WO2000068319A1 - Mixtures of symmetrical and unsymmetrical red reactive dyes - Google Patents

Mixtures of symmetrical and unsymmetrical red reactive dyes Download PDF

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Publication number
WO2000068319A1
WO2000068319A1 PCT/US2000/006434 US0006434W WO0068319A1 WO 2000068319 A1 WO2000068319 A1 WO 2000068319A1 US 0006434 W US0006434 W US 0006434W WO 0068319 A1 WO0068319 A1 WO 0068319A1
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Prior art keywords
formula
mixture
dyestuff
following
alkyl
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PCT/US2000/006434
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French (fr)
Inventor
Ming-Mei Yeh
Ting-Jui Chang
Sheena Lee
Da-Jong Yin
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Everlight Usa, Inc.
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Priority to AU40087/00A priority Critical patent/AU4008700A/en
Priority to EP00919391A priority patent/EP1179034B1/en
Publication of WO2000068319A1 publication Critical patent/WO2000068319A1/en
Priority to HK02104991.9A priority patent/HK1043145B/en

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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/38General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
    • D06P1/382General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group directly attached to heterocyclic group
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0046Mixtures of two or more azo dyes
    • C09B67/0055Mixtures of two or more disazo dyes
    • C09B67/0057Mixtures of two or more reactive disazo dyes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/916Natural fiber dyeing
    • Y10S8/918Cellulose textile
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92Synthetic fiber dyeing
    • Y10S8/924Polyamide fiber

Definitions

  • the present invention relates to novel mixtures of reactive red dyes comprising three components, which in the free acid form, may be represented by the following formulae, a) a reactive red dye of the formula (I)
  • R is a hydrogen atom or C]__4 alkyl
  • X is a fluorine, chlorine or bromine atom
  • a and A' are different and each is independently a phenyl or naphthyl group, which may be unsubstituted or substituted by one or more groups selected from C]__4 alkyl, C]__4 alkoxyl or
  • Z is C]__4 alkyl, C]__4 alkoxyl or -SO2Q where Q is
  • the azo group is in the 2-position of the naphthalene nucleus and that the 1-position of the naphthalene is substituted by a sulphonic acid residue as below,
  • Z is C__ alkyl, C]__4 alkoxyl or —SO2Q where Q is
  • compositions containing various percentages of dyes of the present invention can be obtained directly by varying the molar ratios of the reactants during manufacture. Furthermore, materials with good dyeing properties and with various red colour tones, depending on ratio percentage of the individual reactive red dyes in the compositions, can be obtained.
  • the present invention also relates to the preparation, and use as a reactive dye, of a compound of formula (I), alone, as well as in admixture with compounds of formulae (II) and (II'), for dyeing and printing cellulose containing fibres .
  • Dye mixtures comprising reactive dyes of the formulae (I), (II) and (II 1 ) give dyeings having outstanding technical properties, in particular good wash-off, wet fastness and dyeing properties.
  • compositions of the present invention can be synthesized by the following method.
  • the process for preparing dye compositions of the present invention is very special.
  • the desired compositions containing reactive red dyes of the present invention can be obtained directly by using designed quantities of starting materials during the reaction steps.
  • the individual components of dye mixtures are synthesized individually first, then subsequently mixed together in the required ratios.
  • the process used to produce dye mixtures of the present invention is totally different from these known processes. Additionally the greater solubility of dye mixtures of the present invention, relative to that of the individual components, allows the use of more concentrated reaction mixtures leading to more productive processes.
  • l-amino-8-hydroxynaphthalenedisulphonic acid is dissolved in neutral aqueous solution then reacted with a trihalogenotriazine of formula (a) ,
  • each X is a fluorine, chlorine or bromine atom.
  • the reaction is carried out by stirring the mixture of starting materials, at a temperature between 0 ⁇ 30°C, preferably below 20°C, and the pH is allowed to fall to below pH3 whereupon the intermediate (b) , having the structure depicted below, is obtained.
  • X has the same definition as above.
  • A-NH2 and A' -NH2 include 4(2- sulphatoethylsulphonyl-) aniline, 3 (2-sulphatoethylsulphonyl- ) aniline, 2-amino-5- (2-sulphatoethylsulphonyl- ) benzenesulphonic acid, 2-amino-4- (2-sulphatoethylsulphonyl- ) benzenesulphonic acid, 3-aminobenzenesulphonic acid, 4-amino benzenesulphonic acid, 2-aminobenzenesulphonic acid, 6- aminobenzene-1, 3-disulphonic acid, 5-aminobenzene-l, 4- disulphonic acid, 2-amino-5-methylbenzenesulphonic acid, 2- amino-4-methylbenzenesulphonic acid, 2-amino-5- methoxybenzenesulphonic acid, 2-amino-5-nitrobenzenesulphonic acid, 2-a
  • intermediate (c) and intermediate (d) are then reacted with 3, 5-diaminobenzoic acid or methyl 3,5- diaminobenzoate .
  • the pH is controlled by the use of an acid binder.
  • the reactive red dyestuff of the present invention of formula (I) is then obtained, together with dyestuffs of formulae (II) and (II 1 ).
  • the temperature is maintained at between 20-80°C, preferably 3C-50°C.
  • Acid binder is used to neutralize the acid produced and control the pH during the reaction.
  • the pH of the well stirred reaction mixture is maintained at between 5 to 9, preferably 6 to 7.
  • Suitable acid binders include the alkali metal hydroxides, carbonates or hydrogen carbonates. Especially valuable are the carbonates or hydrogen carbonates of sodium, potassium and lithium. The carbonate or hydrogen carbonate of sodium is especially preferred.
  • the resulting solution contains a comound of formula (I), a compound of formula (II) and a compound of formula (II 1 )
  • X, R, A, and A' have the same definition as above.
  • the dyestuff mixtures of the present invention can be made by the method described above.
  • the reaction conditions used have also been described thoroughly in the previous illustration.
  • the quantities of compounds of formulae (c) and (d) it is possible to obtain a mixture in which the major product is the unsymmetrical red reactive dye of formula (I) which can be purified using known methods, such as selective precipitation in presence of added electrolyte.
  • the compound of formula (I) can be obtained in a two stage process in which the dichlorotriazine
  • the dyestuffs of the present invention can be used in the form of powders, grains, particles or liquids which may also contain retarding agents, surfactants, dispersing agents or other auxiliary agents.
  • the dyestuff mixtures of the present invention all contain anionic groups, such as sulphonic acid groups. For convenience they are depicted here in the free acid form but under usual conditions will be present in the form of salts.
  • anionic groups such as sulphonic acid groups.
  • the dyestuffs of the present invention are manufactured, purified or used, they exist in the form of water soluble salts, especially alkaline metal salts, such as sodium, potassium or ammonium salts.
  • the reactive red dyestuffs mixture of the present invention comprising dyes of formulae (I), (II) and (II 1 ), and also the unsymmetrical dye of formula (I), can be used to dye natural or synthetic yarn, woven or knitted fabrics that contain amide groups, such as wool, silk or polyamide. They are especially suitable for dyeing or printing hydroxyl containing fibres such as and natural or reconstituted cellulose fibres such as cotton, linen, viscose and lyocel fibres. They are also suitable for the dyeing of blends of these fibres with synthetic fibres such as polyester or polyacrylonitrile .
  • the dyeing methods used are those generally used when applying reactive dyestuffs. Dyeing cellulose fibre for example, the dyeing process is carried out with the assistance of acid-binding agents such as sodium hydroxide, sodium phosphate, sodium carbonate or sodium bicarbonate before, during or after dyeing; auxiliary agents can also be used as required.
  • Example 1 An ice cold neutral solution of l-hydroxy-8- aminonaphthalene-3, 6-disulphonic acid (31.9 parts) in water (120 parts) was added, with stirring, to a freshly prepared suspension of 2, 4 , 6-trichloro-s-triazine (18.5 parts) in ice and water (140 parts). The mixture was stirred for 3 hours at 0 to 5 °C to give a solution of l-hydroxy-8- (2 , 4-dichloro- s-triazin- ⁇ -ylamino-) naphthalene-3, ⁇ -disulphonic acid (solution 1) .
  • solution 1 A solution (solution 1) of l-hydroxy-8- (2, 4-dichloro-s- triazin-6-ylamino-) naphthalene-3, 6-disulphonic acid was prepared as described in Example 1 above.
  • solution 1 A solution of l-hydroxy-8- (2 , 4-dichloro-s-triazin-6- ylamino-) naphthalene-3, 6-disulphonic acid (solution 1) was prepared as described in Example 1.
  • Example 5 A mixture of 2-sulphobenzendiazonium chloride and 1,5- disulphonaphthalene-2-diazonium chloride was prepared by diazotising a mixture of 2-aminobenzenesulphonic acid (2.9 parts) and 2-aminonaphthalene-l, 5-disulphonic acid (25.3. parts) with nitrous acid.
  • the ratio of components, which was determined by HPLC was compound (I- 2)30.75%; compound ( II-3) 64.16% and compound (II-4 ) 5.08%.
  • a red powder was obtained through spray drying which, under the usual dyeing procedure, furnished red dyeings with Good fastness properties.
  • Example 3 Using the procedure described in Example 3 a red dyestuff mixture consisting dyes of formula (I-l), formula (II-l) and formula (II-2) was obtained. This mixture was separated by known procedures . A reactive red dye having formula (I-l) was obtained. This material exhibited excellent build-up and fastness properties when applied to woven cotton fabric.
  • Example 7 A procedure similar to that of Example 5 was employed to obtain a red dyestuff composition composed of formula (I- 2), formula (II-3) and formula (II-4). Then the composition was further separated by known procedures. A reactive red dye having formula (1-2) was thus obtained. This yielded red dyeings with excellent build-up on knitted cotton fabric.
  • the reactive red dyestuffs or dye mixtures of the present invention can be used to dye yarn, woven or knitted fabrics that contain amide groups, such as wool, silk or polyamide. They can also be used to dye cellulosic fibres like cotton, linen or reconstituted celluilose.
  • the dyed material can be treated with acid binder solution such as sodium hydroxide, sodium phosphate, sodium carbonate or sodium bicarbonate before, during or after the application of dye.
  • acid binder solution such as sodium hydroxide, sodium phosphate, sodium carbonate or sodium bicarbonate.
  • auxiliary reagents can also be used as required.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
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Abstract

The present invention relates to novel, three component, mixtures comprising red reactive dyes which in the free acid forms are represented by formulae (I), (II) and (II'), a) a red reactive dye of formula (I), b) a reactive red dye of formula (II), c) a reactive red dye of formula (II') where the variables are as described in the claims. The mixtures are suitable for dyeing and printing cellulose containing fibre materials and produce dyeings and prints which exhibit good build up and fastness properties.

Description

MIXTURES OF SYMMETRICAL AND UNSYMMETRICAL RED REACTIVE DYES
FTFLD OF THE INVENTION The preparation of novel, three component, mixtures of red reactive dyestuffs and a process for their application to cellulose textiles.
SUMMARY OF THE INVENTION The present invention relates to novel mixtures of reactive red dyes comprising three components, which in the free acid form, may be represented by the following formulae, a) a reactive red dye of the formula (I)
Figure imgf000003_0001
(I) b) a reactive red dye of the formula (II)
Figure imgf000004_0001
(ID c) a reactive red dye of the formula (II'
Figure imgf000004_0002
( I I '
in each of the formulae (I), (II) and (II1) R is a hydrogen atom or C]__4 alkyl; X is a fluorine, chlorine or bromine atom;
A and A' are different and each is independently a phenyl or naphthyl group, which may be unsubstituted or substituted by one or more groups selected from C]__4 alkyl, C]__4 alkoxyl or
-S02Q where Q is —OH —CH=CH2 —C2H-4OSO3H or —C2H4CI . In each of the compounds of formula (I), (II) and (II') of the present invention, both of the groups A and A' can be substituted or unsubstituted. When A or A' is substituted phenyl, it is preferred that A or A' is a substituted phenyl sulphonic acid as below,
Figure imgf000005_0001
wherein, Z is C]__4 alkyl, C]__4 alkoxyl or -SO2Q where Q is
—OH , —CH=CH2 , —C2H4OSO3H or —C2H4C1.
When A or A1 is substituted naphthyl, it is preferred that the azo group is in the 2-position of the naphthalene nucleus and that the 1-position of the naphthalene is substituted by a sulphonic acid residue as below,
Figure imgf000005_0002
wherein, Z is C__ alkyl, C]__4 alkoxyl or —SO2Q where Q is
—OH , —CH=CH2 , —C2H4OSO3H or —C2H4C1.
Compositions containing various percentages of dyes of the present invention can be obtained directly by varying the molar ratios of the reactants during manufacture. Furthermore, materials with good dyeing properties and with various red colour tones, depending on ratio percentage of the individual reactive red dyes in the compositions, can be obtained.
The present invention also relates to the preparation, and use as a reactive dye, of a compound of formula (I), alone, as well as in admixture with compounds of formulae (II) and (II'), for dyeing and printing cellulose containing fibres .
Dye mixtures comprising reactive dyes of the formulae (I), (II) and (II1) give dyeings having outstanding technical properties, in particular good wash-off, wet fastness and dyeing properties.
By preparing mixtures in which the reactive red dyestuffs of the present invention are combined in different ratios dyed materials with outstanding wash off, level dyeing and wash fastness properties can be obtained.
DESCRIPTON OF THE PREFERRED EMRODTMFNTS
Compositions of the present invention can be synthesized by the following method. The process for preparing dye compositions of the present invention is very special. The desired compositions containing reactive red dyes of the present invention can be obtained directly by using designed quantities of starting materials during the reaction steps. In most known manufacturing processes, of dye compositions containing mixtures of dyes, the individual components of dye mixtures are synthesized individually first, then subsequently mixed together in the required ratios. However, the process used to produce dye mixtures of the present invention is totally different from these known processes. Additionally the greater solubility of dye mixtures of the present invention, relative to that of the individual components, allows the use of more concentrated reaction mixtures leading to more productive processes. First, l-amino-8-hydroxynaphthalenedisulphonic acid is dissolved in neutral aqueous solution then reacted with a trihalogenotriazine of formula (a) ,
Figure imgf000007_0001
(a) wherein each X is a fluorine, chlorine or bromine atom.
The reaction is carried out by stirring the mixture of starting materials, at a temperature between 0~30°C, preferably below 20°C, and the pH is allowed to fall to below pH3 whereupon the intermediate (b) , having the structure depicted below, is obtained.
Figure imgf000007_0002
(b)
X has the same definition as above.
Then a mixture of the diazonium salts A-N2+ and A'-N2+, prepared by diazotisation of a mixture of amines A- H2 and A'-NH2, is allowed to react with compound (b) , to yield a solution containing a mixture of intermediate (c) and intermediate (d)
Figure imgf000008_0001
( c )
Figure imgf000008_0002
(d)
wherein, X, A, and A' are as defined above.
Preferred examples of A-NH2 and A' -NH2 include 4(2- sulphatoethylsulphonyl-) aniline, 3 (2-sulphatoethylsulphonyl- ) aniline, 2-amino-5- (2-sulphatoethylsulphonyl- ) benzenesulphonic acid, 2-amino-4- (2-sulphatoethylsulphonyl- ) benzenesulphonic acid, 3-aminobenzenesulphonic acid, 4-amino benzenesulphonic acid, 2-aminobenzenesulphonic acid, 6- aminobenzene-1, 3-disulphonic acid, 5-aminobenzene-l, 4- disulphonic acid, 2-amino-5-methylbenzenesulphonic acid, 2- amino-4-methylbenzenesulphonic acid, 2-amino-5- methoxybenzenesulphonic acid, 2-amino-5-nitrobenzenesulphonic acid, 2-amino-5-nitrobenzenesulphonic acid, 2- aminonaphthalene-1-sulphonic acid; 2-aminonaphthalene-l, 5- disulphonic acid, 2-amino-5- (2-sulphatoethylsulphonyl-) naphthalene-1-sulphonic acid and 2-amino-β- (2- sulphatoethylsulphonyl-) naphthalene-1-sulphonic acid.
The mixture of intermediate (c) and intermediate (d) is then reacted with 3, 5-diaminobenzoic acid or methyl 3,5- diaminobenzoate . During the reaction the pH is controlled by the use of an acid binder. The reactive red dyestuff of the present invention of formula (I) is then obtained, together with dyestuffs of formulae (II) and (II1). The temperature is maintained at between 20-80°C, preferably 3C-50°C. Acid binder is used to neutralize the acid produced and control the pH during the reaction. The pH of the well stirred reaction mixture is maintained at between 5 to 9, preferably 6 to 7. Suitable acid binders include the alkali metal hydroxides, carbonates or hydrogen carbonates. Especially valuable are the carbonates or hydrogen carbonates of sodium, potassium and lithium. The carbonate or hydrogen carbonate of sodium is especially preferred.
After completing the reaction, the resulting solution contains a comound of formula (I), a compound of formula (II) and a compound of formula (II1)
Figure imgf000010_0001
Figure imgf000010_0002
Figure imgf000010_0003
(II')
wherein, X, R, A, and A' have the same definition as above. The dyestuff mixtures of the present invention can be made by the method described above. The reaction conditions used have also been described thoroughly in the previous illustration. By appropriate choice of the quantities of compounds of formulae (c) and (d) it is possible to obtain a mixture in which the major product is the unsymmetrical red reactive dye of formula (I) which can be purified using known methods, such as selective precipitation in presence of added electrolyte. Also the compound of formula (I) can be obtained in a two stage process in which the dichlorotriazine
(c) is reacted at low pH, and at 20°C to 40°C, with 1 molar equivalent of 3, 5-diaminobenzoic acid or methyl-3, 5- diaminobenzoate, and then the resulting product is further reacted with a molar equivalent of the other dichlorotriazine
(d) to give the unsymmetrical product represented by the formula (I) . Mixing the different compounds of formula (I), (II) and (II1) in different ratios yields reactive red dyestuff mixtures which produce dyeings of excellent quality. The ratio of each dye component can be varied over a wide range. In general, the minimum relative percentage by weight of each dye component is 1%, and the maximum percentage by weight is 85%.
The dyestuffs of the present invention can be used in the form of powders, grains, particles or liquids which may also contain retarding agents, surfactants, dispersing agents or other auxiliary agents.
The dyestuff mixtures of the present invention all contain anionic groups, such as sulphonic acid groups. For convenience they are depicted here in the free acid form but under usual conditions will be present in the form of salts. When the dyestuffs of the present invention are manufactured, purified or used, they exist in the form of water soluble salts, especially alkaline metal salts, such as sodium, potassium or ammonium salts.
The reactive red dyestuffs mixture of the present invention, comprising dyes of formulae (I), (II) and (II1), and also the unsymmetrical dye of formula (I), can be used to dye natural or synthetic yarn, woven or knitted fabrics that contain amide groups, such as wool, silk or polyamide. They are especially suitable for dyeing or printing hydroxyl containing fibres such as and natural or reconstituted cellulose fibres such as cotton, linen, viscose and lyocel fibres. They are also suitable for the dyeing of blends of these fibres with synthetic fibres such as polyester or polyacrylonitrile . The dyeing methods used are those generally used when applying reactive dyestuffs. Dyeing cellulose fibre for example, the dyeing process is carried out with the assistance of acid-binding agents such as sodium hydroxide, sodium phosphate, sodium carbonate or sodium bicarbonate before, during or after dyeing; auxiliary agents can also be used as required.
More detailed examples are used to illustrate and explain the present invention. The examples below, which are given simply by way of illustration, must not be taken to limit the scope of the invention. In the examples, compounds of the present invention are depicted as free acids, but their actual form can be that of metallic salts, or more possibly alkali metal salts, especially sodium salts.
Example 1. An ice cold neutral solution of l-hydroxy-8- aminonaphthalene-3, 6-disulphonic acid (31.9 parts) in water (120 parts) was added, with stirring, to a freshly prepared suspension of 2, 4 , 6-trichloro-s-triazine (18.5 parts) in ice and water (140 parts). The mixture was stirred for 3 hours at 0 to 5 °C to give a solution of l-hydroxy-8- (2 , 4-dichloro- s-triazin-β-ylamino-) naphthalene-3, β-disulphonic acid (solution 1) .
At the same time a mixture of 2-sulphobenzendiazonium chloride and 1, 5-disulphonaphthalene-2-diazonium chloride was prepared by diazotising a mixture of 2-amincbenzenesulphonic acid (1.7 parts) and 2-aminonaphthalene-l, 5-disulphonic acid (27.3 parts) with nitrous acid. Solution 1 was added to this mixture of diazonium salts, the pH was raised to between 6 and 7 and the mixture was stirred for 3 hours, at pH 6 to 7, and at less than 10 °C, after which time coupling was essentially complete. 3, 5-Diaminobenzoic acid (7.6 parts) was added and the mixture was stirred at 30 to 40°C and at pH 6 to 7 to give a mixture of compounds (1-1) , (II-l) and (II- 2), λmax=524.5nm. The ratio of each component, determined by HPLC, was as follows; formula (1-1) 20.92%; formula (II-l) 78.00%; and formula (II-2) 1.07%. After drying, a red powder was obtained which dyed cotton in a deep red shade with excellent fastness properties.
Figure imgf000013_0001
1 - 1 :
Figure imgf000014_0001
Figure imgf000014_0002
( I I -2 )
Example 2
A cold solution of l-hydroxy-8- (2, 4-dichloro-s-triazin- β-ylamino-) naphthalene-3, 6-disulphonic acid was prepared as described above (solution 1) .
At the same time a mixture of 2-sulphobenzendiazonium chloride and 1, 5-disulphonaphthalene-2-diazonium chloride was prepared by diazotising a mixture of 2-aminobenzenesulphonic acid (2.9 parts) and 2-aminonaphthalene-l, 5-disulphonic acid (25.3 parts) with nitrous acid. Solution 1 was added to this mixture of diazonium salts, the pH was raised to between 6 and 7 and the mixture was stirred for 3 hours, at pH 6 to 7, and at less than 10 °C, after which time coupling was essentially complete. 3 , 5-Diaminobenzoic acid (7.6 parts) was added and the mixture was stirred at 30 to 40°C and at pH 6 to 7 to give a mixture of compounds (1-1), (II-l) and (II- 2), λmax=524.5nm. The ratio of components, determined by HPLC was compound (1-1) 26.34%; compound ( II-l ) 69.22% and compound (11-2)4.44%. A red powder was obtained by spray drying. The dyestuff mixture dyed cotton a deep red shade with good build up and excellent properties.
Example 3
A solution (solution 1) of l-hydroxy-8- (2, 4-dichloro-s- triazin-6-ylamino-) naphthalene-3, 6-disulphonic acid was prepared as described in Example 1 above.
At the same time a mixture of 2-sulphobenzendiazonium chloride and 1, 5-disulphonaphthalene-2-diazonium chloride was prepared by diazotising a mixture of 2-aminobenzenesulphonic acid (8.7 parts) and 2-aminonaphthalene-l, 5-disulphonic acid (15.2 parts) with nitrous acid. Solution 1 was added to this mixture of diazonium salts, the pH was raised to between 6 and 7 and the mixture was stirred for 3 hours, at pH 6 to 7, and at less than 10 °C, after which time coupling was essentially complete. 3, 5-Diaminobenzoic acid (7.6 parts) was added and the mixture was stirred at 30 to 40°C and at pH 6 to 7 to give a mixture of compounds (1-1), (II-l) and (II- 2), λmax=520. Onm. The ratio of components, which was determined by HPLC was compound (1-1) 51.48%; compound (II-l) 19.29% and compound (II-2 ) 29.43%. A red powder was obtained by spray drying. The dyestuff mixture was used to dye a piece of knitted cotton a deep red shade; the dyeings thus obtained exhibited excellent fastness properties. Example 4
A solution of l-hydroxy-8- (2 , 4-dichloro-s-triazin-6- ylamino-) naphthalene-3, 6-disulphonic acid (solution 1) was prepared as described in Example 1.
At the same time a mixture of 2-sulphobenzendiazonium chloride and 1, 5-disulphonaphthalene-2-diazonium chloride was prepared by diazotising a mixture of 2-aminobenzenesulphonic acid (13.8 parts) and 2-aminonaphthalene-l, 5-disulphonic acid (6.1 parts) with nitrous acid. Solution 1 was added to this mixture of diazonium salts, the pH was raised to between 6 and 7 and the mixture was stirred for 3 hours, at pH 6 to 7, and at less than 10 °C, after which time coupling was essentially complete. 3, 5-Diaminobenzoic acid (7.6 parts) was added and the mixture was stirred at 30 to 40°C and at pH 6 to 7 to give a mixture of compounds (1-1), (II-l) and (II- 2), λmax=514.5nm. The ratio of components, which was determined by HPLC was as follows; compound (1-1) 22.63%; compound (II-l) 4.26% and compound (II-2) 73.67%. A red powder was obtained on spray drying. The dyestuff mixture was used to dye cotton fabric in a deep red shade with excellent properties.
Example 5 A mixture of 2-sulphobenzendiazonium chloride and 1,5- disulphonaphthalene-2-diazonium chloride was prepared by diazotising a mixture of 2-aminobenzenesulphonic acid (2.9 parts) and 2-aminonaphthalene-l, 5-disulphonic acid (25.3. parts) with nitrous acid. A solution of 1-hydroxy-S- (2, 4-dichloro-s-triazin-6-ylamino-) naphthalene-3, 6- disulphonic acid, prepared from l-hydroxy-8-aminonaphthalene- 3, 6-disulphonic acid (31.9 parts) as described in Example 1, was added to this mixture of diazonium salts, the pH was raised to between 6 and 7 ana the mixture was stirred for 3 hours, at pH 6 to 7, and at less than 10 °C, after which time coupling was essentially complete. Methyl-3,5- diaminobenzoate (8.3 parts) was added and the mixture was stirred at 30 to 40 °C and at pH 6 to 7 to give a mixture of compounds (1-2), (II-3) and (II-4), Xmax=519.5nm. The ratio of components, which was determined by HPLC was compound (I- 2)30.75%; compound ( II-3) 64.16% and compound (II-4 ) 5.08%. A red powder was obtained through spray drying which, under the usual dyeing procedure, furnished red dyeings with Good fastness properties.
Figure imgf000017_0001
II-3)
Figure imgf000018_0001
( I I - 4 )
Example 6
Using the procedure described in Example 3 a red dyestuff mixture consisting dyes of formula (I-l), formula (II-l) and formula (II-2) was obtained. This mixture was separated by known procedures . A reactive red dye having formula (I-l) was obtained. This material exhibited excellent build-up and fastness properties when applied to woven cotton fabric.
Example 7 A procedure similar to that of Example 5 was employed to obtain a red dyestuff composition composed of formula (I- 2), formula (II-3) and formula (II-4). Then the composition was further separated by known procedures. A reactive red dye having formula (1-2) was thus obtained. This yielded red dyeings with excellent build-up on knitted cotton fabric.
Dye testing:
The following procedure was used. a. Separately take the above dyestuffs (Examples 1 to 7) one part and dissolve in 1000 parts of distilled water to give a solution of dye. b. Then take two dyeing bottles washed with distilled water and put aliquots of dyeing solution, 40 parts and 80 parts, into the bottles, finally add 4.8 parts Glauber's salt to each bottle. c. Add distilled water to each bottle up to a total of 85 parts by volume. d. Add 5 parts of a solution of pure base (320g/l) to each bottle. e. Place two parts of prewetted full cotton woven fabric into each dyeing bottle. The top of the bottle is covered with a lid and shaken thoroughly. f. Put the dyeing bottle into a thermobath, heat up to 80°C over 5 minutes and keep at the same temperature for 60 minutes. The fabric is taken out and washed with cold water, then put into a big stainless bucket and washed with hot water for 10 minutes. Then the fabric is put into another big stainless steel bucket with 2 g/1 soaping agent, and washed with boiling water for 10 minutes . g. The fabric is taken out, washed with cold water, then dried. The reactive red dyestuffs or dye mixtures of the present invention can be used to dye yarn, woven or knitted fabrics that contain amide groups, such as wool, silk or polyamide. They can also be used to dye cellulosic fibres like cotton, linen or reconstituted celluilose. They are especially suitable for dyeing or printing hyaroxyl group containing yarn and fabrics, for example cotton and reconstituted cellulose. They can also be used for dyeing or printing blends of these fibres with synthetic fibres such as polyesters, polyacrylonitrile etc. The dyeing methods used are those generally employed when applying reactive dyestuffs When dyeing cellulose fibre, for instance, the dyed material can be treated with acid binder solution such as sodium hydroxide, sodium phosphate, sodium carbonate or sodium bicarbonate before, during or after the application of dye. Required amounts of auxiliary reagents can also be used as required.
From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. Thus, other embodiments are also within the claims.

Claims

What is claimed is:
1. A red reactive dye mixture comprising three red reactive dyes which may be represented, in the free acid forms, by the formulae (1), (II) and (II1), a) Formula (I)
Figure imgf000021_0001
b) Formula (II)
Figure imgf000021_0002
(ID
c) Formula (II
Figure imgf000022_0001
:ιi'
In each of the formulae (I), (II) and (II') R is a hydrogen atom or an alkyl group containing one to four carbon atoms;
X is a fluorine, chlorine or bromine atom; A and A' are different and each is independently a phenyl or naphthyl group, which may be unsubstituted or substituted by one or more groups selected from, alkyl C _4 alkoxyl C]__ or -S02Q where Q is
—OH —CH=CH2, —C2H4OSO3H or —C2H4C1 r
2. A dyestuff mixture according to claim 1, wherein each X is a chlorine atom.
3. A dyestuff mixture according to claim 1, wherein A and A' are independently selected from either (i) a substituted phenyl sulphonic acid of the following structure,
Figure imgf000022_0002
or (ii) a substituted naphthyl sulphonic acid of the following formula,
Figure imgf000023_0001
wherein Z is H, -SO2Q, Cl-4 alkyl, C _4 alkoxyl or , -SO2Q where Q is —OH —CH=CH2 , —C2H4OSO3H or —C2H4C1.
4. A dyestuff mixtures according claim to 1, wherein A is the following substituted phenyl sulphonic acid,
Figure imgf000023_0002
wherein Z is H, C _ alkyl, Cχ_4 alkoxyl or -SO2Q where Q is
—OH —CH=CH2, —C2H4OSO3H or —C2H4C1 ; and A' is the following substituted naphthyl sulphonic acid,
Figure imgf000023_0003
wherein Z is H, Cχ_4 alkyl, C _4 alkoxyl or -SO2Q where Q is -OH -CH=CH , -C2H4OSO3H, or -C2H4CI.
5. A dyestuff mixture according to claim 1, comprising three components, represented by the formulae (I-l), (II-l) and (II-2) which are present in the ratios shown,
Figure imgf000024_0001
(i-i)
(I-l) is present in an amount representing 1% to 85% by weight of the total dye present,
Figure imgf000024_0002
( i i-i )
(II-l) is present in an amount representing 1% to 85% by weight,
Figure imgf000024_0003
(II-2) (II-2) is present in 1% to 85% by weight.
6. A dyestuff mixture according to claim 1, comprising three components represented by the formulae (1-2), (II-3)
T) and (II-4)
Figure imgf000025_0001
1-2: present in 1% to 85% by weight;
Figure imgf000025_0002
(II-3) present in 1% to 85% by weight; and
Figure imgf000025_0003
(II-4) present in 1% to 85% by weight.
7. A dyestuff of formula (I)
Figure imgf000026_0001
:D wherein
R is a hydrogen atom or an alkyl group containing one to four carbon atoms;
X is a fluorine, chlorine or bromine atom; A and A1 are different and each is independently a phenyl or naphthyl group, which may be unsubstituted or substituted by one or more groups selected from, alkyl C]_-4 alkoxyl Cχ-,4 or -S02Q where Q is —OH —CH=CH2 , —C2H-4OSO3H or —C2H4C1.
8. A dyestuff according to claim 7 wherein each X is a chlorine atom.
9. A dyestuff according to claim 7, wherein A and A' are independently selected from either (i) a substituted phenyl sulphonic acid of the following structure,
Figure imgf000026_0002
or (ii) a substituted naphthyl sulphonic acid of the following formula,
Figure imgf000027_0001
wherein Z is H, -SO2Q , C1- alkyl , Cχ_4 alkoxyl or ,
-S02Q where Q is — OH CH=CH2 , — C2H4OSO3H or — C2H4C1 .
10 . A dyestuff according claim to 7 , wherein A is the following substituted phenyl sulphonic acid,
Figure imgf000027_0002
wherein Z is H, C]__4 alkyl, C]__4 alkoxyl or -SO2Q where Q is
—OH —CH=CH2, —C2H4OSO3H or —C2H4C1 ; and A' is the following substituted naphthyl sulphonic acid,
Figure imgf000027_0003
wherein Z is H, C]__ alkyl, Cχ_ alkoxyl or -SO2Q where Q is
-OH -CH=CH2, -C2H4OSO3H, or -C2H4CI.
11. A dyestuff of claim 7, wherein said formula (I) is the following structure (I-l).
Figure imgf000028_0001
12. A dyestuff according to claim 7, wherein the said formula (I) is a dyestuff of the formula (1-2) .
Figure imgf000028_0002
13. A process for preparing the mixture of claim 1 which comprises the following steps:
A) l-amino-8-hydroxynaphthyl-disulfonic acid is reacted with the following trihalogentriazine of formula (a) ,
Figure imgf000028_0003
wherein X is fluorine, chlorine or bromine atom, to get the following formula (b) intermediate,
Figure imgf000029_0001
(b) wherein X is defined as the above;
B) a mixture of the diazonium salts derived from A-NH2 and A'-NH2, wherein A and A' are defined as the above, are reacted with an intermediate represented by formula (b) to give a mixture solution containing compounds represented the following formulae (c) and (d) ;
Figure imgf000029_0002
(c)
Figure imgf000030_0001
(d) wherein X, A and A' are defined as the above; and
C) the above mixture, in solution, is reacted with 3,5- diaminobenzoic acid or methyl 3, 5-diaminobenzoate to give a solution containing dyes represented by the formula (I), (II] and (II' ) .
14. A process according to claim 13, wherein X is a chlorine atom.
15. A process according to claim 13, wherein A and A' are the following substituted phenyl sulphonic acid,
Figure imgf000030_0002
or the following substituted naphthyl sulphonic acid
Figure imgf000030_0003
wherein Z is H, -SO2Q, 1-4 alkyl or C _4 alkoxyl, Q is -OH
-CH=CH2, -C2H4OSO3H, or -C2H4CI.
16. A process according to claim 13 wherein A is the following substituted phenyl sulphonic acid,
Figure imgf000031_0001
wherein Z is H, -SO2Q, C _ alkyl or C _4 alkoxyl, Q is -OH
-CH=CH2, -C2H4OSO3H, or -C2H4CI; and A' is the following substituted naphthyl sulphonic acid,
Figure imgf000031_0002
wherein Z is defined as the above,
17. A process for the coloration of cellulosic and amide containing fabrics and fibres, or blends of these with other fibres, which comprises reacting the said fabric or fibre with the red reactive dye mixture as claimed in claim 1 in the presence of heat and alkali.
PCT/US2000/006434 1999-05-05 2000-03-29 Mixtures of symmetrical and unsymmetrical red reactive dyes WO2000068319A1 (en)

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WO2012025279A1 (en) * 2010-08-25 2012-03-01 Huntsman Advanced Materials (Switzerland) Gmbh Mixtures of fibre-reactive dyes and their use in a method for trichromatic dyeing or printing

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EP2464694B1 (en) * 2009-08-14 2014-03-05 Huntsman Advanced Materials (Switzerland) GmbH Fibre-reactive azo dyes, their preparation and their use
CN107501998A (en) * 2017-09-25 2017-12-22 无锡润新染料有限公司 A kind of double chromogen reactive printing reds and preparation method thereof
CN112679981B (en) * 2020-12-21 2021-12-14 江苏德美科化工有限公司 High-temperature high-chlorine-resistance active red dye for cotton and preparation method thereof

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WO2004085545A1 (en) * 2003-03-27 2004-10-07 Ciba Specialty Chemicals Holding Inc. Fibre-reactive azo dyes, their preparation and their use
WO2012025279A1 (en) * 2010-08-25 2012-03-01 Huntsman Advanced Materials (Switzerland) Gmbh Mixtures of fibre-reactive dyes and their use in a method for trichromatic dyeing or printing
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