EP0442844B2 - Process for dyeing of wool with reactive dyes - Google Patents
Process for dyeing of wool with reactive dyes Download PDFInfo
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- EP0442844B2 EP0442844B2 EP91810078A EP91810078A EP0442844B2 EP 0442844 B2 EP0442844 B2 EP 0442844B2 EP 91810078 A EP91810078 A EP 91810078A EP 91810078 A EP91810078 A EP 91810078A EP 0442844 B2 EP0442844 B2 EP 0442844B2
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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
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/14—Wool
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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
- D06P1/00—General 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
- D06P1/44—General 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 insoluble pigments or auxiliary substances, e.g. binders
- D06P1/60—General 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 insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
- D06P1/607—Nitrogen-containing polyethers or their quaternary derivatives
- D06P1/6076—Nitrogen-containing polyethers or their quaternary derivatives addition products of amines and alkylene oxides or oxiranes
-
- 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
- D06P3/14—Wool
- D06P3/148—Wool using reactive dyes
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- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
- Y10S516/07—Organic amine, amide, or n-base containing
-
- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/916—Natural fiber dyeing
- Y10S8/917—Wool or silk
Definitions
- the present invention relates to a new method for fiber and flat level dyeing of wool with reactive dyes, the material dyed according to the new process and a means of carrying out the Procedure.
- the present method is particularly suitable for producing light to medium shades.
- auxiliary mixture as component (c) can be a nonionic compound of the formula wherein R "is an alkyl or alkenyl radical having 12 to 22 carbon atoms and x and y are integers, the sum of x and y being 80 to 140.
- auxiliary mixtures which, as component (a), are a compound of the formula (3a) and as component (b) a compound of the formula (4b) or auxiliary mixtures which, as component (a) contain a compound of formula (3b) and as component (b) a compound of formula (4a).
- M in the formulas (1), (3) and (4) denotes hydrogen, alkali metal, such as sodium, potassium and in particular ammonium.
- the residues Q. Q ', Q 1 and Q' 1 and A ⁇ , A ' ⁇ , A 1 ⁇ and A 2 ⁇ in formulas (1) and (3) are derived from quaternizing agents , QC 1 to C 4 -Alkyl, -CH 2 -CO-NH 2 . or is.
- quaternizing agents are e.g. Acetyl bromide, ethyl bromide, ethylene chlorohydrin, Ethylene bromohydrin, epichlorohydrin, epibromohydrin, dimethyl sulfate, diethyl sulfate and in particular Chloroacetamide into consideration.
- the aliphatic radicals R 1 , R 2 , R 3 , R 4 , R 5 and R 6 in the formulas (1), (3) and (4) are alkyl or alkenyl radicals having 12 to 24, preferably 16 to 22, carbon atoms Consideration.
- the following may be mentioned as examples: the n-dodecyl, myristyl, n-hexadecyl, n-heptadecyl, n-octadecyl, arachidyl, behenyl, dodecenyl, hexadecenyl, oleyl and octadecenyl radical.
- the compounds of components (a), (b) and (c) are e.g. (in part) from US-A-4,444,564 known.
- the compounds of component (a) according to formula (1a) are prepared by 2 to 15 moles of ethylene oxide to aliphatic amines, which is an aliphatic radical having 12 to 24 carbon atoms have accumulated and optionally the adduct in the acidic monoester and optionally the acidic monoester converted into the alkali or ammonium salts or the adduct one of the quaternizing agents mentioned above.
- the compounds of component (b) accordingly Formula (1b) are prepared by adding 25 to 200 moles of ethylene oxide to aliphatic amines which have an aliphatic radical having 12 to 24 carbon atoms, attached and optionally that Addition product in the acidic ester and optionally the acidic ester in the alkali or ammonium salts transferred or the adduct with one of the ouating agents mentioned above implements.
- the compounds of formula (2) are prepared by adding 80 to 140 moles of ethylene oxide to a compound of formula where R "has the meaning given under formula (2).
- the amines which are required as starting materials for the preparation of the compounds of the formulas (1), (3) and (4) can have saturated or unsaturated, branched or unbranched hydrocarbon radicals having 12 to 24, preferably 16 to 22, carbon atoms.
- the amines can be chemically uniform or in the form of mixtures.
- the amine mixtures used are preferably those which arise when natural fats or oils, such as tallow fat, soybean or coconut oil, are converted into the corresponding amines.
- Dodecylamine, hexadecylamine, octadecylamine, arachidylamine, behenylamine and octadecenylamine may be mentioned as amines.
- Tallow fatty amine is a mixture of approx. 30% hexadecylamine, 25% octadecylamine and 45% octadecenylamine.
- Both the ethylene oxide addition and the esterification can be carried out according to methods known per se be performed.
- sulfuric acid or its functional derivatives such as e.g. Chlorosulfonic acid and especially sulfamic acid are used.
- the esterification is usually carried out by simply mixing the reactants with heating, expediently carried out at a temperature between 50 and 100 ° C.
- the free acids can then be converted into the alkali metal or ammonium salts by the usual way Bases such as Ammonia, sodium or potassium hydroxide can be added.
- an auxiliary mixture which 10 to 80 parts, preferably 20 to 70 parts of component (a), 5 to 70 parts, preferably 5 to 50 Parts of component (b) and 0 to 70, preferably 0 to 50 parts of the compound of component (c) and contains ad 100 parts of water.
- auxiliary mixture consists of components (a), (b) and optionally (c) is added to the dyebath, range between 0.5 and 4 percent by weight, based on the fiber material to be dyed. Preferably 1 to 2 percent by weight of the Auxiliary mixture, based on the fiber material.
- the weight ratio of components (a) and (b) is between 1: 5 and 10: 1, preferably between 1: 2 and 5: 1.
- Wool can be considered as the fiber material that can be dyed according to the invention.
- the fiber material can be in various forms. Examples include: Flake, sliver, yarn, fabric, knitwear or carpets.
- the wool can be normal or felt-free be equipped.
- This class of dyes is referred to in the Color Index 3rd edition 1971 as "reactive dyes”. It deals mainly dyes that contain at least one with polyhydroxy fibers (cellulose fibers) or polyamide fibers, especially wool, reactive group, a precursor for this or one with Contain polyhydroxyl fibers or polyamide fibers reactive substituents.
- Suitable bases for the reactive dyes are, in particular, those from the series of mono-, dis- or Polyazo dyes including the formazan dyes and the anthraquinone, xanthene, nitro, Triphenylmethane, naphthoquinoneimine, dioxazine and phthalocyanine dyes.
- being the azo and phthalo cyanine dyes can be both metal-free and metal-containing.
- reactive groups and precursors which form such reactive groups are Epoxy groups, the ethylene imide group, the vinyl grouping in vinyl sulfone or in acrylic acid residue and the ⁇ -sulfatoethylsulfone group, the ⁇ -chloroethylsuffone group or the ⁇ -dialkylaminoethylsulfone group called.
- the reactive substituents in reactive dyes are those which are easily removable and leave an electrophilic residue.
- substituents are 1 or 2 halogen atoms in an aliphatic one Acyl residue e.g. in the ⁇ -position or ⁇ - and ⁇ -position of a propionyl radical or in the ⁇ - and / or ⁇ -position of an acrylic acid residue. or 1 to 3 halogen atoms on the following ring system: pyridazine, Pyrimidine, pyridazone, triazine, quinoxaline or phthalazine.
- Dyes with two or more identical or different reactive groups can also be used be used.
- Preferred reactive dyes contain chloroacetyl, bromoacrylic or as reactive substituents Dibromopropionyl.
- the reactive dyes can be acidic, salt-forming substituents, e.g. Carboxylic acid groups, sulfuric acid and phosphonic acid ester groups, phosphonic acid groups or preferably sulfonic acid groups contain.
- Reactive dyes with at least one sulfonic acid group are preferred with an azo or anthraquinone base, which preferably has two to three sulfonic acid groups having.
- Mixtures of reactive dyes can also be used, with bichromatic or trichromatic dyeings can be generated.
- the coloring takes place after the pull-out procedure.
- the amount of dyes added to the dye liquor depends on the desired color strength. Generally, amounts are from 0.01 to 10 Percent by weight, preferably 0.01 to 2 percent by weight, based on the fiber material used, proven.
- the liquor ratio can be chosen within a wide range e.g. 1: 3 to 1: 100, preferably 1: 8 to 1:30.
- the dye baths can contain mineral acids, e.g. Sulfuric acid or phosphoric acid, organic acids, expediently aliphatic carboxylic acids such as formic acid, acetic acid, oxalic acid or citric acid and / or salts such as ammonium acetate, ammonium sulfate or sodium acetate.
- the acids serve especially the adjustment of the pH of the liquors used according to the invention, which is between 4 and 5 lies.
- the dye liquors can also contain other additives, e.g. Wool protection, dispersing and wetting agents and also contain defoamers.
- Special devices are not required in the method according to the invention. They can usual dyeing machines, such as, for example, open baths, worsted, stranded yarn or packers, Jigger, paddle, tree dyeing, circulation or jet dyeing or reel skids be used.
- dyeing machines such as, for example, open baths, worsted, stranded yarn or packers, Jigger, paddle, tree dyeing, circulation or jet dyeing or reel skids be used.
- the dyeing is advantageously carried out at a temperature in the range from 60 to 120 ° C., preferably 70 to 105 ° C.
- the dyeing time is within the usual range and is usually 20 to 120 minutes.
- the dyeing process can be followed by an alkaline after-treatment, e.g. With aqueous ammonia, alkali metal hydroxides, alkali metal carbonates. -hydrogen carbonates or hexamethylenetetraamine be connected.
- the pH of the dye baths containing alkali is expediently 7.5 to 9, preferably 8 to 8.5.
- the dyeing of the fiber material is expediently carried out in such a way that the material to be dyed with a aqueous liquor containing the acid, the auxiliary mixture of components (a) and (b) and, if appropriate contains component (c) and has a temperature of 30 to 60 ° C, briefly treated and the the same bath adds the reactive dye. Then you slowly increase the temperature to in one Color range from 80 to 100 ° C and for 20 to 90 minutes, preferably 30 to 60 minutes.
- the dyed material is then, if necessary, after the addition of alkalis, preferably sodium hydrogen carbonate or treated with sodium carbonate for 10 to 20 minutes at 70 to 90 ° C. In the end it will pulled out colored material and rinsed, acidified and dried as usual.
- Fiber and surface level dyeings are obtained in particular by the dyeing process according to the invention in light to medium shades with good light and wet fastness properties.
- the pH of the liquor is 4.5.
- the 12 mg of the dye of the formula 24 mg of the dye of the formula and 44 mg of the dye of the formula contains, the dyebath is kept at 40 ° for about 5 minutes and then heated to 60 ° at a rate of 1 ° / min and held at 60 ° for 20 minutes. The mixture is then heated to 98 ° at 1 ° / min and dyed for 30 minutes. After the liquor has cooled to 70 °, rinsing is carried out as usual. A fiber- and flat-level dyeing with good fastness properties is obtained.
- EXAMPLE 3 The procedure is as described in Example 1, with the difference that 0.2 g of the adduct of 34 mol of ethylene oxide and 1 mol of a C 20 -C 22 fatty amine is used instead of auxiliary B 2 . A fiber- and flat-level dyeing with good fastness properties is obtained.
- EXAMPLE 4 The procedure is as described in Example 1, with the difference that 0.2 g of the quaternized adduct of 34 mol of ethylene oxide and 1 mol of a C 20 -C 22 fatty amine is used instead of auxiliary B 2 . A fiber- and flat-level dyeing with good fastness properties is obtained.
- EXAMPLE 5 The procedure is as described in Example 1, with the difference that 0.2 g of the adduct of 30 mol of ethylene oxide and 1 mol of tallow fatty amine is used instead of B 2 . A fiber- and flat-level dyeing with good fastness properties is obtained.
- EXAMPLE 9 The procedure is as described in Example 2, with the difference that, instead of the dye mixture, 80 mg of the dye of the formula is used.
- Example 10 One proceeds as described in Example 9 with the difference. that instead of 80 mg of the dye of the formula (105), 80 mg of the dye of the formula starts.
- EXAMPLE 11 The procedure is as described in Example 9, with the difference that instead of 80 mg of the dye of the formula (105), 200 mg of the dye of the formula used.
- EXAMPLE 12 The procedure is as described in Example 9, with the difference that instead of 80 mg of the dye of the formula (105), 320 mg of the dye of the formula used.
- EXAMPLE 13 The procedure is as described in Example 9, with the difference that instead of 80 mg of the dye of the formula (105), 100 mg of the dye of the formula used.
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Description
Die vorliegende Erfindung betrifft ein neues Verfahren zum faser- und flächenegalen Färben von Wolle mit Reaktivfarbstoffen, das nach dem neuen Verfahren gefärbte Material und ein Mittel zur Ausführung des Verfahrens.The present invention relates to a new method for fiber and flat level dyeing of wool with reactive dyes, the material dyed according to the new process and a means of carrying out the Procedure.
Aus der US-A-4 444 564 ist es bekannt, Fasern aus natürlichen Polyamiden im faserschonenden pH-Bereich zu färben. Allerdings können mit diesem Verfahren mit Reaktivfarbstoffen nur dunkle Farbtöne zufriedenstellend hergestellt werden.From US-A-4 444 564 it is known to make fibers from natural polyamides in the fiber-protecting pH range to color. However, only dark shades can be used with this process using reactive dyes be produced satisfactorily.
Ueberraschenderweise wurde nun ein neues Verfahren gefunden, das es ermöglicht, auch Wolle mit Reaktivfarbstoffen im faserschonenden pH-Bereich faser- und flächenegal besonders in hellen bis mittleren Farbtönen herzustellen.Surprisingly, a new process has now been found that also allows wool to be used Reactive dyes in the pH-preserving pH range, regardless of fiber and area, especially in light to medium To produce shades.
Gegenstand der vorliegenden Erfindung ist somit ein Verfahren zum faser- und flächenegalen Färben
von Wolle mit Reaktivfarbstoffen in Gegenwart eines Hilfsmittelgemisches, das dadurch gekennzeichnet ist,
dass man zum Färben dieser Materialien eine wässrige Flotte verwendet, welche mindestens einen
Reaktivfarbstoff und ein Hilfsmittelgemisch enthaltend als Komponente (a) mindestens eine Verbindung der
Formel
und als Komponente (b) mindestens eine Verbindung der Formel
enthält, worin
Das vorliegende Verfahren eignet sich besonders zur Herstellung von hellen bis mittleren Farbtönen.The present method is particularly suitable for producing light to medium shades.
Bevorzugt sind Hilfsmittelgemisch-Komponenten der Formeln (1a) und (1b), bei denen die Summe (m1 + n1) 5 bis 12 und (p1 + q1) 25 bis 100 bedeuten.Auxiliary mixture components of the formulas (1a) and (1b) are preferred, in which the sum (m 1 + n 1 ) is 5 to 12 and (p 1 + q 1 ) is 25 to 100.
Zusätzlich kann das Hilfsmittelgemisch als Komponente (c) eine nichtionogene Verbindung der Formel worin R" einen Alkyl- oder Alkenylrest mit 12 bis 22 Kohlenstoffatomen und x und y ganze Zahlen bedeuten, wobei die Summe von x und y 80 bis 140 ist, enthalten.In addition, the auxiliary mixture as component (c) can be a nonionic compound of the formula wherein R "is an alkyl or alkenyl radical having 12 to 22 carbon atoms and x and y are integers, the sum of x and y being 80 to 140.
Bevorzugt kommen Hilfsmittelgemische zum Einsatz, die als Komponente (a) eine Verbindung der
Formel
als Komponente (b) mindestens eine Verbindung der Form
und als Komponente (c) eine Verbindung der Formel (2) enthalten, worin
Ein weiteres bevorzugtes Hilfsmittelgemisch enthält als Komponente (a) eine Verbindung der Formel
und als Komponente (b) eine Verbindung der Formel
worin
Weiterhin bevorzugt sind Hilfsmittelgemische, die als Komponente (a) eine Verbindung der Formel (3a) und als Komponente (b) eine Verbindung der Formel (4b) oder Hilfsmittelgemische, die als Komponente (a) eine Verbindung der Formel (3b) und als Komponente (b) eine Verbindung der Formel (4a) enthalten.Preference is further given to auxiliary mixtures which, as component (a), are a compound of the formula (3a) and as component (b) a compound of the formula (4b) or auxiliary mixtures which, as component (a) contain a compound of formula (3b) and as component (b) a compound of formula (4a).
M in den Formeln (1), (3) und (4) bedeutet Wasserstoff, Alkalimetall, wie z.B. Natrium, Kalium und insbesondere Ammonium. Die Reste Q. Q', Q1 und Q'1 sowie A⊖, A'⊖, A1 ⊖ und A2 ⊖ in den Formeln (1) und (3) leiten sich von Quaternierungsmitteln ab, wobei Q C1 bis C4-Alkyl, -CH2-CO-NH2. oder ist.M in the formulas (1), (3) and (4) denotes hydrogen, alkali metal, such as sodium, potassium and in particular ammonium. The residues Q. Q ', Q 1 and Q' 1 and A ⊖ , A '⊖ , A 1 ⊖ and A 2 ⊖ in formulas (1) and (3) are derived from quaternizing agents , QC 1 to C 4 -Alkyl, -CH 2 -CO-NH 2 . or is.
Als Beispiele solcher Quaternierungsmittel kommen z.B. Acetylbromide, Ethylbromide, Ethylenchlorhydrin, Ethylenbromhydrin, Epichlorhydrin, Epibromhydrin, Dimethylsulfat, Diethylsulfat und insbesondere Chloracetamid in Betracht.Examples of such quaternizing agents are e.g. Acetyl bromide, ethyl bromide, ethylene chlorohydrin, Ethylene bromohydrin, epichlorohydrin, epibromohydrin, dimethyl sulfate, diethyl sulfate and in particular Chloroacetamide into consideration.
Als aliphatische Reste R1, R2, R3, R4, R5 und R6 in den Formeln (1), (3) und (4) kommen Alkyl- oder Alkenylreste mit 12 bis 24, vorzugsweise 16 bis 22 Kohlenstoffatomen in Betracht. Als Beispiele seien genannt: der n-Dodecyl-, Myristyl-, n-Hexadecyl-, n-Heptadecyl-, n-Octadecyl-, Arachidyl-, Behenyl-, Dodecenyl-, Hexadecenyl-, Oleyl- und Octadecenylrest.The aliphatic radicals R 1 , R 2 , R 3 , R 4 , R 5 and R 6 in the formulas (1), (3) and (4) are alkyl or alkenyl radicals having 12 to 24, preferably 16 to 22, carbon atoms Consideration. The following may be mentioned as examples: the n-dodecyl, myristyl, n-hexadecyl, n-heptadecyl, n-octadecyl, arachidyl, behenyl, dodecenyl, hexadecenyl, oleyl and octadecenyl radical.
Die Verbindungen der Komponenten (a), (b) und (c) sind z.B. (teilweise) aus der US-A-4 444 564 bekannt.The compounds of components (a), (b) and (c) are e.g. (in part) from US-A-4,444,564 known.
Die Verbindungen der Komponente (a) entsprechend Formel (1a) werden hergestellt, indem man 2 bis 15 Mol Ethylenoxid an aliphatische Amine, die einen aliphatischen Rest mit 12 bis 24 Kohlenstoffatomen aufweisen, anlagert und gegebenenfalls das Anlagerungsprodukt in den sauren Monoester und gegebenenfalls den sauren Monoester in die Alkali- oder Ammoniumsalze überführt oder das Anlagerungsprodukt mit einem der oben genannten Quaternierungsmittel umsetzt. Die Verbindungen der Komponente (b) entsprechend Formel (1b) werden hergestellt, indem man 25 bis 200 Mol Ethylenoxid an aliphatische Amine, die einen aliphatischen Rest mit 12 bis 24 Kohlenstoffatomen aufweisen, anlagert und gegebenenfalls das Anlagerungsprodukt in den sauren Ester und gegebenenfalls den sauren Ester in die Alkali- oder Ammoniumsalze überführt oder das Anlagerungsprodukt mit einem der oben genannten Ouaternierungsmittel umsetzt.The compounds of component (a) according to formula (1a) are prepared by 2 to 15 moles of ethylene oxide to aliphatic amines, which is an aliphatic radical having 12 to 24 carbon atoms have accumulated and optionally the adduct in the acidic monoester and optionally the acidic monoester converted into the alkali or ammonium salts or the adduct one of the quaternizing agents mentioned above. The compounds of component (b) accordingly Formula (1b) are prepared by adding 25 to 200 moles of ethylene oxide to aliphatic amines which have an aliphatic radical having 12 to 24 carbon atoms, attached and optionally that Addition product in the acidic ester and optionally the acidic ester in the alkali or ammonium salts transferred or the adduct with one of the ouating agents mentioned above implements.
Die Verbindungen der Formel (2) werden hergestellt, indem man 80 bis 140 Mol Ethylenoxid an eine Verbindung der Formel worin R" die unter Formel (2) angegebene Bedeutung hat, anlagert.The compounds of formula (2) are prepared by adding 80 to 140 moles of ethylene oxide to a compound of formula where R "has the meaning given under formula (2).
Die Amine, die als Ausgangsstoffe für die Herstellung der Verbindungen der Formeln (1), (3) und (4) benötigt werden, können gesättigte oder ungesättigte, verzweigte oder unverzweigte Kohlenwasserstoffreste mit 12 bis 24, vorzugsweise 16 bis 22 Kohlenstoffatomen aufweisen. Die Amine können chemisch einheitlich sein oder in Form von Gemischen vorliegen. Als Amingemische werden vorzugsweise solche herangezogen, wie sie bei der Ueberführung von natürlichen Fetten oder Oelen wie z.B. Talgfett, Soja- oder Kokosöl in die entsprechenden Amine entstehen. Als Amine seien im einzelnen Dodecylamin, Hexadecylamin, Octadecylamin, Arachidylamin, Behenylamin und Octadecenylamin genannt. Bevorzugt ist ein Gemisch aus C18 bis C22-Fettaminen und Tälgfettamin. Talgfettamin ist ein Gemisch aus ca. 30 % Hexadecylamin, 25 % Octadecylamin und 45 % Octadecenylamin.The amines which are required as starting materials for the preparation of the compounds of the formulas (1), (3) and (4) can have saturated or unsaturated, branched or unbranched hydrocarbon radicals having 12 to 24, preferably 16 to 22, carbon atoms. The amines can be chemically uniform or in the form of mixtures. The amine mixtures used are preferably those which arise when natural fats or oils, such as tallow fat, soybean or coconut oil, are converted into the corresponding amines. Dodecylamine, hexadecylamine, octadecylamine, arachidylamine, behenylamine and octadecenylamine may be mentioned as amines. A mixture of C 18 to C 22 fatty amines and tallow fatty amine is preferred. Tallow fatty amine is a mixture of approx. 30% hexadecylamine, 25% octadecylamine and 45% octadecenylamine.
Sowohl die Ethylenoxidanlagerung als auch die Veresterung können nach an sich bekannten Methoden durchgeführt werden. Zur Veresterung können Schwefelsäure oder deren funktionelle Derivate wie z.B. Chlorsulfonsäure und insbesondere Sulfaminsäure dienen.Both the ethylene oxide addition and the esterification can be carried out according to methods known per se be performed. For the esterification, sulfuric acid or its functional derivatives such as e.g. Chlorosulfonic acid and especially sulfamic acid are used.
Die Veresterung wird in der Regel durch einfaches Vermischen der Reaktionspartner unter Erwärmen, zweckmässig auf eine Temperatur zwischen 50 und 100°C, durchgeführt. Die freien Säuren können anschliessend in die Alkalimetall- oder Ammoniumsalze übergeführt werden, indem auf übliche Weise Basen wie z.B. Ammoniak, Natrium- oder Kaliumhydroxid zugegeben werden.The esterification is usually carried out by simply mixing the reactants with heating, expediently carried out at a temperature between 50 and 100 ° C. The free acids can then be converted into the alkali metal or ammonium salts by the usual way Bases such as Ammonia, sodium or potassium hydroxide can be added.
Für das erfindungsgemässe Verfahren verwendet man ein Hilfsmittelgemisch, das 10 bis 80 Teile, vorzugsweise 20 bis 70 Teile der Komponente (a), 5 bis 70 Teile, vorzugsweise 5 bis 50 Teile der Komponente (b) und 0 bis 70, vorzugsweise 0 bis 50 Teile der Verbindung der Komponente (c) und ad 100 Teile Wasser enthält.For the process according to the invention, an auxiliary mixture is used which 10 to 80 parts, preferably 20 to 70 parts of component (a), 5 to 70 parts, preferably 5 to 50 Parts of component (b) and 0 to 70, preferably 0 to 50 parts of the compound of component (c) and contains ad 100 parts of water.
Die Einsatzmengen, in denen das Hilfsmittelgemisch bestehend aus den Komponenten (a), (b) und gegebenenfalls (c) dem Färbebad zugesetzt wird, bewegen sich zwischen 0,5 und 4 Gewichtsprozent, bezogen auf das zu färbende Fasermaterial. Vorzugsweise verwendet man 1 bis 2 Gewichtsprozent des Hilfsmittelgemisches, bezogen auf das Fasermaterial.The amounts in which the auxiliary mixture consists of components (a), (b) and optionally (c) is added to the dyebath, range between 0.5 and 4 percent by weight, based on the fiber material to be dyed. Preferably 1 to 2 percent by weight of the Auxiliary mixture, based on the fiber material.
Das Gewichtsverhältnis der Komponenten (a) und (b) liegt zwischen 1:5 und 10:1, vorzugsweise zwischen 1:2 und 5:1.The weight ratio of components (a) and (b) is between 1: 5 and 10: 1, preferably between 1: 2 and 5: 1.
Als Fasermaterial, das erfindungsgemäss gefärbt werden kann, kommt Wolle in Betracht. Das Fasermaterial kann dabei in den verschiedenen Aufmachungen vorliegen. Beispielsweise kommen in Betracht: Flocke, Kammzug, Garn, Gewebe, Maschenware oder Teppiche. Die Wolle kann normal oder filzfrei ausgerüstet sein.Wool can be considered as the fiber material that can be dyed according to the invention. The fiber material can be in various forms. Examples include: Flake, sliver, yarn, fabric, knitwear or carpets. The wool can be normal or felt-free be equipped.
Für das Färben von normaler Wolle bzw. von filzfrei ausgerüsteter Wolle nach dem vorliegenden Verfahren kommen als Reaktivfarbstoffe die unter diesem Begriff bekannten organischen Farbstoffe - unabhängig von der Art ihrer reaktiven Gruppe - in Betracht.For dyeing normal wool or felt-free finished wool according to the present one Processes come as reactive dyes the organic dyes known under this term - regardless of the type of their reactive group - into consideration.
Diese Farbstoffklasse wird im Colour Index 3. Auflage 1971 als "Reaktive Dyes" bezeichnet. Es handelt sich dabei vorwiegend um solche Farbstoffe, die mindestens eine mit Polyhydroxylfasern (Cellulosefasern) oder Polyamidfasern, besonders Wolle, reaktionsfähige Gruppe, eine Vorstufe hierfür oder einen mit Polyhydroxylfasern oder Polyamidfasern reaktionsfähigen Substituenten enthalten. This class of dyes is referred to in the Color Index 3rd edition 1971 as "reactive dyes". It deals mainly dyes that contain at least one with polyhydroxy fibers (cellulose fibers) or polyamide fibers, especially wool, reactive group, a precursor for this or one with Contain polyhydroxyl fibers or polyamide fibers reactive substituents.
Als Grundkörper der Reaktivfarbstoffe eignen sich besonders solche aus der Reihe der Mono-, Dis-oder Polyazofarbstoffe einschliesslich der Formazanfarbstoffe sowie der Anthrachinon-, Xanthen-, Nitro-, Triphenylmethan-, Naphthochinonimin-, Dioxazin- und Phthalocyaninfarbstoffe. wobei die Azo- und Phthalo cyaninfarbstoffe sowohl metallfrei als auch metallhatig sein können.Suitable bases for the reactive dyes are, in particular, those from the series of mono-, dis- or Polyazo dyes including the formazan dyes and the anthraquinone, xanthene, nitro, Triphenylmethane, naphthoquinoneimine, dioxazine and phthalocyanine dyes. being the azo and phthalo cyanine dyes can be both metal-free and metal-containing.
Als reaktionsfähige Gruppen und Vorstufen, die solche reaktionsfähige Gruppen bilden, seien beispielsweise Epoxygruppen, die Ethylenimidgruppe, die Vinylgruppierung in Vinylsulfon- oder im Acrylsäurerest sowie die β-Sulfatoethylsulfongruppe, die β-Chlorethylsuffongruppe oder die β-Dialkylaminoethylsulfongruppe genannt.Examples of reactive groups and precursors which form such reactive groups are Epoxy groups, the ethylene imide group, the vinyl grouping in vinyl sulfone or in acrylic acid residue and the β-sulfatoethylsulfone group, the β-chloroethylsuffone group or the β-dialkylaminoethylsulfone group called.
Als reaktionsfähige Substituenten in Reaktivfarbstoffen dienen solche, die leicht abspaltbar sind und einen elektrophilen Rest hinterlassen.The reactive substituents in reactive dyes are those which are easily removable and leave an electrophilic residue.
Als solche Substituenten kommen beispielsweise 1 oder 2 Halogenatome in einem aliphatischen Acylrest z.B. in β-Stellung oder α- und β-Stellung eines Propionylrestes oder in α- und/oder β-Stellung eines Acrylsäurerestes. oder 1 bis 3 Halogenatome an folgenden Ringsystem in Betracht: Pyridazin, Pyrimidin, Pyridazon, Triazin, Chinoxalin oder Phthalazin.Examples of such substituents are 1 or 2 halogen atoms in an aliphatic one Acyl residue e.g. in the β-position or α- and β-position of a propionyl radical or in the α- and / or β-position of an acrylic acid residue. or 1 to 3 halogen atoms on the following ring system: pyridazine, Pyrimidine, pyridazone, triazine, quinoxaline or phthalazine.
Es können auch Farbstoffe mit zwei oder mehreren gleich- oder verschiedenartigen Reaktivgruppen verwendet werden.Dyes with two or more identical or different reactive groups can also be used be used.
Bevorzugte Reaktivfarbstoffe enthalten als reaktionsfähige Substituenten Chloracetyl, Bromacryl oder Dibrompropionyl.Preferred reactive dyes contain chloroacetyl, bromoacrylic or as reactive substituents Dibromopropionyl.
Die Reaktivfarbstoffe können saure, salzbildende Substituenten, wie z.B. Carbonsäuregruppen, Schwefelsäure- und Phosphonsäureestergruppen, Phosphonsäuregruppen oder vorzugsweise Sulfonsäuregruppen enthalten.The reactive dyes can be acidic, salt-forming substituents, e.g. Carboxylic acid groups, sulfuric acid and phosphonic acid ester groups, phosphonic acid groups or preferably sulfonic acid groups contain.
Bevorzugt sind Reaktivfarbstoffe mit mindestens einer Sulfonsäuregruppe, insbesondere Reaktivfarbstoffe mit einem Azo- oder Anthrachinongrundkörper, welcher vorzugsweise zwei bis drei Sulfonsäuregruppen aufweist.Reactive dyes with at least one sulfonic acid group, in particular reactive dyes, are preferred with an azo or anthraquinone base, which preferably has two to three sulfonic acid groups having.
Es können auch Mischungen von Reaktivfarbstoffen eingesetzt werden, wobei Bichromie- oder Trichromiefärbungen erzeugt werden können.Mixtures of reactive dyes can also be used, with bichromatic or trichromatic dyeings can be generated.
Die Färbung erfolgt nach dem Ausziehverfahren. Die Menge der der Färbeflotte zugesetzten Farbstoffe richtet sich nach der gewünschten Farbstärke. Im allgemeinen haben sich Mengen von 0,01 bis 10 Gewichtsprozent, vorzugsweise 0,01 bis 2 Gewichtsprozent, bezogen auf das eingesetzte Fasermaterial, bewährt.The coloring takes place after the pull-out procedure. The amount of dyes added to the dye liquor depends on the desired color strength. Generally, amounts are from 0.01 to 10 Percent by weight, preferably 0.01 to 2 percent by weight, based on the fiber material used, proven.
Das Flottenverhältnis kann innerhalb eines weiten Bereiches gewählt werden z.B. 1:3 bis 1:100, vorzugsweise 1:8 bis 1:30.The liquor ratio can be chosen within a wide range e.g. 1: 3 to 1: 100, preferably 1: 8 to 1:30.
Die Färbebäder können Mineralsäuren, wie z.B. Schwefelsäure oder Phosphorsäure, organische Säuren, zweckmässig aliphatische Carbonsäuren wie Ameisensäure, Essigsäure, Oxalsäure oder Zitronensäure und/oder Salze wie Ammoniumacetat, Ammoniumsulfat oder Natriumacetat enthalten. Die Säuren dienen vor allem der Einstellung des pH-Wertes der erfindungsgemäss verwendeten Flotten, der zwischen 4 und 5 liegt.The dye baths can contain mineral acids, e.g. Sulfuric acid or phosphoric acid, organic acids, expediently aliphatic carboxylic acids such as formic acid, acetic acid, oxalic acid or citric acid and / or salts such as ammonium acetate, ammonium sulfate or sodium acetate. The acids serve especially the adjustment of the pH of the liquors used according to the invention, which is between 4 and 5 lies.
Die Färbeflotten können auch weitere Zusätze, wie z.B. Wollschutz-, Dispergier- und Netzmittel sowie auch Entschäumer enthalten.The dye liquors can also contain other additives, e.g. Wool protection, dispersing and wetting agents and also contain defoamers.
Besondere Vorrichtungen sind beim erfindungsgemässen Verfahren nicht erforderlich. Es können die üblichen Färbeapparaturen, wie beispielsweise offene Bäder, Kammzug-, Stranggarn- oder Packapparate, Jigger-, Paddelapparate, Baumfärbeapparate, Zirkulations- oder Düsenfärbeapparate oder Haspelkufen verwendet werden.Special devices are not required in the method according to the invention. They can usual dyeing machines, such as, for example, open baths, worsted, stranded yarn or packers, Jigger, paddle, tree dyeing, circulation or jet dyeing or reel skids be used.
Das Färben erfolgt mit Vorteil bei einer Temperatur im Bereich von 60 bis 120°C, vorzugsweise 70 bis 105°C. Die Färbedauer hält sich im üblichen Rahmen und beträgt in der Regel 20 bis 120 Minuten.The dyeing is advantageously carried out at a temperature in the range from 60 to 120 ° C., preferably 70 to 105 ° C. The dyeing time is within the usual range and is usually 20 to 120 minutes.
Nach Beendigung der Färbung kann dem Färbeprozess eine alkalische Nachbehandlung, wie z.B. mit wässerigem Ammoniak, Alkalimetallhydroxiden, Alkalimetallcarbonaten. -hydrogencarbonaten oder Hexamethylentetraamin angeschlossen werden. Der pH-Wert der Alkali enthaltenden Färbebäder beträgt zweckmässigerweise 7,5 bis 9, vorzugsweise 8 bis 8,5.After the dyeing process, the dyeing process can be followed by an alkaline after-treatment, e.g. With aqueous ammonia, alkali metal hydroxides, alkali metal carbonates. -hydrogen carbonates or hexamethylenetetraamine be connected. The pH of the dye baths containing alkali is expediently 7.5 to 9, preferably 8 to 8.5.
Das Färben des Fasermaterials wird zweckmässig so durchgeführt, dass man das Färbegut mit einer wässerigen Flotte, die die Säure, das Hilfsmittelgemisch aus den Komponenten (a) und (b) und gegebenenfalls der Komponente (c) enthält und eine Temperatur von 30 bis 60°C aufweist, kurz behandelt und dem gleichen Bade den Reaktivfarbstoff zusetzt. Hierauf steigert man die Temperatur langsam, um in einem Bereich von 80 bis 100°C und während 20 bis 90 Minuten, vorzugsweise 30 bis 60 Minuten zu färben. Anschliessend wird das Färbegut bei Bedarf nach Zusatz von Alkalien, vorzugsweise Natriumhydrogencarbonat oder Natriumcarbonat noch 10 bis 20 Minuten bei 70 bis 90°C behandelt. Am Schluss wird das gefärbte Material herausgezogen und wie üblich gespült, abgesäuert und getrocknet. The dyeing of the fiber material is expediently carried out in such a way that the material to be dyed with a aqueous liquor containing the acid, the auxiliary mixture of components (a) and (b) and, if appropriate contains component (c) and has a temperature of 30 to 60 ° C, briefly treated and the the same bath adds the reactive dye. Then you slowly increase the temperature to in one Color range from 80 to 100 ° C and for 20 to 90 minutes, preferably 30 to 60 minutes. The dyed material is then, if necessary, after the addition of alkalis, preferably sodium hydrogen carbonate or treated with sodium carbonate for 10 to 20 minutes at 70 to 90 ° C. In the end it will pulled out colored material and rinsed, acidified and dried as usual.
Man erhält nach dem erfindungsgemässen Färbeverfahren faser- und flächenegale Färbungen, besonders in hellen bis mittleren Farbtönen mit guten Licht- und Nassechtheiten.Fiber and surface level dyeings are obtained in particular by the dyeing process according to the invention in light to medium shades with good light and wet fastness properties.
Die nachfolgenden Beispiele veranschaulichen die Erfindung. Darin sind die Teile Gewichtsteile und Prozente Gewichtsprozente. Die Temperaturen sind in °C angegeben.The following examples illustrate the invention. The parts are parts by weight and Percentages by weight. The temperatures are given in ° C.
Beispiel 1: 40 g Wollgewebe werden in einem Zirkulationsapparat nach der Baumfärbemethode
während 10 Minuten bei 40° vorbehandelt. Die Flotte besteht aus
Der pH-Wert der Flotte beträgt 4,5.The pH of the liquor is 4.5.
Nach Zugabe einer Lösung, die 12 mg des Farbstoffes der Formel 24 mg des Farbstoffes der Formel und 44 mg des Farbstoffes der Formel enthält, wird die Färbeflotte noch ca. 5 Minuten bei 40° gehalten und dann mit einer Aufheizrate von 1 °/min auf 60° erwärmt und 20 Minuten bei 60° gehalten. Anschliessend wird mit 1 °/min auf 98° erwärmt und 30 Minuten gefärbt. Nach Abkühlen der Flotte auf 70° wird wie üblich gespült. Man erhält eine faser- und flächenegale Färbung mit guten Echtheitseigenschaften.After adding a solution, the 12 mg of the dye of the formula 24 mg of the dye of the formula and 44 mg of the dye of the formula contains, the dyebath is kept at 40 ° for about 5 minutes and then heated to 60 ° at a rate of 1 ° / min and held at 60 ° for 20 minutes. The mixture is then heated to 98 ° at 1 ° / min and dyed for 30 minutes. After the liquor has cooled to 70 °, rinsing is carried out as usual. A fiber- and flat-level dyeing with good fastness properties is obtained.
Beispiel 2: Man verfährt wie in Beispiel 1 beschrieben mit dem Unterschied, dass anstelle des
Hilfsmittels B2
Beispiel 3: Man verfährt wie in Beispiel 1 beschrieben mit dem Unterschied, dass anstelle des Hilfsmittels B2 0,2 g des Anlagerungsproduktes von 34 Mol Ethylenoxid an 1 Mol eines C20-C22-Fettamins eingesetzt wird. Man erhält eine faser- und flächenegale Färbung mit guten Echtheitseigenschaften. EXAMPLE 3 The procedure is as described in Example 1, with the difference that 0.2 g of the adduct of 34 mol of ethylene oxide and 1 mol of a C 20 -C 22 fatty amine is used instead of auxiliary B 2 . A fiber- and flat-level dyeing with good fastness properties is obtained.
Beispiel 4: Man verfährt wie in Beispiel 1 beschrieben mit dem Unterschied, dass anstelle des Hilfsmittels B2 0,2 g des quaternierten Anlagerungsproduktes von 34 Mol Ethylenoxid an 1 Mol eines C20-C22-Fettamins eingesetzt wird. Man erhält eine faser- und flächenegale Färbung mit guten Echtheitseigenschaften. EXAMPLE 4 The procedure is as described in Example 1, with the difference that 0.2 g of the quaternized adduct of 34 mol of ethylene oxide and 1 mol of a C 20 -C 22 fatty amine is used instead of auxiliary B 2 . A fiber- and flat-level dyeing with good fastness properties is obtained.
Beispiel 5: Man verfährt wie in Beispiel 1 beschrieben mit dem Unterschied, dass anstelle von B2 0,2 g des Anlagerungsproduktes von 30 Mol Ethylenoxid an 1 Mol Talgfettamin eingesetzt wird. Man erhält eine faser- und flächenegale Färbung mit guten Echtheitseigenschaften. EXAMPLE 5 The procedure is as described in Example 1, with the difference that 0.2 g of the adduct of 30 mol of ethylene oxide and 1 mol of tallow fatty amine is used instead of B 2 . A fiber- and flat-level dyeing with good fastness properties is obtained.
Beispiel 6: 1 kg Wollkammgarn in Form einer Kreuzspule wird in einem Zirkulationsapparat mit 9 l
Wasser von 40°,
Beispiel 7: Man verfährt wie in Beispiel 7, mit dem Unterschied, dass man eine Farbstofflösung,
bestehend aus
Beispiel 8: Man verfährt wie in Beispiel 6 mit dem Unterschied, dass man anstelle der Hilfsmittelgemischkombinationen
aus A1 und B1 30 g des Hilfsmittelgemisches C1 verwendet, das folgende Zusammensetzung
aufweist:
Beispiel 9: Man verfährt wie in Beispiel 2 beschrieben mit dem Unterschied, dass an Stelle der Farbstoffmischung 80 mg des Farbstoffes der Formel verwendet wird. EXAMPLE 9 The procedure is as described in Example 2, with the difference that, instead of the dye mixture, 80 mg of the dye of the formula is used.
Beispiel 10: Man verfährt wie in Beispiel 9 beschrieben mit dem Unterschied. dass man anstelle von 80 mg des Farbstoffs der Formel (105) 80 mg des Farbstoffes der Formel einsetzt. Example 10: One proceeds as described in Example 9 with the difference. that instead of 80 mg of the dye of the formula (105), 80 mg of the dye of the formula starts.
Beispiel 11: Man verfährt wie in Beispiel 9 beschrieben mit dem Unterschied, dass man anstelle von 80 mg des Farbstoffs der Formel (105) 200 mg des Farbstoffes der Formel verwendet. EXAMPLE 11 The procedure is as described in Example 9, with the difference that instead of 80 mg of the dye of the formula (105), 200 mg of the dye of the formula used.
Beispiel 12: Man verfährt wie in Beispiel 9 beschrieben mit dem Unterschied, dass man anstelle von 80 mg des Farbstoffs der Formel (105) 320 mg des Farbstoffs der Formel verwendet. EXAMPLE 12 The procedure is as described in Example 9, with the difference that instead of 80 mg of the dye of the formula (105), 320 mg of the dye of the formula used.
Beispiel 13: Man verfährt wie in Beispiel 9 beschrieben mit dem Unterschied, dass man anstelle von 80 mg des Farbstoffs der Formel (105) 100 mg des Farbstoffes der Formel verwendet. EXAMPLE 13 The procedure is as described in Example 9, with the difference that instead of 80 mg of the dye of the formula (105), 100 mg of the dye of the formula used.
Claims (14)
- A process for producing non-skittery and level dyeings on wool with reactive dyes in the presence of an auxiliary combination, which process comprises dyeing said material with an aqueous liquor comprising at least one reactive dye and an auxiliary combination comprising, as component (a), at least one compound of formula and, as component (b), at least one compound of formula whereinR1 and R2 are each independently of the other an aliphatic radical of 12 to 24 carbon atoms,A⊖ and A'⊖ are an anion,Z1, Z2, Z'1 and Z'2 are each independently of one another hydrogen, SO3M or PO3M, wherein M is hydrogen, alkali metal or aminonium, t1 is 0 or 1 and t2 is 0 or 1 and when t1 is 0, Z1 and Z2 are hydrogen or one radical from Z1 and Z2 is hydrogen and the other is SO3M or PO3M, and, when t2 is 0, Z'1 and Z'2 are hydrogen or one radical from Z'1 and Z'2 is hydrogen and the other is SO3M or PO,M, m1, n1, p1 and q1 are integers, the sum of (m1+n1) being 2 to 15 and that of (p1+q1) being 25 to 200, and finishing the dyeing, irrespective of the depth of shade, at a pH from 4.0 to 5.0.
- A process according to claim 1, wherein wool is dyed in light to medium shades.
- A process according to either claim 1 or claim 2, wherein the sum of (m1+n1) is 5 to 12 and that of (p1+q1) is 25 to 100.
- A process according to any one of claims 1 to 4, which comprises the use of an auxiliary combination wherein component (a) is a compound of formula and component (b) is a compound of formula and component (c) is a compound of formula (2), whereinR3 and R4 are each independently of the other an aliphatic radical of 12 to 24 carbon atoms,Q1 and Q'1 are each independently of the other C1 to C4alkyl or -CH2-CO-NH2,Z3, Z4, Z'3 and Z'4 are each independently of one another hydrogen or SO3M,M is hydrogen, alkali metal or ammonium,m2, n2, p2 and q2 are integers, the sum of (m2+n2) being 2 to 15 and that of (p2+q2) being 25 to 100, andA1 ⊖ and A2 ⊖ are an anion.
- A process according to any one of claims 1 to 4, which comprises the use of an auxiliary combination wherein component (a) is a compound of formula and component (b) is a compound of formula whereinR5 and R6 are each independently of the other an aliphatic radical of 12 to 24 carbon atoms,Z5 and Z6 are hydrogen or one radical from Z5 and Z6 is hydrogen and the other is SO3M,Z'5 and Z'6 are hydrogen or one radical from Z'5 and Z'6 is hydrogen and the other is SO3M,M is hydrogen, alkali metal or ammonium, andm3, n3, p3 and q3 are integers, the sum of (m3+n3) being 5 to 12 and that of (p3+q3) being 25 to 100.
- A process according to any one of claims 1 to 4, which comprises the use of an auxiliary combination wherein component (a) is a compound of formula (3a) according to claim 5 and wherein component (b) is a compound of formula (4b) according to claim 6.
- A process according to any one of claims 1 to 4, which comprises the use of an auxiliary combination wherein component (a) is a compound of formula (3b) according to claim 5 and wherein component (b) is a compound of formula (4a) according to claim 6.
- A process according to any one of claims 1 to 8, which comprises the use of an auxiliary combination comprising10 to 80 parts of component (a),5 to 70 parts of component (b) and0 to 70 parts of component (c)and water to make up 100 parts.
- A process according to any one of claims 1 to 9, wherein the weight ratio of component (a) to component (b) is from 1:5 to 10:1.
- A process according to any one of claims 1 to 10, which comprises the use of reactive dyes which contain at least one sulfo group.
- A process according to claim 11, which comprises the use of reactive dyes which contain chloroacetyl, bromoacetyl or dibromopropionyl as reactive substituents.
- A process according to any one of claims 1 to 12, wherein dyeing is carried out at a temperature between 60 and 120°C.
- A process according to any one of claims 1 to 13, wherein dyeing is carried out at a liquor ratio of 1:3 to 1:100, preferably from 1:8 to 1:30.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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CH477/90 | 1990-02-14 | ||
CH47790 | 1990-02-14 |
Publications (3)
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EP0442844A1 EP0442844A1 (en) | 1991-08-21 |
EP0442844B1 EP0442844B1 (en) | 1995-02-01 |
EP0442844B2 true EP0442844B2 (en) | 1998-01-21 |
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EP91810078A Expired - Lifetime EP0442844B2 (en) | 1990-02-14 | 1991-02-05 | Process for dyeing of wool with reactive dyes |
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US (1) | US5145486A (en) |
EP (1) | EP0442844B2 (en) |
JP (1) | JPH04214476A (en) |
KR (1) | KR910015749A (en) |
AU (1) | AU638793B2 (en) |
CA (1) | CA2036224A1 (en) |
DE (1) | DE59104446D1 (en) |
ES (1) | ES2067902T5 (en) |
NZ (1) | NZ237087A (en) |
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EP0548013A1 (en) * | 1991-12-16 | 1993-06-23 | Ciba-Geigy Ag | Process for dyeing of wool with help of low-temperature plasma or Corona-pretreatment |
IT1261839B (en) * | 1992-08-03 | 1996-06-03 | Sandoz Ag | PROCEDURE FOR THE PRODUCTION OF SPECIAL COLORING EFFECTS ON TEXTILE PRODUCTS AND MIXTURES OF DYES USED. |
DE59409028D1 (en) * | 1993-07-28 | 2000-02-03 | Ciba Sc Holding Ag | Process for dyeing wool-containing fiber materials |
DE19848894A1 (en) * | 1998-10-23 | 2000-04-27 | Bayer Ag | Phosphoric acid esters, useful as leveling agents for the dyeing of nitrogen containing fibers, preferably wool, are prepared by reaction of phosphoroxy chloride with a mixture of alcohols. |
CN100449054C (en) * | 2003-06-26 | 2009-01-07 | 西巴特殊化学品控股有限公司 | Aqueous liquid compositions of cyclodextrine or cyclodextrine derivatives and a process using the said composition |
EP1777337A1 (en) * | 2005-10-07 | 2007-04-25 | Clariant International Ltd. | Method of dyeing polyamide fibres |
DE102008058921A1 (en) * | 2008-11-25 | 2010-05-27 | Henkel Ag & Co. Kgaa | New dyes |
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US3919283A (en) * | 1965-03-18 | 1975-11-11 | Ciba Geigy Ag | Sulfate derivatives of polyglycol compounds |
DE2847913B1 (en) * | 1978-11-04 | 1980-02-07 | Hoechst Ag | Process for dyeing wool with reactive dyes |
EP0089004B1 (en) * | 1982-03-12 | 1986-04-16 | Ciba-Geigy Ag | Process for dyeing fibrous material from natural polyamides |
FR2574791A1 (en) * | 1984-12-14 | 1986-06-20 | Sandoz Sa | FATTY AMINO ACID SULFATES, THEIR PREPARATION AND THEIR USE AS AUXILIARY PRODUCTS |
EP0312493B1 (en) * | 1987-10-14 | 1992-07-15 | Ciba-Geigy Ag | Process for dyeing natural polyamide fibres with reactive dyes |
EP0414631A1 (en) * | 1989-02-22 | 1991-02-27 | Ciba-Geigy Ag | Auxiliary agent mixture and its use in dyeing polyester fibre materials |
EP0417040A1 (en) * | 1989-09-06 | 1991-03-13 | Ciba-Geigy Ag | Dyeing process for wool |
-
1991
- 1991-02-05 DE DE59104446T patent/DE59104446D1/en not_active Expired - Fee Related
- 1991-02-05 EP EP91810078A patent/EP0442844B2/en not_active Expired - Lifetime
- 1991-02-05 ES ES91810078T patent/ES2067902T5/en not_active Expired - Lifetime
- 1991-02-11 US US07/654,139 patent/US5145486A/en not_active Expired - Fee Related
- 1991-02-12 KR KR1019910002313A patent/KR910015749A/en not_active Application Discontinuation
- 1991-02-12 AU AU70994/91A patent/AU638793B2/en not_active Ceased
- 1991-02-12 NZ NZ237087A patent/NZ237087A/en unknown
- 1991-02-12 CA CA002036224A patent/CA2036224A1/en not_active Abandoned
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US5145486A (en) | 1992-09-08 |
JPH04214476A (en) | 1992-08-05 |
EP0442844A1 (en) | 1991-08-21 |
NZ237087A (en) | 1993-04-28 |
AU638793B2 (en) | 1993-07-08 |
CA2036224A1 (en) | 1991-08-15 |
ES2067902T5 (en) | 1998-04-16 |
DE59104446D1 (en) | 1995-03-16 |
EP0442844B1 (en) | 1995-02-01 |
KR910015749A (en) | 1991-09-30 |
ES2067902T3 (en) | 1995-04-01 |
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