CA2255485C - Aqueous dye solutions and their use - Google Patents
Aqueous dye solutions and their use Download PDFInfo
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- CA2255485C CA2255485C CA002255485A CA2255485A CA2255485C CA 2255485 C CA2255485 C CA 2255485C CA 002255485 A CA002255485 A CA 002255485A CA 2255485 A CA2255485 A CA 2255485A CA 2255485 C CA2255485 C CA 2255485C
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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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
- C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
- C09B1/32—Dyes with amino groups substituted by hydrocarbon radicals substituted by aryl groups
- C09B1/34—Dyes with amino groups substituted by hydrocarbon radicals substituted by aryl groups sulfonated
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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
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
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Abstract
Concentrated aqueous dye solutions, which comprise 5 to 50 % by weight of at least one dye of formula (1) wherein X and Y are each independently of the other hydrogen or C1-C4alkyl or C1- C4alkoxy, and Z is C2-C6alkanoylamino or C2-C4hydroxyalkylsulfamoyl, M+ is the ammonium cation ~ ~of an amine of formula
Description
Agueous dye solutions and their use The present invention relates to concentrated aqueous solutions of blue-dyeing anthraqui-none dyes, to a process for their preparation and to their use for dyeing or printing hydroxyl group-containing or nitrogen-containing fibre material.
Dye solutions have a number of advantages over solid commercial forms, such as powder or granules, including for example no formation of dust when the dye liquors or printing pastes are prepared, no wetting problems caused by formation of lumps, no mottled dyeings owing to insufficiently dissolved dye particles. Not least because of these advantages, combined with the good meterability of the liquid commercial form, liquid formulations are now in-creasingly available on the market, the trend moving towards ever more concentrated solu-tions as they allow substantial savings in transport and storage costs.
However, the storability of dye solutions in general and in concentrated preparations in parti-cular is frequently problematical. The more concentrated a dye solution, the more readily do recrystallisations occur during storage, and more or less large agglomerates form which, for example when such preparations are used in textile printing, are extremely marring in the form of specks, or which plug or contaminate e.g. pipelines, pumps or valves of the trans-port, metering or dyeing appliances used. In addition, a solid sediment often forms which can be stirred up only with difficulty. In such cases it is often impossible to dissolve the dye again.
Accordingly, this invention has for its object to provide concentrated aqueous solutions of blue-dyeing anthraquinone dyes where the above problems can largely be avoided.
This invention therefore relates to concentrated aqueous dye solutions, which comprise 5 to 50 % by weight, based on the total weight of the solution, of at least one dye of formula (1) SO3 M+
X
(1), O NH Y
Z
wherein X and Y are each independently of the other hydrogen or C,-C4alkyl or C,-C4alkoxy, and Z is C2-C6alkanoylamino or C2-C4hydroxyalkylsulfamoyl, R' M+ is the ammonium cation H-N\ R2 of an amine of formula Ri I -R2 (2), wherein R, and R2 are each independently of the other hydrogen, C,-Csalkyl, or hydroxy-or amino-substituted C2-C6alkyl which may be interrupted by an oxygen atom, and R3 is hydroxy- or amino-substituted C2-C6alkyl which may be interrupted by an oxygen atom, with the proviso that R,, R2 and R3 are not a radical of formula -CH2-CH(OH)-CH3 if X and Y are methyl and Z is 2-hydroxyethylsulfamoyl or if X and Y are hydrogen and Z is propionylamino.
X and Y defined as C,-C4alkyl are suitably each independently of the other e.g. methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl or isobutyl, in particular methyl or ethyl and, pre-ferably, methyl.
X and Y defined as C,-C4alkoxy are suitably each independently of the other e.g. methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy, in particular methoxy or ethoxy and, pre-ferably, methoxy.
Dye solutions have a number of advantages over solid commercial forms, such as powder or granules, including for example no formation of dust when the dye liquors or printing pastes are prepared, no wetting problems caused by formation of lumps, no mottled dyeings owing to insufficiently dissolved dye particles. Not least because of these advantages, combined with the good meterability of the liquid commercial form, liquid formulations are now in-creasingly available on the market, the trend moving towards ever more concentrated solu-tions as they allow substantial savings in transport and storage costs.
However, the storability of dye solutions in general and in concentrated preparations in parti-cular is frequently problematical. The more concentrated a dye solution, the more readily do recrystallisations occur during storage, and more or less large agglomerates form which, for example when such preparations are used in textile printing, are extremely marring in the form of specks, or which plug or contaminate e.g. pipelines, pumps or valves of the trans-port, metering or dyeing appliances used. In addition, a solid sediment often forms which can be stirred up only with difficulty. In such cases it is often impossible to dissolve the dye again.
Accordingly, this invention has for its object to provide concentrated aqueous solutions of blue-dyeing anthraquinone dyes where the above problems can largely be avoided.
This invention therefore relates to concentrated aqueous dye solutions, which comprise 5 to 50 % by weight, based on the total weight of the solution, of at least one dye of formula (1) SO3 M+
X
(1), O NH Y
Z
wherein X and Y are each independently of the other hydrogen or C,-C4alkyl or C,-C4alkoxy, and Z is C2-C6alkanoylamino or C2-C4hydroxyalkylsulfamoyl, R' M+ is the ammonium cation H-N\ R2 of an amine of formula Ri I -R2 (2), wherein R, and R2 are each independently of the other hydrogen, C,-Csalkyl, or hydroxy-or amino-substituted C2-C6alkyl which may be interrupted by an oxygen atom, and R3 is hydroxy- or amino-substituted C2-C6alkyl which may be interrupted by an oxygen atom, with the proviso that R,, R2 and R3 are not a radical of formula -CH2-CH(OH)-CH3 if X and Y are methyl and Z is 2-hydroxyethylsulfamoyl or if X and Y are hydrogen and Z is propionylamino.
X and Y defined as C,-C4alkyl are suitably each independently of the other e.g. methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl or isobutyl, in particular methyl or ethyl and, pre-ferably, methyl.
X and Y defined as C,-C4alkoxy are suitably each independently of the other e.g. methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy, in particular methoxy or ethoxy and, pre-ferably, methoxy.
Z defined as C2-C6alkanoylamino is typically acetylamino, propionylamino, butyrylamino, pentanoylamino or hexanoylamino and, preferably, C2-C4alkanoylamino, such as acetylami-no, propionylamino or butyrylamino and, in particular, acetyiamino or propionylamino.
Z defined as C2-C4hydroxyalkylsulfamoyl is typically 2-hydroxyethyisulfamoyl, 2- or 3-hydro-xypropylsulfamoyl or 2-, 3-, or 4-hydroxybutylsulfamoyl and, preferably, 2-hydroxyethylsul-famoyl.
R, and R2 defined as C,-C6alkyl are suitably each independently of the other typically methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl or hexyl and, preferably, C,-C4alkyl, such as methyl or ethyl.
R,, R2 and R3 defined as hydroxy- or amino-substituted C2-C6alkyl which may be interrupted by an oxygen atom are suitably each independently of one another typically radicals of formulae -CH2CH2OH, -CH2-CH(OH)-CH3, -CH2CH2NH2, -(CH2)2-0-(CH2)2-OH, -(CH2)2-O-CH2-CH2-OH or -(CH2)2-O-CH2-CH(CH3)-OH and, preferably, -CH2CH2OH, -CH2-CH(OH)-CH3 or -(CH2)2-O-CH2-CH(CH3)-OH.
-3a-According to another aspect of the present invention, there is provided a concentrated aqueous dye solution, which comprises 5 to 50 % by weight, based on the total weight of the solution, of at least one dye of formula (1) S03 M+
\ ( I / X
(1), O NH Y
Z
wherein X and Y are each independently of the other hydrogen or C1-C4alkyl or C1-C4alkoxy, and Z is C2-C6alkanoylamino or C2-C4hydroxyalkylsulfamoyl, M+ is the ammonium cation +/Rl H-N-R2 of an amine of formula N-R2 (2), wherein Rl, R2 and R3 are a radical of formula -(CH2) 2-0-CHZ-CH (CH3) -OH
or of formula - (CH2) Z-O-CH (CH3) -CH2-OH.
-3b-The novel concentrated aqueous dye solutions can comprise other additives, for example urea, caprolactam, N-methylpyrrolidone or polyethylene glycol.
In a preferred embodiment of this invention, the novel dye solutions comprise caprolactam or N-methylpyrrolidone, preferably caprolactam.
In the novel dye solutions, the cited additives are present in amounts from 0.01 to 30 % by weight, preferably from 0.1 to 20 % by weight and, more preferably, from 1 to 20 % by weight, based on the total weight of the dye solution.
The novel concentrated aqueous solutions may furthermore comprise fungistatic and/or bacteriostatic substances.
Preferred dye solutions are those, wherein X and Y are each independently of the other hydrogen or methyl, and Z is C2-C4alkanoylamino or C2-C4hydroxyalkylsulfamoyl and, pre-ferably, acetylamino, propionyiamino or 2-hydroxyethylsulfamoyl.
Z defined as C2-C4hydroxyalkylsulfamoyl is typically 2-hydroxyethyisulfamoyl, 2- or 3-hydro-xypropylsulfamoyl or 2-, 3-, or 4-hydroxybutylsulfamoyl and, preferably, 2-hydroxyethylsul-famoyl.
R, and R2 defined as C,-C6alkyl are suitably each independently of the other typically methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl or hexyl and, preferably, C,-C4alkyl, such as methyl or ethyl.
R,, R2 and R3 defined as hydroxy- or amino-substituted C2-C6alkyl which may be interrupted by an oxygen atom are suitably each independently of one another typically radicals of formulae -CH2CH2OH, -CH2-CH(OH)-CH3, -CH2CH2NH2, -(CH2)2-0-(CH2)2-OH, -(CH2)2-O-CH2-CH2-OH or -(CH2)2-O-CH2-CH(CH3)-OH and, preferably, -CH2CH2OH, -CH2-CH(OH)-CH3 or -(CH2)2-O-CH2-CH(CH3)-OH.
-3a-According to another aspect of the present invention, there is provided a concentrated aqueous dye solution, which comprises 5 to 50 % by weight, based on the total weight of the solution, of at least one dye of formula (1) S03 M+
\ ( I / X
(1), O NH Y
Z
wherein X and Y are each independently of the other hydrogen or C1-C4alkyl or C1-C4alkoxy, and Z is C2-C6alkanoylamino or C2-C4hydroxyalkylsulfamoyl, M+ is the ammonium cation +/Rl H-N-R2 of an amine of formula N-R2 (2), wherein Rl, R2 and R3 are a radical of formula -(CH2) 2-0-CHZ-CH (CH3) -OH
or of formula - (CH2) Z-O-CH (CH3) -CH2-OH.
-3b-The novel concentrated aqueous dye solutions can comprise other additives, for example urea, caprolactam, N-methylpyrrolidone or polyethylene glycol.
In a preferred embodiment of this invention, the novel dye solutions comprise caprolactam or N-methylpyrrolidone, preferably caprolactam.
In the novel dye solutions, the cited additives are present in amounts from 0.01 to 30 % by weight, preferably from 0.1 to 20 % by weight and, more preferably, from 1 to 20 % by weight, based on the total weight of the dye solution.
The novel concentrated aqueous solutions may furthermore comprise fungistatic and/or bacteriostatic substances.
Preferred dye solutions are those, wherein X and Y are each independently of the other hydrogen or methyl, and Z is C2-C4alkanoylamino or C2-C4hydroxyalkylsulfamoyl and, pre-ferably, acetylamino, propionyiamino or 2-hydroxyethylsulfamoyl.
In a preferred embodiment of the novel dye solutions, R, is hydrogen, methyl, ethyl, hydroxy-substituted C2-C3alkyl or a radical of formula -(CH2)2-O-CH2-CHR-OH, wherein R is hydrogen or methyl.
In a particularly preferred embodiment of the novel dye solutions, R, is hydroxy-substituted C2-C3alkyl or a radical of formula -(CH2)2-O-CH2-CHR-OH, wherein R is hydrogen or methyl, preferably methyl.
In a very particularly preferred embodiment of the novel dye solutions, R, is hydroxy-substi-tuted propyl, in particular a radical of formula -CH2-CH(OH)-CH3.
R2 is preferably hydrogen, methyl, ethyl, hydroxy-substituted C2-C3alkyl or a radical of formu-la -(CH2)2-O-CH2-CHR-OH, wherein R is hydrogen or methyl.
R2 is particularly preferably hydroxy-substituted C2-C3alkyl or a radical of formula -(CH2)2-O-CH2-CHR-OH, wherein R is hydrogen or methyl, preferably methyl.
R2 is very particularly preferably hydroxy-substituted propyl, in particular a radical of formula -CH2-CH(OH)-CH3.
R3 is preferably hydroxy-substituted C2-C3alkyl or a radical of formula -(CH2)2-O-CH2-CHR-OH, wherein R is hydrogen or methyl, preferably methyl.
R3 is particularly preferably hydroxy-substituted propyl, in particular a radical of formula -CH2-CH(OH)-CH3.
Preferred dye solutions are those, wherein R2 and R3 are each independently of the other hydroxy-substituted C2-C3alkyl or a radical of formula -(CH2)2-O-CH2-CHR-OH, wherein R is hydrogen or methyl, preferably methyl.
R,, R2 and R3 defined as a hydroxy-substituted C2-C3alkyl radical are preferably 2-hydroxy-ethyl or a radical of formula -CH2-CH(OH)-CH3.
In a particularly preferred embodiment of the novel dye solutions, R, is hydroxy-substituted C2-C3alkyl or a radical of formula -(CH2)2-O-CH2-CHR-OH, wherein R is hydrogen or methyl, preferably methyl.
In a very particularly preferred embodiment of the novel dye solutions, R, is hydroxy-substi-tuted propyl, in particular a radical of formula -CH2-CH(OH)-CH3.
R2 is preferably hydrogen, methyl, ethyl, hydroxy-substituted C2-C3alkyl or a radical of formu-la -(CH2)2-O-CH2-CHR-OH, wherein R is hydrogen or methyl.
R2 is particularly preferably hydroxy-substituted C2-C3alkyl or a radical of formula -(CH2)2-O-CH2-CHR-OH, wherein R is hydrogen or methyl, preferably methyl.
R2 is very particularly preferably hydroxy-substituted propyl, in particular a radical of formula -CH2-CH(OH)-CH3.
R3 is preferably hydroxy-substituted C2-C3alkyl or a radical of formula -(CH2)2-O-CH2-CHR-OH, wherein R is hydrogen or methyl, preferably methyl.
R3 is particularly preferably hydroxy-substituted propyl, in particular a radical of formula -CH2-CH(OH)-CH3.
Preferred dye solutions are those, wherein R2 and R3 are each independently of the other hydroxy-substituted C2-C3alkyl or a radical of formula -(CH2)2-O-CH2-CHR-OH, wherein R is hydrogen or methyl, preferably methyl.
R,, R2 and R3 defined as a hydroxy-substituted C2-C3alkyl radical are preferably 2-hydroxy-ethyl or a radical of formula -CH2-CH(OH)-CH3.
In a preferred embodiment of the novel dye solutions, R,, R2 and R3 are each independently of one another hydroxy-substituted C2-C3alkyl, preferably 2-hydroxyethyl or a radical of for-mula -CH2-CH(OH)-CH3 or a radical of formula -(CH2)2-O-CH2-CH(CH3)-OH.
In a very particularly preferred embodiment of the novel dye solutions, R,, R2 and R3 are a radical of formula -CH2-CH(OH)-CH.
The novel dye solutions preferably comprise 10 to 50 % by weight and, more preferably, 20 to 50 % by weight, of at least one dye of formula (1), based on the total weight of the solution.
Preferred dye solutions are those, which comprise two dyes of formula (1).
The novel dye solutions particularly preferably comprise two dyes of formula (3), (4) or (5) S03 M+ S03 M+
(3), (4) Iq SO3 M ' or CH
S02 NH-(CH2)2 OH
wherein M+ has the meanings and preferred meanings defined above.
Thus, the novel dye solutions comprise, for example, (i) a dye of formula (3) and a dye of formula (5), (ii) a dye of formula (4) and a dye of formula (5), or (iii) a dye of formula (3) and a dye of formula (4).
Very particularly preferred dye solutions according to (i) or (ii) are those which, based on the total amount of the dyes of formulae (3) and (5) or of formulae (4) and (5), comprise at least % by weight, preferably at least 10 % by weight and, more preferably, at least 15 % by weight, of a dye of formula (5).
Other very particularly preferred dye solutions according to (iii) are those which, based on the total amount of the dyes of formulae (3) and (4), comprise at least 5 % by weight, prefer-ably at least 10 % by weight and, more preferably, at least 20 % by weight, of a dye of for-mula (3).
This invention also relates to a process for the preparation of the novel dye solutions, which comprises dissolving at least one dye of formula (1), wherein M+ is a hydrogen ion, together with an amine of formula (2) in water, or dissolving at least one dye of formula (1), wherein M+ is the ammonium cation H-N-RRZ of an amine of formula (2), in water, X, Y, Z, R,, R2 and R3 each independently of one another having the above meanings.
The dyes of formula (1), wherein M+ is a hydrogen ion, are known or can be prepared in analogy to known processes in a manner known per se.
The preparation is conveniently carried out by slurrying the free acids of the anthraquinone dyes of formula (1), wherein M+ is a hydrogen ion, in dry or moist form, for example in the form of the filter press cake obtained after synthesis, in water and then neutralising this slurry e.g. with an aqueous solution of the amine of formula (2) at a pH of e.g. 6 to 8, prefer-ably of 6.5 to 7.5, at room temperature or at slightly elevated temperature, for example at 35 to 50 C, until a homogeneous solution forms. The preparation can, of course, also be carried out at a higher temperature. If required, the dye solution so obtained is clarified by filtration.
If appropriate, the water used for slurrying the dyes or, if an aqueous solution of the amine is used, the aqueous solution of the amine, may already comprise the above additives, expe-diently whenever the cited additives are in solid form at room temperature.
The cited addi-tives can also be added in the desired amounts after the dye acids have been slurried or neutralised. If the cited additives are in solid form at room temperature, they are convenientiy dissolved in the required amount of water prior to addition.
The amount of the cited additives can vary within wide limits and depends on the solubility of the dye, on the amount of dye to be dissolved and on the structure of the amine used.
The novel dye solutions comprising two dyes of of formula (1) are obtained, for example, by mixing first (i) the two dye acids in the desired mixture ratio, or (ii) by preparing a mixture of the two dye acids by reacting 1 -amino-4-bromo-anthraquinone-2-sulfonic acid with two aromatic amines of formula (6) X
H2N O Y (6), Z
wherein X, Y and Z have the meanings given above, and then processing the dry dye mixture accord-ing to (i) or the moist filter cake according to (ii), using the process described above.
In another of its aspects, this invention relates to dyes of formula (1), wherein X, Y, Z, R,, R2 and R3 have the meanings and preferred meanings given above, with the proviso that R,, R2 and R3 are not a radical of formula -CH2-CH(OH)-CH3 if X and Y are methyl and Z is 2-hyd-roxyethylsulfamoyl or if X and Y are hydrogen and Z is propionylamino.
Dyes of formula (1) can be obtained, for example, by reacting 1 -amino-4-bromo-anthraqui-none-2-sulfonic acid with an aromatic amine of formula (6) and then with an amine of formu-la (2). The first reaction is preferably carried out in aqueous solution at a temperature in the range from, for example, 50 to 100 C, preferably from 65 to 85 C, in the presence of e.g.
copper chloride or copper sulfate. The reaction with an amine of formula (2) is carried out, for example, by neutralising an aqueous dye solution with the corresponding amine.
The novel dyes and the novel dye solutions comprising said dyes can be used in the custo-mary dyeing and printing processes. Besides water and the dyes, the dye liquors or printing pastes can contain further additives, for example wetting agents, antifoams, levelling agents or agents affecting the properties of the textile material, for example softeners, additives for flameproof finishing, or dirt-, water- and oil-repelling agents, water softeners and natural or synthetic thickeners, for example alginates and cellulose ethers.
The novel dyes and the novel dye solutions containing said dyes are also suitable for dyeing from short liquors, for example in continuous dyeing processes or in batchwise and continu-ous foam dyeing processes.
The novel dyes are distinguished in particular by good exhaustion behaviour, good solubility and good stability of the printing paste as well as by good compatibility.
The dye solutions of this invention have good storage stability. They are storage-stable for several months in the temperature range from, for example, -5 to +40 C and are substantial-ly insensitive to variations in temperature.
The novel dye solutions furthermore have good resistance to hard water and, for example during the preparation of the dyeing liquor, can be diluted with water in any ratio without the dissolved dyes precipitating.
Level dyeings having good allround fastness properties are obtained, in particular having good fastness to rubbing, wetting, wet-rubbing and light.
The novel dyes and the novel dye solutions comprising said dyes are suitable for dyeing or printing hydroxyl group-containing or nitrogen-containing fibre material. They are particularly suitable for dyeing or printing natural polyamide materials, such as wool or, in particular, syn-thetic polyamide materials, such as polyamide 6 or polyamide 6.6, or silk, and they are also suitable for dyeing or printing blended fabrics or blended yarns of wool and synthetic poly-amide.
The cited material, in particular textile material, can be in any form of presentation, for exam-ple in the form of fibre, yarn, wovens or knits and, in particular, in the form of carpets.
In a very particularly preferred embodiment of the novel dye solutions, R,, R2 and R3 are a radical of formula -CH2-CH(OH)-CH.
The novel dye solutions preferably comprise 10 to 50 % by weight and, more preferably, 20 to 50 % by weight, of at least one dye of formula (1), based on the total weight of the solution.
Preferred dye solutions are those, which comprise two dyes of formula (1).
The novel dye solutions particularly preferably comprise two dyes of formula (3), (4) or (5) S03 M+ S03 M+
(3), (4) Iq SO3 M ' or CH
S02 NH-(CH2)2 OH
wherein M+ has the meanings and preferred meanings defined above.
Thus, the novel dye solutions comprise, for example, (i) a dye of formula (3) and a dye of formula (5), (ii) a dye of formula (4) and a dye of formula (5), or (iii) a dye of formula (3) and a dye of formula (4).
Very particularly preferred dye solutions according to (i) or (ii) are those which, based on the total amount of the dyes of formulae (3) and (5) or of formulae (4) and (5), comprise at least % by weight, preferably at least 10 % by weight and, more preferably, at least 15 % by weight, of a dye of formula (5).
Other very particularly preferred dye solutions according to (iii) are those which, based on the total amount of the dyes of formulae (3) and (4), comprise at least 5 % by weight, prefer-ably at least 10 % by weight and, more preferably, at least 20 % by weight, of a dye of for-mula (3).
This invention also relates to a process for the preparation of the novel dye solutions, which comprises dissolving at least one dye of formula (1), wherein M+ is a hydrogen ion, together with an amine of formula (2) in water, or dissolving at least one dye of formula (1), wherein M+ is the ammonium cation H-N-RRZ of an amine of formula (2), in water, X, Y, Z, R,, R2 and R3 each independently of one another having the above meanings.
The dyes of formula (1), wherein M+ is a hydrogen ion, are known or can be prepared in analogy to known processes in a manner known per se.
The preparation is conveniently carried out by slurrying the free acids of the anthraquinone dyes of formula (1), wherein M+ is a hydrogen ion, in dry or moist form, for example in the form of the filter press cake obtained after synthesis, in water and then neutralising this slurry e.g. with an aqueous solution of the amine of formula (2) at a pH of e.g. 6 to 8, prefer-ably of 6.5 to 7.5, at room temperature or at slightly elevated temperature, for example at 35 to 50 C, until a homogeneous solution forms. The preparation can, of course, also be carried out at a higher temperature. If required, the dye solution so obtained is clarified by filtration.
If appropriate, the water used for slurrying the dyes or, if an aqueous solution of the amine is used, the aqueous solution of the amine, may already comprise the above additives, expe-diently whenever the cited additives are in solid form at room temperature.
The cited addi-tives can also be added in the desired amounts after the dye acids have been slurried or neutralised. If the cited additives are in solid form at room temperature, they are convenientiy dissolved in the required amount of water prior to addition.
The amount of the cited additives can vary within wide limits and depends on the solubility of the dye, on the amount of dye to be dissolved and on the structure of the amine used.
The novel dye solutions comprising two dyes of of formula (1) are obtained, for example, by mixing first (i) the two dye acids in the desired mixture ratio, or (ii) by preparing a mixture of the two dye acids by reacting 1 -amino-4-bromo-anthraquinone-2-sulfonic acid with two aromatic amines of formula (6) X
H2N O Y (6), Z
wherein X, Y and Z have the meanings given above, and then processing the dry dye mixture accord-ing to (i) or the moist filter cake according to (ii), using the process described above.
In another of its aspects, this invention relates to dyes of formula (1), wherein X, Y, Z, R,, R2 and R3 have the meanings and preferred meanings given above, with the proviso that R,, R2 and R3 are not a radical of formula -CH2-CH(OH)-CH3 if X and Y are methyl and Z is 2-hyd-roxyethylsulfamoyl or if X and Y are hydrogen and Z is propionylamino.
Dyes of formula (1) can be obtained, for example, by reacting 1 -amino-4-bromo-anthraqui-none-2-sulfonic acid with an aromatic amine of formula (6) and then with an amine of formu-la (2). The first reaction is preferably carried out in aqueous solution at a temperature in the range from, for example, 50 to 100 C, preferably from 65 to 85 C, in the presence of e.g.
copper chloride or copper sulfate. The reaction with an amine of formula (2) is carried out, for example, by neutralising an aqueous dye solution with the corresponding amine.
The novel dyes and the novel dye solutions comprising said dyes can be used in the custo-mary dyeing and printing processes. Besides water and the dyes, the dye liquors or printing pastes can contain further additives, for example wetting agents, antifoams, levelling agents or agents affecting the properties of the textile material, for example softeners, additives for flameproof finishing, or dirt-, water- and oil-repelling agents, water softeners and natural or synthetic thickeners, for example alginates and cellulose ethers.
The novel dyes and the novel dye solutions containing said dyes are also suitable for dyeing from short liquors, for example in continuous dyeing processes or in batchwise and continu-ous foam dyeing processes.
The novel dyes are distinguished in particular by good exhaustion behaviour, good solubility and good stability of the printing paste as well as by good compatibility.
The dye solutions of this invention have good storage stability. They are storage-stable for several months in the temperature range from, for example, -5 to +40 C and are substantial-ly insensitive to variations in temperature.
The novel dye solutions furthermore have good resistance to hard water and, for example during the preparation of the dyeing liquor, can be diluted with water in any ratio without the dissolved dyes precipitating.
Level dyeings having good allround fastness properties are obtained, in particular having good fastness to rubbing, wetting, wet-rubbing and light.
The novel dyes and the novel dye solutions comprising said dyes are suitable for dyeing or printing hydroxyl group-containing or nitrogen-containing fibre material. They are particularly suitable for dyeing or printing natural polyamide materials, such as wool or, in particular, syn-thetic polyamide materials, such as polyamide 6 or polyamide 6.6, or silk, and they are also suitable for dyeing or printing blended fabrics or blended yarns of wool and synthetic poly-amide.
The cited material, in particular textile material, can be in any form of presentation, for exam-ple in the form of fibre, yarn, wovens or knits and, in particular, in the form of carpets.
In the following Examples, parts are by weight and temperatures are given in degrees Celsius. The relationship between parts by weight and parts by volume is the same as that between the gramme and the cubic centimetre.
Example 1: A sulfonation flask is charged with 880 parts of water and then 382 parts of 1-amino-4-bromo-anthraquinone-2-sulfonic acid, 82 parts of 3-propionamidoaniline and 75 parts of 3-acetamidoaniline are added. After adding 201 parts of sodium hydrogencarbo-nate, the mixture is heated to 75 C. Stirring continuously, 1 part of copper and 1 part of copper chloride is added. The reaction is complete after about 6 hours. After adding 2180 parts of water and 345 parts of 32% HCL, the mixture is stirred for 30 minutes at 80 C
and the product obtained is collected by suction filtration and washed with a warm solution of 25 parts of HCI in 800 parts of water. This gives 780 parts of a still moist product which com-prises the dyes of formulae (101) and (102) I I
(101) and O NH
(102) in a weight ratio of 50:50. 28.5 parts of the moist product are slurried in 31.1 parts of de-mineralised water and the resulting paste is neutralised with 10.1 parts of triethanolamine at a pH of 7 to 7.2. Subsequently, 30.0 parts of c-caprolactam and 0.3 part of a commercially available bactericide are added and the dye solution is clarified by filtration. This liquid for-mulation has the following composition:
Example 1: A sulfonation flask is charged with 880 parts of water and then 382 parts of 1-amino-4-bromo-anthraquinone-2-sulfonic acid, 82 parts of 3-propionamidoaniline and 75 parts of 3-acetamidoaniline are added. After adding 201 parts of sodium hydrogencarbo-nate, the mixture is heated to 75 C. Stirring continuously, 1 part of copper and 1 part of copper chloride is added. The reaction is complete after about 6 hours. After adding 2180 parts of water and 345 parts of 32% HCL, the mixture is stirred for 30 minutes at 80 C
and the product obtained is collected by suction filtration and washed with a warm solution of 25 parts of HCI in 800 parts of water. This gives 780 parts of a still moist product which com-prises the dyes of formulae (101) and (102) I I
(101) and O NH
(102) in a weight ratio of 50:50. 28.5 parts of the moist product are slurried in 31.1 parts of de-mineralised water and the resulting paste is neutralised with 10.1 parts of triethanolamine at a pH of 7 to 7.2. Subsequently, 30.0 parts of c-caprolactam and 0.3 part of a commercially available bactericide are added and the dye solution is clarified by filtration. This liquid for-mulation has the following composition:
34.8 % by weight of a mixture of the dyes of formulae (3) and (4) in the form of the salts of triethanolamine, the weight ratio of the dyes being as indicated above, 30.0 % by weight of E-caprolactam, 0.3 % by weight of a commercially available bactericide, and 34.9 % by weight of water.
Example 2: The procedure of Example 1 is repeated, but replacing 82 parts of 3-propion-amidoaniline with 138 parts of 3-propionamidoaniline, and 75 parts of 3-acetamidoaniline with 51.2 parts of 5-amino-1,2-xylene-3-sulfo-2'-hydroxyethylamide, to give 840 parts of a still moist product which comprises the dyes of formulae (102) and (103) So3H
(103) S02 NH-(CH2)2 OH
in a weight ratio of 80:20. 34.0 parts of the moist product are slurried in 50.6 parts of de-mineralised water and the resulting paste is neutralised with 15.1 parts of aqueous triiso-propanolamine (66%) at a pH of 7 to 7.2. Subsequently, 0.3 part of a commercially available bactericide is added and the dye solution is clarified by filtration. This liquid formulation has the following composition:
37.7 % by weight of a mixture of the dyes of formulae (4) and (5) in the form of the salts of triisopropanolamine, the weight ratio of the dyes being as indicated above, 0.3 % by weight of a commercially available bactericide, and 62.0 % by weight of water.
Example 3: The procedure of Example 1 is repeated, but replacing 82 parts of 3-propion-amidoaniline with 43 parts of 3-propionamidoaniline, and 75 parts of 3-acetamidoaniline with 192 parts of 5-amino-1,2-xylene-3-sulfo-2'-hydroxyethylamide, to give 880 parts of a still moist product which comprises the dyes of formulae (102) and (103) in a weight ratio of 25:75. 35.0 parts of the moist product are then slurried in 25.0 parts of demineralised water and the resulting paste is neutralised with 15.0 parts of aqueous triisopropanolamine (66%) at a pH of 7 to 7.2. Subsequently, 20.0 parts of c-caprolactam and 0.3 part of a commercially available bactericide are added and the dye solution is clarified by filtration. This liquid for-mulation has the following composition:
25.1 % by weight of a mixture of the dyes of formulae (4) and (5) in the form of the salts of triisopropanolamine, wherein the weight ratio of the dyes is as indicated above, 20.0 % by weight of E-caprolactam, 0.3 % by weight of a commercially available bactericide, and 54.6 % by weight of water.
Example 4: The procedure of Example 1 is repeated, but replacing 82 parts of 3-propion-amidoaniline with 128 parts of 5-amino-1,2-xylene-3-sulfo-2'-hydroxyethylamide, to give 860 parts of a still moist product which comprises the dyes of formulae (101) and (103) in a weight ratio of 50:50. 39.1 parts of the moist product are slurried in 28.3 parts of deminera-lised water and the resulting paste is neutralised with 7.3 parts of triethanolamine at a pH of 7 to 7.2. Subsequently, 25.0 parts of E-caprolactam and 0.3 part of a commercially available bactericide are added and the dye solution is clarified by filtration. This liquid formulation has the following composition:
25.8 % by weight of a mixture of the dyes of formulae (3) and (5) in the form of the salts of triethanolamine, wherein the weight ratio of the dyes is as indicated above, 25.0 % by weight of E-caprolactam, 0.3 % by weight of a commercially available bactericide, and 48.9 % by weight of water.
Example 5: 37.0 parts of the moist product of the dyes of formulae (101) and (103) of Example 4 are slurried in 28.4 parts of demineralised water and the resulting paste is then neutralised with 14.3 parts of aqueous triisopropanolamine (66%) at a pH of 7 to 7.2.
20.0 parts of E-caprolactam and 0.3 part of a commercially available bactericide are then added and the dye solution is clarified by filtration. This liquid formulation has the following composition:
Example 2: The procedure of Example 1 is repeated, but replacing 82 parts of 3-propion-amidoaniline with 138 parts of 3-propionamidoaniline, and 75 parts of 3-acetamidoaniline with 51.2 parts of 5-amino-1,2-xylene-3-sulfo-2'-hydroxyethylamide, to give 840 parts of a still moist product which comprises the dyes of formulae (102) and (103) So3H
(103) S02 NH-(CH2)2 OH
in a weight ratio of 80:20. 34.0 parts of the moist product are slurried in 50.6 parts of de-mineralised water and the resulting paste is neutralised with 15.1 parts of aqueous triiso-propanolamine (66%) at a pH of 7 to 7.2. Subsequently, 0.3 part of a commercially available bactericide is added and the dye solution is clarified by filtration. This liquid formulation has the following composition:
37.7 % by weight of a mixture of the dyes of formulae (4) and (5) in the form of the salts of triisopropanolamine, the weight ratio of the dyes being as indicated above, 0.3 % by weight of a commercially available bactericide, and 62.0 % by weight of water.
Example 3: The procedure of Example 1 is repeated, but replacing 82 parts of 3-propion-amidoaniline with 43 parts of 3-propionamidoaniline, and 75 parts of 3-acetamidoaniline with 192 parts of 5-amino-1,2-xylene-3-sulfo-2'-hydroxyethylamide, to give 880 parts of a still moist product which comprises the dyes of formulae (102) and (103) in a weight ratio of 25:75. 35.0 parts of the moist product are then slurried in 25.0 parts of demineralised water and the resulting paste is neutralised with 15.0 parts of aqueous triisopropanolamine (66%) at a pH of 7 to 7.2. Subsequently, 20.0 parts of c-caprolactam and 0.3 part of a commercially available bactericide are added and the dye solution is clarified by filtration. This liquid for-mulation has the following composition:
25.1 % by weight of a mixture of the dyes of formulae (4) and (5) in the form of the salts of triisopropanolamine, wherein the weight ratio of the dyes is as indicated above, 20.0 % by weight of E-caprolactam, 0.3 % by weight of a commercially available bactericide, and 54.6 % by weight of water.
Example 4: The procedure of Example 1 is repeated, but replacing 82 parts of 3-propion-amidoaniline with 128 parts of 5-amino-1,2-xylene-3-sulfo-2'-hydroxyethylamide, to give 860 parts of a still moist product which comprises the dyes of formulae (101) and (103) in a weight ratio of 50:50. 39.1 parts of the moist product are slurried in 28.3 parts of deminera-lised water and the resulting paste is neutralised with 7.3 parts of triethanolamine at a pH of 7 to 7.2. Subsequently, 25.0 parts of E-caprolactam and 0.3 part of a commercially available bactericide are added and the dye solution is clarified by filtration. This liquid formulation has the following composition:
25.8 % by weight of a mixture of the dyes of formulae (3) and (5) in the form of the salts of triethanolamine, wherein the weight ratio of the dyes is as indicated above, 25.0 % by weight of E-caprolactam, 0.3 % by weight of a commercially available bactericide, and 48.9 % by weight of water.
Example 5: 37.0 parts of the moist product of the dyes of formulae (101) and (103) of Example 4 are slurried in 28.4 parts of demineralised water and the resulting paste is then neutralised with 14.3 parts of aqueous triisopropanolamine (66%) at a pH of 7 to 7.2.
20.0 parts of E-caprolactam and 0.3 part of a commercially available bactericide are then added and the dye solution is clarified by filtration. This liquid formulation has the following composition:
27.5 % by weight of a mixture of the dyes of formulae (3) and (5) in the form of the salts of triethanolamine, wherein the weight ratio of the dyes is as indicated above, 20.0 % by weight of E-caprolactam, 0.3 % by weight of a commercially available bactericide, and 52.2 % by weight of water.
The formulations obtained in accordance with Examples 1 to 5 are storage-stable in the tem-perature range from -5 to +40 C and dye polyamide fabric in a blue shade.
Replacing the triethanolamine of Examples 1 and 4 and the aqueous triisopropanolamine of Examples 2, 3 and 5 each by an equimolar amount of the amine of formula N-[(CH2)2-O-CH2-CH(CH3)-OH]3 and not adding the c-caprolactam used in Examples 1, 3, 4 and 5 also gives formulations which are storage-stable in the temperature range from -5 to +40 C and which dye polyamide fabric in a blue shade.
Example 6: A sulfonation flask is charged with 880 parts of water and then 382 parts of 1-amino-4-bromo-anthraquinone-2-sulfonic acid and 158 parts of 3-acetamidoaniline are added. After adding 200 parts of sodium hydrogencarbonate, the mixture is heated to 75 C.
Stirring continuously, 1 part of copper and 1 part of copper chloride are added. The reaction is complete after about 6 hours. Subsequently, 2180 parts of water and 345 parts of 32% HCL are added. The mixture is stirred for 30 minutes at 80 C and the product obtained is collected by suction filtration and washed with a warm solution of 25 parts of HCI in 800 parts of water. This gives 750 parts of a still moist product which comprises 36.5 % by weight of the dye of formula (101).
67.2 parts of the moist product are slurried in 4.2 parts of demineralised water and the resulting paste is then neutralised with 27.3 parts of the amine of formula N-[(CH2)2-O-CH(CH3)CH2-OH]3 at a pH of 7Ø Subsequently, 0.3 part of a commercially available bactericide ( Proxel GXL, of Zeneca) and 1 part of a commercially available penetration accelerator ( Albegal FFA, of Ciba Specialty Chemicals AG) are added and the dye solution is clarified by filtration. This liquid formulation has the following composition:
51.2 % by weight of the dye of formula (101) in the form of the salts of tris(hydroxyisopropo-xyethyl)amine, 0.3 % by weight of a commercially available bactericide, 1.0 % by weight of a commercially available penetration accelerator, and 47.5 % by weight of water.
The formulation obtained is storage-stable in the temperature range from -5 to +40 C and dyes polyamide fabric in a blue shade.
Dveing Example I
parts of polyamide 6.6 fabric are dyed in 500 parts of an aqueous liquor containing 2 g/I
of ammonium acetate and which is adjusted to pH 5 with acetic acid. The amount of the liquid formulation of Example 1 is 2 %, based on the weight of the fibre. The dyeing time is 30 to 90 minutes at 98 C. The dyed polyamide 6.6 fabric is then taken out of the liquor and washed and dried as usual.
Dyeing Example II
10 parts of polyamide 6.6 fabric are dyed in 500 parts of an aqueous liquor containing 1 g/I
of monosodium phosphate and which is adjusted to pH 6 with disodium phosphate.
The amount of the liquid formulation of Example 1 is 2 %, based on the weight of the fibre. The dyeing time is 30 to 90 minutes at 98 C. The dyed polyamide 6.6 fabric is then taken out of the liquor and washed and dried as usual.
Dyeing Examgle III
10 parts of woollen piece goods are dyed in 500 parts of an aqueous liquor.
The liquor con-tains 2 % of the liquid formulation according to Example 1, 5 % of calcined Glauber's salt and 2 % of 80% acetic acid, based on the weight of the fibre. The dyeing time ist 30 to 60 minutes at 98 C.
The formulations obtained in accordance with Examples 1 to 5 are storage-stable in the tem-perature range from -5 to +40 C and dye polyamide fabric in a blue shade.
Replacing the triethanolamine of Examples 1 and 4 and the aqueous triisopropanolamine of Examples 2, 3 and 5 each by an equimolar amount of the amine of formula N-[(CH2)2-O-CH2-CH(CH3)-OH]3 and not adding the c-caprolactam used in Examples 1, 3, 4 and 5 also gives formulations which are storage-stable in the temperature range from -5 to +40 C and which dye polyamide fabric in a blue shade.
Example 6: A sulfonation flask is charged with 880 parts of water and then 382 parts of 1-amino-4-bromo-anthraquinone-2-sulfonic acid and 158 parts of 3-acetamidoaniline are added. After adding 200 parts of sodium hydrogencarbonate, the mixture is heated to 75 C.
Stirring continuously, 1 part of copper and 1 part of copper chloride are added. The reaction is complete after about 6 hours. Subsequently, 2180 parts of water and 345 parts of 32% HCL are added. The mixture is stirred for 30 minutes at 80 C and the product obtained is collected by suction filtration and washed with a warm solution of 25 parts of HCI in 800 parts of water. This gives 750 parts of a still moist product which comprises 36.5 % by weight of the dye of formula (101).
67.2 parts of the moist product are slurried in 4.2 parts of demineralised water and the resulting paste is then neutralised with 27.3 parts of the amine of formula N-[(CH2)2-O-CH(CH3)CH2-OH]3 at a pH of 7Ø Subsequently, 0.3 part of a commercially available bactericide ( Proxel GXL, of Zeneca) and 1 part of a commercially available penetration accelerator ( Albegal FFA, of Ciba Specialty Chemicals AG) are added and the dye solution is clarified by filtration. This liquid formulation has the following composition:
51.2 % by weight of the dye of formula (101) in the form of the salts of tris(hydroxyisopropo-xyethyl)amine, 0.3 % by weight of a commercially available bactericide, 1.0 % by weight of a commercially available penetration accelerator, and 47.5 % by weight of water.
The formulation obtained is storage-stable in the temperature range from -5 to +40 C and dyes polyamide fabric in a blue shade.
Dveing Example I
parts of polyamide 6.6 fabric are dyed in 500 parts of an aqueous liquor containing 2 g/I
of ammonium acetate and which is adjusted to pH 5 with acetic acid. The amount of the liquid formulation of Example 1 is 2 %, based on the weight of the fibre. The dyeing time is 30 to 90 minutes at 98 C. The dyed polyamide 6.6 fabric is then taken out of the liquor and washed and dried as usual.
Dyeing Example II
10 parts of polyamide 6.6 fabric are dyed in 500 parts of an aqueous liquor containing 1 g/I
of monosodium phosphate and which is adjusted to pH 6 with disodium phosphate.
The amount of the liquid formulation of Example 1 is 2 %, based on the weight of the fibre. The dyeing time is 30 to 90 minutes at 98 C. The dyed polyamide 6.6 fabric is then taken out of the liquor and washed and dried as usual.
Dyeing Examgle III
10 parts of woollen piece goods are dyed in 500 parts of an aqueous liquor.
The liquor con-tains 2 % of the liquid formulation according to Example 1, 5 % of calcined Glauber's salt and 2 % of 80% acetic acid, based on the weight of the fibre. The dyeing time ist 30 to 60 minutes at 98 C.
Claims (10)
1. A concentrated aqueous dye solution, which comprises 5 to 50 % by weight, based on the total weight of the solution, of at least one dye of formula (1) wherein X and Y are each independently of the other hydrogen or C1-C4alkyl or C1-C4alkoxy, and Z is C2-C6alkanoylamino or C2-C4hydroxyalkylsulfamoyl, M+ is the ammonium cation of an amine of formula wherein R1, R2 and R3 are a radical of formula -(CH2)2-O-CH2-CH(CH3)-OH or of formula -(CH2)2-O-CH(CH3)-CH2-OH.
2. A dye solution according to claim 1, which comprises caprolactam or N-methylpyrrolido-ne.
3. A dye solution according to either claim 1 or claim 2, wherein X and Y are each indepen-dently of the other hydrogen or methyl, and Z is C2-C4alkanoylamino or C2-C4hydroxyalkylsul-famoyl.
4. A dye solution according to any one of claims 1 to 3, wherein X and Y are each indepen-dently of the other hydrogen or methyl, and Z is acetylamino, propionylamino or 2-hydroxy-ethylsulfamoyl.
5. A dye solution according to any one of claims 1 to 4, which comprises 10 to 50 % by weight of at least one dye of formula (1).
6. A dye solution according to any one of claims 1 to 5, which comprises two dyes of formula (1).
7. A dye solution according to any one of claims 1 to 6, which comprises two dyes of formula (3), (4) or (5) wherein M+ has the meaning defined in claim 1.
8. A process for the preparation of a dye solution according to any one of claims 1 to 7, which comprises dissolving at least one dye of formula (1), wherein M+ is a hydrogen ion, together with an amine of formula (2) in water, or dissolving at least one dye of formula (1), wherein M+ is the ammonium cation ~ ~of an amine of formula (2), in water, X, Y, Z, R1, R2 and R3 each independently of one another having the meanings defined in claim 1
9. Use of the dye solution according to any one of claims I to 7 for dyeing or printing hydro-xyl group-containing or nitrogen-containing fibre material.
10. Use according to claim 9 for dyeing or printing natural or synthetic polyamide fibre mate-rial.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP97810962 | 1997-12-10 | ||
| EP97810962.7 | 1997-12-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2255485A1 CA2255485A1 (en) | 1999-06-10 |
| CA2255485C true CA2255485C (en) | 2008-09-09 |
Family
ID=8230513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002255485A Expired - Fee Related CA2255485C (en) | 1997-12-10 | 1998-12-08 | Aqueous dye solutions and their use |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPH11256060A (en) |
| KR (1) | KR19990062913A (en) |
| CN (1) | CN1229109A (en) |
| CA (1) | CA2255485C (en) |
| DE (1) | DE59806999D1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1910474B1 (en) * | 2005-07-20 | 2010-04-14 | Clariant Finance (BVI) Limited | Acid dye composition of anthraquinone dyes |
| US20090016975A1 (en) * | 2007-07-12 | 2009-01-15 | Robert Bianchini | Fade-resistant coloring composition containing an acid dye and a cationic conditioning agent for a keratin-containing substrate |
| CN102604411B (en) * | 2012-01-19 | 2014-06-11 | 上海雅运纺织化工股份有限公司 | Synthesis and dyeing application of anthraquinone type blue acid dye compound |
-
1998
- 1998-12-01 DE DE59806999T patent/DE59806999D1/en not_active Expired - Lifetime
- 1998-12-08 CA CA002255485A patent/CA2255485C/en not_active Expired - Fee Related
- 1998-12-09 CN CN98127160A patent/CN1229109A/en active Pending
- 1998-12-09 KR KR1019980053845A patent/KR19990062913A/en not_active Application Discontinuation
- 1998-12-10 JP JP10350995A patent/JPH11256060A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN1229109A (en) | 1999-09-22 |
| KR19990062913A (en) | 1999-07-26 |
| CA2255485A1 (en) | 1999-06-10 |
| JPH11256060A (en) | 1999-09-21 |
| DE59806999D1 (en) | 2003-02-27 |
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