compound of the present invention, as the copper complex formazan copper tetrazo compound of tetrazo compound or the salt of these compounds can be used as the cellulosic fibre material comprising papermaking material to dye there is high vividness, high density and fastness medium blue look to the soluble azo dyes of purple.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 blueing dyestuff thus.
Claims (4)
1. a dye composite, it comprises two kinds of substantive dyestuff, and described two kinds of substantive dyestuff are respectively the compound or its salt represented by formula (4) and the compound or its salt represented by formula (5):
2. dye composite according to claim 1, wherein, the ratio of components between the compound or its salt represented by formula (4) and the compound or its salt represented by formula (5) is 5:95 ~ 90:10 in mass.
3., by a method for cellulose dyeing, it comprises the solution using dye composite according to claim 1 and 2.
4. a dyed material, it is obtained by dyeing process according to claim 3.
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 |
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| CN103459513A CN103459513A (en) | 2013-12-18 |
| CN103459513B true CN103459513B (en) | 2016-04-20 |
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| JP (1) | JP5913291B2 (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 |
Family Cites Families (9)
| 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 |
| JPS58174461A (en) * | 1982-04-06 | 1983-10-13 | Canon Inc | Recording solution |
| JPS58176277A (en) * | 1982-04-09 | 1983-10-15 | Canon Inc | Recording liquid |
| JPS59140263A (en) * | 1983-02-01 | 1984-08-11 | Nippon Kayaku Co Ltd | Dis-azo compound and dyeing method using the same |
| 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 |
| JPH09235482A (en) * | 1996-02-28 | 1997-09-09 | Nippon Kayaku Co Ltd | Aqueous liquid composition and method for dyeing therewith |
| MY139010A (en) * | 2005-01-21 | 2009-08-28 | Ciba Holding Inc | 6-azo-5, 5'-dihydroxy -7,7'-disulfo-2-2'-dinaphthylamine derivatives |
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- 2012-04-02 CN CN201280017271.7A patent/CN103459513B/en active Active
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| Publication number | Publication date |
|---|---|
| CN103459513A (en) | 2013-12-18 |
| JP5913291B2 (en) | 2016-04-27 |
| WO2012137736A1 (en) | 2012-10-11 |
| JPWO2012137736A1 (en) | 2014-07-28 |
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