EP0105034A1 - Dyeing aid and process for dyeing of polyacrylonitrile fibre material - Google Patents
Dyeing aid and process for dyeing of polyacrylonitrile fibre material Download PDFInfo
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- EP0105034A1 EP0105034A1 EP83810418A EP83810418A EP0105034A1 EP 0105034 A1 EP0105034 A1 EP 0105034A1 EP 83810418 A EP83810418 A EP 83810418A EP 83810418 A EP83810418 A EP 83810418A EP 0105034 A1 EP0105034 A1 EP 0105034A1
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- Prior art keywords
- lower alkyl
- formula
- dyeing
- carbon atoms
- quaternary ammonium
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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
- 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
- D06P1/64—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 low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/6428—Compounds containing aminoxide groups
-
- 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
- D06P1/655—Compounds containing ammonium groups
- D06P1/66—Compounds containing ammonium groups containing quaternary ammonium groups
Definitions
- the present mixture of auxiliaries is suitable as a wetting, venting, retarding and leveling agent when dyeing slow, normal or fast-drawing polyacrylonitrile fibers with migrating or non-migrating cationic dyes or mixtures thereof.
- the quaternary ammonium salts which can be used as component (A) can have migrating or non-migrating properties.
- migrating quaternary ammonium salts are preferably used, which advantageously have only a low retarding effect at the end of the dyeing process.
- Quaternary ammonium salts whose cation weight is less than 400, especially less than 250, whose parachor is less than 1200, in particular less than 800 and whose log P is less than 8, preferably less than 7.0, are particularly suitable. Among these, preference is given to those whose cation weight is less than 275, whose parachor is less than 700 and whose log P is less than 6.4.
- An ⁇ the anion of an organic or inorganic acid e.g. the chloride, bromide, sulfate, benzenesulfonate, p-toluenesulfonate, methosulfate, ethosulfate or methophosphate ion mean.
- Lower alkyl generally represents those groups or group components which have 1 to 5, in particular 1 to 3, carbon atoms, such as, for example, Methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl or amyl.
- R preferably denotes an alkyl radical or alkenyl radical each having 5 to 21 carbon atoms, especially 7 to 14 carbon atoms.
- alkyl radicals are pentyl, hexyl, octyl, decyl, dodecyl, cocosyl, myristyl, hexadecyl, heptadecyl, octadecyl, arachidyl or behenyl.
- R is preferably pentyl, hexyl, octyl, decyl, dodecyl, cocosyl or myristyl or a mixture of these alkyl radicals.
- Q is preferably the direct bond between R and -CH 2 -.
- the Y radicals can be the same or different from one another.
- Y 1 and Y 2 mean, for example, cyclopentyl or preferably cyclohexyl.
- Y 1 and Y 2 are preferably methyl, ethyl or especially 2-hydroxyethyl.
- Y 3 represents a lower alkyl radical, it is in particular methyl or ethyl. If Y 3 is hydroxy-lower alkyl or cyano-lower alkyl, then it is primarily 2-hydroxyethyl, 3-hydroxypropyl or 2-cyanoethyl.
- epoxy lower alkyl Y 3 preferably denotes the epoxypropyl group.
- carbamoyl lower alkyl Y 3 is in particular the carbamoylmethyl group. Y 3 is preferably methyl, ethyl or benzyl.
- Y 1 and Y 2 together with the nitrogen atom represent a heterocyclic radical, this is, for example, pyrrolidino, piperidino, pipecolino, thiomorpholino or preferably morpholino.
- Anions are both anions of inorganic acids, e.g. the chloride, bromide, fluoride, sulfate or phosphate ion as well as organic acids, e.g. aromatic or aliphatic sulfonic acids, e.g. the benzenesulfonate, p-toluenesulfonate, chlorobenzenesulfonate, methanesulfonate or ethanesulfonate ion and the anions of acidic alkyl esters of inorganic acids, such as e.g. the methosulfate, ethosulfate or methophosphate ion into consideration. Above all, the chloride or methosulfate ion.
- quaternary ammonium salts of the formula where V is hydrogen, methyl or ethyl, R is an alkyl or Alkenyl radical each having 6 to 18 carbon atoms and An ⁇ has the meaning given above, are used.
- the compounds are of the formula wherein R 3 is n-octyl or n-dodecyl, particularly suitable.
- Quaternary ammonium salts of the formula are also suitable wherein R 22 Y 3 ' Y 4 , Y 5 and An ⁇ have the meaning given and n is 2 or 3.
- Examples of these compounds of formula (5) are quaternary ammonium salts by definition, which e.g. by reaction of coconut oil fatty acid chloride with N, N-dimethylpropylenediamine and then by quaternization with methyl chloride, dimethyl sulfate, glycol chlorohydrin, epichlorohydrin or benzyl chloride.
- Examples of suitable compounds of the formula (7) are: N-octadecyl-guanidinium chloride, N-hexadecyl-N'-methyl-N "-2-hydroxyethylguanidinium chloride and 2-octylaminoimidazolium acetate.
- Mixtures of quaternary ammonium salts according to the definition can also be used as component (A) in the auxiliary mixture according to the invention.
- amine oxides that are suitable as component (B) suitably correspond to the formula wherein X 1 , X 2 and X 3 ' independently of one another each represent an aliphatic, cycloaliphatic, araliphatic or aromatic radical, at least one of the X radicals representing an aliphatic radical having 5 to 22, preferably 8 to 18, carbon atoms.
- Mixtures which contain two or more of the amine oxides of the formula (8) or (9) can also be present in the auxiliary mixture according to the invention.
- the amine oxides of the formula (8) or (9) are used in amounts of 10 to 25, preferably 12 to 20, percent by weight, based on the total weight of the aqueous auxiliary mixture.
- auxiliary preparations according to the invention can be prepared by simply stirring the components (A) and (B) mentioned, preferably in water. Homogeneous, preferably aqueous, clear mixtures are obtained which are very stable in storage at room temperature. Components (A) and (B) are generally present in a weight ratio of 9: 1 to 3: 7, preferably 6: 1 to 1: 1 and in particular 4: 1 to 2: 1.
- the new formulations are used in particular as wetting, venting and in particular leveling and retarding agents in the dyeing of polyacrylonitrile fiber materials. They therefore allow the leveled substrate to be perfectly level.
- the present invention accordingly also relates to a process for dyeing polyacrylonitrile fibers with cationic dyes.
- the process is characterized in that this material is dyed in the presence of the auxiliary mixture according to the invention.
- Components (A) and (B) can also be added separately to the dyebath.
- auxiliary mixture according to the invention is added to the dyebath, advantageously range between 0.1 to 5 percent by weight, preferably 0.5 to 3 percent by weight, based on the weight of the material to be dyed.
- Both migrating and non-migrating dyes can be used as cationic dyes.
- migrating cationic dyes are those with a more or less delocalized positive charge, the cation weight of which is less than 310, the parachor of which is less than 750 and the log P of which is less than 3.2.
- the Parachor is according to the article by O.R. Quayle [Chem. Rev. 53, 439 (1953)] and log P means the relative lipophilicity, the calculation of which by C. Hanach et al [J.Med.Chem. 16, 1207 (1973)].
- the influence of the charge of the dye cations was not taken into account, which results in 6 log units higher log P values.
- Preferred migrating cationic dyes are those whose cation weight is less than 275, whose parachor is less than 680 and whose log P is less than 2.8,
- Non-migrating cationic dyes are, in particular, those whose cation weight is greater than 310 and whose parachor is greater than 750.
- the cationic, migrating and non-migrating dyes can belong to different classes of dyes.
- they are salts, for example chlorides, sulfates or metal halides, for example zinc chloride double salts of azo dyes, such as monoazo dyes or hydrazone dyes, anthraquinone, diphenylmethane, triphenylmethane, methine, azomethine, coumarin, ketonimine, cyanine, xanthene , Azine, oxazine or thiazine dyes.
- azo dyes such as monoazo dyes or hydrazone dyes, anthraquinone, diphenylmethane, triphenylmethane, methine, azomethine, coumarin, ketonimine, cyanine, xanthene , Azine, oxazine or thiazine dyes.
- cationic dyes can also be used will.
- Dye combinations of at least 2 or preferably 3 migrating or non-migrating cationic dyes are particularly preferred for producing level dichromia or trichromatic dyeings, it also being possible to use mixtures of migrating and non-migrating cationic dyes.
- the amount of dyes added to the liquor depends on the desired depth of color. In general, amounts of dye of 0.01 to 5, preferably 0.05 to 2 percent by weight, based on the weight of the material to be dyed, have proven to be advantageous.
- the dye liquor can also electrolytes, especially inorganic, such as alkali metal salts, expediently sodium salts, such as e.g. Sodium chloride or sodium sulfate, potassium salts such as e.g. Potassium chloride or potassium sulfate, ammonium salts such as e.g. Contain ammonium chloride or ammonium sulfate.
- electrolytes especially inorganic, such as alkali metal salts, expediently sodium salts, such as e.g. Sodium chloride or sodium sulfate, potassium salts such as e.g. Potassium chloride or potassium sulfate, ammonium salts such as e.g. Contain ammonium chloride or ammonium sulfate.
- electrolytes can be used in amounts of 1 to 20, preferably 5 to 10 percent by weight, based on the material to be colored.
- the dye liquors can also contain acids, e.g. Mineral acids, such as sulfuric acid or phosphoric acid or organic acids, suitably contain lower aliphatic carboxylic acids, such as formic, acetic or oxalic acid. These acids are used primarily to adjust the pH of the liquors used according to the invention, which is generally 2 to 8, preferably 3 to 6. To stabilize a certain pH, alkali metal acetate, e.g. Sodium acetate or ammonium acetate, citrate or phosphate may be present in the dye liquor.
- acids e.g. Mineral acids, such as sulfuric acid or phosphoric acid or organic acids, suitably contain lower aliphatic carboxylic acids, such as formic, acetic or oxalic acid. These acids are used primarily to adjust the pH of the liquors used according to the invention, which is generally 2 to 8, preferably 3 to 6.
- alkali metal acetate e.g. Sodium acetate or ammonium acetate, citrate or
- the dyeings are advantageously carried out from an aqueous liquor using the exhaust process.
- the liquor ratio depends on the equipment, the substrate and the packaging, and the packing density. However, it can be chosen within a wide range, e.g. 1: 4 to 1: 100, but is usually between 1: 5 to 1:40.
- the temperature at which dyeing is carried out is at least 70 ° C and generally it is not higher than 106 ° C. It is preferably in the range from 80 to 103 ° C.
- the process can be carried out in such a way that the material to be dyed is either first briefly treated with the auxiliary mixture according to the invention and then dyed, or preferably treated simultaneously with the auxiliary mixture and the dye.
- the material to be dyed is preferably allowed to advance at 70-90 ° C. in the bath, which is adjusted to a pH of 3 to 5, then the auxiliary mixture and the dye are added and the temperature is raised to 98 ° within 15 to 45 minutes C and dyeing at this temperature for 30 to 60 minutes, or one goes into the dyeing liquor at boiling temperature and dyeing at this temperature for 30 to 60 minutes.
- the dyeing liquor it is also possible for the dyeing liquor to be heated to a temperature of 105 ° C. in the course of 15 to 30 minutes (high-temperature dyeing) and then to be left at this temperature for 15 to 45 minutes.
- the dyeing liquor is slowly cooled and the dyeings are rinsed with water and dried.
- the acrylic fibers which can be dyed by the process according to the invention include the commercially available types of polymeric or mixed-polymer acrylonitrile.
- the proportion of acrylonitrile is expediently at least 80% by weight, based on the weight of the copolymer.
- polyacrylonitrile fibers consist of approximately 85% by weight of acrylonitrile and approximately 15% of copolymer.
- the polyacrylonitrile fibers can have different draw properties, ie the process according to the invention can be applied to all types of polyacrylonitrile fibers, namely to so-called fast-pulling, normal-pulling and slow-pulling polyacrylonitrile fibers.
- the fiber material to be dyed can be in various forms. Examples include: loose material, sliver, cable, yarn, cross-wound bobbins, warp beams, muffs, wound packages, knitted fabrics, fabrics, carpets.
- the fiber materials can also be used as blended fabrics with one another or with other fibers, for example mixtures of polyacrylonitrile / cotton, polyacrylonitrile / polyester or polyacrylonitrile / wool.
- level individual and in particular mixed tone dyeings are achieved at the usual dyeing temperatures and when using non-migrating or migrating dyes.
- areas of the substrate which have hydrophobic impurities and therefore undesirable air bubbles can also be dyed in any way, since the auxiliary mixture according to the invention acts simultaneously as a deaerating and retarding agent.
- the method according to the invention enables any over-dyeing of irregular dyeings in black. It also allows nuances at cooking temperature.
- the dyeings obtained are distinguished by good fastness properties, in particular wet fastness properties such as fastness to washing, water, sweat and decorative.
- the other fastnesses of the dyeings e.g. Lightfastness and fastness to rubbing are not influenced by the use of the auxiliary mixtures according to the invention.
- the percentages are by weight unless otherwise specified.
- the amounts of the dyes relate to commercial, i.e. Coucher goods and with quaternary ammonium compounds and amine oxides on pure substance.
- For the dyes and the quaternary ammonium salts mean: K cation weight, Pa Parachor and log P relative lipophilicity.
- the dyeing liquor is then slowly cooled to 60 ° C. and the yarn is rinsed and dried.
- a well-dyed yarn with a level gray coloration of good wet, light and rub fastness properties is obtained.
- the color is much quieter than the color obtained when the quaternary ammonium compound is used without the amine oxide being used.
- Example 2 Paraffin is partially applied by hand to a fabric made of normal-pulling polyacrylonitrile fibers and fixed at 60 ° C.
- a well-dyed fabric is obtained which shows no marking of the paraffin application.
- Example 3 2000 g of fast-pulling polyacrylonitrile yarn (as muff) are treated in a circulation apparatus with 34 liters of an aqueous dyeing liquor containing 200 g of calcined sodium sulfate and 40 ml of 80% acetic acid for 5 minutes at 70 ° C.
- the liquor is then allowed to circulate at 70 ° C. for a further 5 minutes, the temperature is then increased to 98 ° C. in the course of 30 minutes and dyeing is carried out at this temperature for 15 minutes.
- the yarn is knitted so that the inner and outer part lie side by side.
- the knitwear is characterized by excellent levelness, while maintaining good wet, light and rub fastness.
- Example 4 2 kg of a pre-shrunk yarn made of fast-drawing polyacrylonitrile fibers are treated in a circulation apparatus with 34 liters of an aqueous liquor which contains 200 g of calcined sodium sulfate and 40 ml of 80% acetic acid for 5 minutes at 70 ° C.
- the liquor is then left to circulate at 70 ° C. for a further 5 minutes, the temperature is raised to 98 ° C. in the course of 30 minutes and the fiber material is dyed at this temperature for 60 minutes.
- the liquor is then slowly cooled to 60 ° C., the substrate is rinsed and dried.
- Example 5 100 g of a furniture upholstery fabric consisting of polyacrylonitrile fibers and cotton (65:35) are mixed in a dyeing machine with 4000 ml of an aqueous liquor which contains 5 g of calcined sodium sulfate and is adjusted to a pH of 5 with 80% acetic acid , 5 minutes at 70 ° C treated. After that, the fleet
- the substrate is then treated for a further 5 minutes at 70 ° C. and the bath is then heated to 98 ° C. in the course of 30 minutes, after which the goods are dyed at this temperature for 30 minutes.
- the dyeing liquor is then slowly cooled to 60 ° C.
- the goods are then placed in a second dyebath which contains 30 g of calcined sodium sulfate in 4000 ml of water.
- Example 6 10 g of a mixed fabric consisting of polyacrylonitrile fibers and wool (50:50) are in a dyeing machine with an aqueous liquor containing 0.3 g of ammonium sulfate, 0.5 g of calcined sodium sulfate, 0.05 g of a mixture of a quaternized Addition product of 30 mol ethylene oxide to 1 mol C 20 -C 22 fatty amine and the acidic ester of the adduct 16 mol ethylene oxide to 1 mol tallow fatty acid amide (1: 2) and adjusted to pH 5 with 80% acetic acid, 5 Treated minutes at 50 ° C. After that
- auxiliary preparation (3) consisting of 35% of a quaternary ammonium compound of the formula (22), 10% of N-myristyl-N, N-dimethylamine oxide and 55% of water,
Abstract
Description
Gegenstand der vorliegenden Erfindung ist ein neues Färbereihilfsmittelgemisch, welches dadurch gekennzeichnet ist, dass es mindestens
- (A) ein quaternäres Ammoniumsalz, welches mindestens ein basisches Stickstoffatom aufweist, an welches mindestens ein aliphatischer Rest mit 6 bis 22 Kohlenstoffatomen gebunden ist, und
- (B) ein einen aliphatischen Rest mit 5 bis 22 Kohlenstoffatomen aufweisendes Aminoxid
enthält.The present invention relates to a new dyeing auxiliary mixture, which is characterized in that it is at least
- (A) a quaternary ammonium salt which has at least one basic nitrogen atom to which at least one aliphatic radical having 6 to 22 carbon atoms is bonded, and
- (B) an amine oxide having an aliphatic group of 5 to 22 carbon atoms
contains.
Vorliegendes Hilfsmittelgemisch eignet sich als Netz-, Entlüftungs-, Retardier- und Egalisiermittel beim Färben von langsam-, normal- oder schnellziehenden Polyacrylnitrilfasern mit migrierenden oder nicht- migrierenden kationischen Farbstoffen oder deren Gemischen.The present mixture of auxiliaries is suitable as a wetting, venting, retarding and leveling agent when dyeing slow, normal or fast-drawing polyacrylonitrile fibers with migrating or non-migrating cationic dyes or mixtures thereof.
Die als Komponente (A) verwendbaren quaternären Ammoniumsalze können migrierende oder nicht-migrierende Eigenschaften besitzen. Vorzugsweise werden jedoch migrierende quaternäre Ammoniumsalze eingesetzt, welche vorteilhafterweise gleichzeitig nur eine geringe Retardierwirkung zu Ende des Färbeprozesses besitzen.The quaternary ammonium salts which can be used as component (A) can have migrating or non-migrating properties. However, migrating quaternary ammonium salts are preferably used, which advantageously have only a low retarding effect at the end of the dyeing process.
Besonders geeignet sind solche quaternäre Ammoniumsalze, deren Kationgewicht kleiner als 400, vor allem kleiner als 250, deren Parachor kleiner als 1200, insbesondere kleiner als 800 und deren log P kleiner als 8 vorzugsweise kleiner als 7,0 ist. Unter diesen werden bevorzugt solche verwendet,.deren Kationgewicht kleiner als 275, deren Parachor kleiner als 700 und deren log P kleiner als 6,4 ist.Quaternary ammonium salts whose cation weight is less than 400, especially less than 250, whose parachor is less than 1200, in particular less than 800 and whose log P is less than 8, preferably less than 7.0, are particularly suitable. Among these, preference is given to those whose cation weight is less than 275, whose parachor is less than 700 and whose log P is less than 6.4.
Erfindungsgemäss verwendbare quaternäre Ammoniumsalze sind z.B. quaternäre Ammoniumverbindungen der Formel
- R einen aliphatischen Kohlenwasserstoffrest mit 5 bis 21 Kohlenstoffatomen, vorzugsweise 7 bis 18 Kohlenstoffatomen,
- Q die direkte Bindung oder Sauerstoff,
- Y1 und Y2' unabhängig voneinander, Niederalkyl, Cycloalkyl oder Hydroxyniederalkyl, vorzugsweise Methyl, Ethyl oder 2-Hydroxyethyl oder
- Y1 und Y2 zusammen mit dem sie verbindenden Stickstoffatom einen fünf- oder sechsgliedrigen, gesättigten, heterocyclischen Rest, wie z.B. Pyrrolidino, Piperidino oder Morpholino,
- Y3 Niederalkyl, Hydroxy-Niederalkyl, Epoxy-Niederalkyl, Cyano-Niederalkyl, Carbamoyl-Niederalkyl oder Aralkyl, wie z.B. Benzyl, Chlorbenzyl oder a-Methylbenzyl,
- Y1, Y2 und Y3 zusammen mit dem sie verbindenden Stickstoffatom einen gegebenenfalls durch Niederalkyl substituierten Pyridinring und
- R is an aliphatic hydrocarbon radical having 5 to 21 carbon atoms, preferably 7 to 18 carbon atoms,
- Q the direct bond or oxygen,
- Y 1 and Y 2 ' independently of one another, lower alkyl, cycloalkyl or hydroxy-lower alkyl, preferably methyl, ethyl or 2-hydroxyethyl or
- Y 1 and Y2 together with the nitrogen atom connecting them form a five- or six-membered, saturated, heterocyclic radical, such as, for example, pyrrolidino, piperidino or morpholino,
- Y 3 lower alkyl, hydroxy lower alkyl, epoxy lower alkyl, cyano lower alkyl, carbamoyl lower alkyl or aralkyl, such as, for example, benzyl, chlorobenzyl or a-methylbenzyl,
- Y 1 , Y 2 and Y 3 together with the nitrogen atom connecting them represent a pyridine ring which is optionally substituted by lower alkyl and
An⊖ das Anion einer organischen oder anorganischen Säure, wie z.B. das Chlorid-, Bromid-, Sulfat-, Benzolsulfonat-, p-Toluolsulfonat-, Methosulfat-, Ethosulfat- oder Methophosphation, bedeuten.An⊖ the anion of an organic or inorganic acid, e.g. the chloride, bromide, sulfate, benzenesulfonate, p-toluenesulfonate, methosulfate, ethosulfate or methophosphate ion mean.
Niederalkyl stellt in der Regel solche Gruppen oder Gruppenbestandteile dar, die 1 bis 5, insbesondere 1 bis 3, Kohlenstoffatome aufweisen, wie z.B. Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sek.-Butyl, tert.-Butyl oder Amyl.Lower alkyl generally represents those groups or group components which have 1 to 5, in particular 1 to 3, carbon atoms, such as, for example, Methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl or amyl.
In der Formel (1) bedeutet R vorzugsweise einen Alkylrest oder Alkenylrest mit jeweils 5 bis 21 Kohlenstoffatomen, besonders 7 bis 14 Kohlenstoffatomen. Beispiele für solche Alkylreste sind Pentyl, Hexyl, Octyl, Decyl, Dodecyl, Kokosyl, Myristyl, Hexadecyl, Heptadecyl, Octadecyl, Arachidyl oder Behenyl. Vorzugsweise ist R Pentyl, Hexyl, Octyl, Decyl, Dodecyl, Kokosyl oder Myristyl oder ein Gemisch dieser Alkylreste.In formula (1), R preferably denotes an alkyl radical or alkenyl radical each having 5 to 21 carbon atoms, especially 7 to 14 carbon atoms. Examples of such alkyl radicals are pentyl, hexyl, octyl, decyl, dodecyl, cocosyl, myristyl, hexadecyl, heptadecyl, octadecyl, arachidyl or behenyl. R is preferably pentyl, hexyl, octyl, decyl, dodecyl, cocosyl or myristyl or a mixture of these alkyl radicals.
Q ist vorzugsweise die direkte Bindung zwischen R und -CH2-.Q is preferably the direct bond between R and -CH 2 -.
Die Y-Reste können gleich oder voneinander verschieden sein.The Y radicals can be the same or different from one another.
Als Cycloalkylrest bedeuten Y1 und Y2 beispielsweise Cyclopentyl oder vorzugsweise Cyclohexyl.As the cycloalkyl radical, Y 1 and Y 2 mean, for example, cyclopentyl or preferably cyclohexyl.
Y1 und Y2 sind vorzugsweise Methyl, Ethyl oder vor allem 2-Hydroxyethyl.Y 1 and Y 2 are preferably methyl, ethyl or especially 2-hydroxyethyl.
Stellt Y3 einen Niederalkylrest dar, so ist er insbesondere Methyl oder Ethyl. Bedeutet Y3 Hydroxy-Niederalkyl oder Cyano-Niederalkyl, so handelt es sich vor allem um 2-Hydroxyethyl, 3-Hydroxypropyl oder 2-Cyanoethyl. Als Epoxy-niederalkyl bedeutet Y3 vorzugsweise die Epoxypropylgruppe. Als Carbamoyl-Niederalkyl ist Y3 insbesondere die Carbamoylmethylgruppe. Y3 ist bevorzugt Methyl, Ethyl oder Benzyl.If Y 3 represents a lower alkyl radical, it is in particular methyl or ethyl. If Y 3 is hydroxy-lower alkyl or cyano-lower alkyl, then it is primarily 2-hydroxyethyl, 3-hydroxypropyl or 2-cyanoethyl. As epoxy lower alkyl, Y 3 preferably denotes the epoxypropyl group. As carbamoyl lower alkyl, Y 3 is in particular the carbamoylmethyl group. Y 3 is preferably methyl, ethyl or benzyl.
Wenn Y1 und Y2 zusammen mit dem Stickstoffatom einen heterocyclischen Rest darstellen, so ist dieser beispielsweise Pyrrolidino, Piperidino, Pipecolino, Thiomorpholino oder vorzugsweise Morpholino.If Y 1 and Y 2 together with the nitrogen atom represent a heterocyclic radical, this is, for example, pyrrolidino, piperidino, pipecolino, thiomorpholino or preferably morpholino.
Als Anion An kommen sowohl Anionen anorganischer Säuren, z.B. das Chlorid-, Bromid-, Fluorid-, Sulfat- oder Phosphation als auch organischer Säuren, z.B. aromatischer oder aliphatischer Sulfonsäuren, wie z.B. das Benzolsulfonat-, p-Toluolsulfonat-, Chlorbenzolsulfonat-, Methansulfonat- oder Ethansulfonation sowie die Anionen saurer Alkylester anorganischer Säuren, wie z.B. das Methosulfat-, Ethosulfat- oder Methophosphation in Betracht. An ist vor allem das Chlorid- oder Methosulfation.Anions are both anions of inorganic acids, e.g. the chloride, bromide, fluoride, sulfate or phosphate ion as well as organic acids, e.g. aromatic or aliphatic sulfonic acids, e.g. the benzenesulfonate, p-toluenesulfonate, chlorobenzenesulfonate, methanesulfonate or ethanesulfonate ion and the anions of acidic alkyl esters of inorganic acids, such as e.g. the methosulfate, ethosulfate or methophosphate ion into consideration. Above all, the chloride or methosulfate ion.
Besonders geeignet unter den Verbindungen der Formel (1) sind quaternäre Ammoniumsalze der Formel
- R1 Alkyl mit 5 bis 15 Kohlenstoffatomen,
- Q Sauerstoff oder vorzugsweise die direkte Bindung,
- Y4 und Y5 Niederalkyl oder Hydroxy-Niederalkyl,
- Y6 Methyl, Ethyl oder Benzyl und
-
bedeuten.Quaternary ammonium salts of the formula are particularly suitable among the compounds of the formula (1)
- R 1 alkyl having 5 to 15 carbon atoms,
- Q is oxygen or preferably the direct bond,
- Y 4 and Y 5 lower alkyl or hydroxy lower alkyl,
- Y 6 is methyl, ethyl or benzyl and
-
mean.
Praktisch wichtige Vertreter von quaternären Ammoniumverbindungen der Formel (2) sind N-Hexyl-N,N,N-trimethylammoniumchlorid, N-n-Dodecyl-N,N,N-trimethylammoniumchlorid, N-n-Dodecyl-N,N-di-2-hydroxyethyl-N-benzylammoniumchlorid, N-n-Dodecyl-N,N-di-2-hydroxymethyl-N-methyl- ammoniummethosulfat, N-n-Dodecyloxymethyl-N,N,N-trimethylammoniumchlorid, N-Kokosyl-N,N-di-2-hydroxyethyl-N-methyl-ammoniummethosulfat, N-Cetyl-N,N,N-trimethylammoniumchlorid, N-Oleyl-N,N-dimethyl-N-benzyl- ammoniumchlorid, N-Stearyl-N,N-dimethyl-N-benzylammoniumchlorid, oder vor allem N-Kokosyl-N,N,N-trimethylammonium-methosulfat, N-Kokosyl-N,N-dimethyl-N-benzylammoniumchlorid oder N-Kokosyl-N,N-di-2-hydroxyethyl-N-benzylammoniumchlorid.Practically important representatives of quaternary ammonium compounds of the formula (2) are N-hexyl-N, N, N-trimethylammonium chloride, Nn-dodecyl-N, N, N-trimethylammonium chloride, Nn-dodecyl-N, N-di-2-hydroxyethyl- N-benzylammonium chloride, Nn-dodecyl-N, N-di-2-hydroxymethyl-N-methylammonium methosulfate, Nn-dodecyloxymethyl-N, N, N-trimethylammonium chloride, N-cocosyl-N, N-di-2-hydroxyethyl- N-methyl-ammonium methosulfate, N-cetyl-N, N, N-trimethylammonium chloride, N-oleyl-N, N-dimethyl-N-benzylammonium chloride, N-stearyl-N, N-dimethyl-N-benzylammonium chloride, or before all N-cocosyl-N, N, N-trimethylammonium methosulfate, N-cocosyl-N, N-dimethyl-N-benzylammonium chloride or N-cocosyl-N, N-di-2-hydroxyethyl-N-benzylammonium chloride.
Ferner können quaternäre Ammoniumsalze der Formel
Von diesen sind die Verbindungen der Formel
Ebenfalls geeignet sind quaternäre Ammoniumsalze der Formel
Als Beispiele dieser Verbindungen der Formel (5) seien definitionsgemässe quaternäre Ammoniumsalze genannt, die z.B. durch Umsetzung von Kokosölfettsäurechlorid mit N,N-Dimethylpropylendiamin und anschliessend durch Quaternisierung mit Methylchlorid, Dimethylsulfat, Glykolchlorhydrin, Epichlorhydrin oder Benzylchlorid erhalten werden.Examples of these compounds of formula (5) are quaternary ammonium salts by definition, which e.g. by reaction of coconut oil fatty acid chloride with N, N-dimethylpropylenediamine and then by quaternization with methyl chloride, dimethyl sulfate, glycol chlorohydrin, epichlorohydrin or benzyl chloride.
Weitere quaternäre Ammoniumsalze, welche als Komponente (A) verwendet werden können, entsprechen der Formel
- v1 Alkyl mit 6 bis 18 Kohlenstoffatomen,
- V2 Niederalkyl, Hydroxy-Niederalkyl oder Benzyl und
- R4 Wasserstoff, Alkyl mit 1 bis 18, vorzugsweise 1 bis 4 Kohlenstoffatomen oder Phenyl bedeuten, und
- An⊖ die oben angegebene Bedeutung hat,
oder der Formel
- v 1 alkyl having 6 to 18 carbon atoms,
- V 2 lower alkyl, hydroxy lower alkyl or benzyl and
- R 4 is hydrogen, alkyl having 1 to 18, preferably 1 to 4 carbon atoms or phenyl, and
- Has the meaning given above,
or the formula
Als Beispiele von Verbindungen der Formel (6) seien genannt:
- 1-Dodecyl-3-benzyl-imidazoliumchlorid und 1-Hexadecyl-2-isopropyl-3-methylimidazolium-methosulfat.
- 1-dodecyl-3-benzyl-imidazolium chloride and 1-hexadecyl-2-isopropyl-3-methylimidazolium methosulfate.
Als Beispiele geeigneter Verbindungen der Formel (7) seien genannt: N-Octadecyl-guanidiniumchlorid, N-Hexadecyl-N'-methyl-N"-2-hydroxy- ethylguanidiniumchlorid und 2-Octylaminoimidazoliumacetat.Examples of suitable compounds of the formula (7) are: N-octadecyl-guanidinium chloride, N-hexadecyl-N'-methyl-N "-2-hydroxyethylguanidinium chloride and 2-octylaminoimidazolium acetate.
Im erfindungsgemässen Hilfsmittelgemisch können auch Gemische definitionsgemässer quaternärer Ammoniumsalze als Komponente (A) verwendet werden.Mixtures of quaternary ammonium salts according to the definition can also be used as component (A) in the auxiliary mixture according to the invention.
Unter den Verbindungen der Formeln (1) bis (7) werden diejenigen der Formel (2) besonders bevorzugt, in der Q die direkte Bindung bedeutet. Die definitionsgemässen quaternären Ammoniumsalze werden in Mengen von 20 bis 50 Gewichtsprozent, bezogen auf das Gesamtgewicht des Hilfsmittelgemisches, eingesetzt.Among the compounds of the formulas (1) to (7), those of the formula (2) in which Q denotes the direct bond are particularly preferred. The quaternary ammonium salts by definition are used in amounts of 20 to 50 percent by weight, based on the total weight of the auxiliary mixture.
Die als Komponente (B) in Betracht kommenden Aminoxide entsprechen zweckmässigerweise der Formel
Besonders geeignete Komponenten (B) sind Aminoxide der Formel
- X5 Alkyl oder Alkenyl je mit 8 bis 18 Kohlenstoffatomen,
- X4 und X6 unabhängig voneinander Niederalkyl oder Hydroxy-Niederalkyl,
- n 2 oder 3 und
- r 0 oder 1 bedeuten.
Bevorzugt unter diesen sind Verbindungen der Formel (9), in der r 0 ist.Particularly suitable components (B) are amine oxides of the formula
- X 5 alkyl or alkenyl each having 8 to 18 carbon atoms,
- X 4 and X 6 independently of one another are lower alkyl or hydroxy-lower alkyl,
- n 2 or 3 and
- r is 0 or 1.
Preferred among these are compounds of the formula (9) in which r is 0.
Auch Gemische, welche zwei oder mehrere der Aminoxide der Formel (8) oder (9) enthalten, können im erfindungsgemässen Hilfsmittelgemisch vorhanden sein.Mixtures which contain two or more of the amine oxides of the formula (8) or (9) can also be present in the auxiliary mixture according to the invention.
Praktisch wichtige Vertreter von Aminoxiden der Formel (8) oder (9) sind:
- N-Dodecyl-N,N-dimethylaminoxid
- N-Myristyl-N,N-dimethylaminoxid
- N-Dodecyl-N,N-di-2-hydroxyethylaminoxid
- N-Hexadecyl-N,N-di-2-hydroxyethylaminoxid
- N-Hexadecyl-N,N-dimethylaminoxid
- N-Stearyl-N,N-dimethylaminoxid
- N-Oleyl-N,N-di-2-hydroxyethylaminoxid
- N-Stearyl-N,N-di-2-hydroxyethylaminoxid
- N-Kokosfettsäureamidopropyl-N,N-dimethylaminoxid
- N-Talgfettsäureamidopropyl-N,N-dimethylaminoxid
- N-Kokosyl-N,N-di-2-hydroxyethylaminoxid.
- N-dodecyl-N, N-dimethylamine oxide
- N-myristyl-N, N-dimethylamine oxide
- N-dodecyl-N, N-di-2-hydroxyethylamine oxide
- N-hexadecyl-N, N-di-2-hydroxyethylamine oxide
- N-hexadecyl-N, N-dimethylamine oxide
- N-stearyl-N, N-dimethylamine oxide
- N-oleyl-N, N-di-2-hydroxyethylamine oxide
- N-stearyl-N, N-di-2-hydroxyethylamine oxide
- N-coconut fatty acid amidopropyl-N, N-dimethylamine oxide
- N-tallow fatty acid amidopropyl-N, N-dimethylamine oxide
- N-Cocosyl-N, N-di-2-hydroxyethylamine oxide.
Auch Gemische dieser Aminoxide können vorteilhafterweise verwendet werden.Mixtures of these amine oxides can also be used advantageously.
Die Aminoxide der Formel (8) oder (9) werden in Mengen von 10 bis 25, vorzugsweise 12 bis 20, Gewichtsprozent, bezogen auf das Gesamtgewicht des wässrigen Hilfsmittelgemisches, eingesetzt.The amine oxides of the formula (8) or (9) are used in amounts of 10 to 25, preferably 12 to 20, percent by weight, based on the total weight of the aqueous auxiliary mixture.
Bevorzugte erfindungsgemässe Hilfsmittelgemische enthalten mindestens folgende Komponenten:
- (Aa) ein quaternäres Ammoniumsalz der Formel
- R2 Alkyl oder Alkenyl jeweils mit 6 bis 18 Kohlenstoffatomen,
- Y4 und Y5 Niederalkyl oder Hydroxy-Niederalkyl, insbesondere Methyl, Ethyl oder 2-Hydroxyethyl,
- Y 6 Methyl, Ethyl oder Benzyl und
-
- (Bb) ein Aminoxid der Formel
- (Aa) a quaternary ammonium salt of the formula
- R 2 is alkyl or alkenyl each having 6 to 18 carbon atoms,
- Y 4 and Y 5 lower alkyl or hydroxy lower alkyl, in particular methyl, ethyl or 2-hydroxyethyl,
- Y 6 is methyl, ethyl or benzyl and
-
- (Bb) an amine oxide of the formula
Die erfindungsgemässen Hilfsmittelzubereitungen können durch einfaches Verrühren der genannten Komponenten (A) und (B) vorzugsweise in Wasser hergestellt werden. Man erhält homogene, vorzugsweise wässerige klare Mischungen, die bei Raumtemperatur sehr gut lagerstabil sind. Die Komponenten (A) und (B) liegen in der Regel in einem Gewichtsverhältnis von 9:1 bis 3:7, vorzugsweise 6:1 bis 1:1 und insbesondere 4:1 bis 2:1 vor.The auxiliary preparations according to the invention can be prepared by simply stirring the components (A) and (B) mentioned, preferably in water. Homogeneous, preferably aqueous, clear mixtures are obtained which are very stable in storage at room temperature. Components (A) and (B) are generally present in a weight ratio of 9: 1 to 3: 7, preferably 6: 1 to 1: 1 and in particular 4: 1 to 2: 1.
Diese Hilfsmittelgemische enthalten vorzugsweise, bezogen auf das Gesamtgemisch
- 25 bis 45 Gewichtsprozent der Komponente (A)
- 8 bis 20 Gewichtsprozent der Komponente (B) und
- 35 bis 67 Gewichtsprozent Wasser.
- 25 to 45 percent by weight of component (A)
- 8 to 20 percent by weight of component (B) and
- 35 to 67 weight percent water.
Die neuen Formulierungen werden insbesondere als Netz-, Entlüftungs-und insbesondere Egalisier- und Retardiermittel beim Färben von Polyacrylnitrilfasermaterialien verwendet. Sie erlauben somit eine einwandfreie Egalität des gefärbten Substrates zu erzielen.The new formulations are used in particular as wetting, venting and in particular leveling and retarding agents in the dyeing of polyacrylonitrile fiber materials. They therefore allow the leveled substrate to be perfectly level.
Gegenstand der vorliegenden Erfindung ist demnach auch ein Verfahren zum Färben von Polyacrylnitrilfasern mit kationischen Farbstoffen. Das Verfahren ist dadurch gekennzeichnet, dass man dieses Material in.Gegenwart des erfindungsgemässen Hilfsmittelgemisches färbt. Dabei können Komponenten (A) und (B) auch getrennt dem Färbebad zugegeben werden.The present invention accordingly also relates to a process for dyeing polyacrylonitrile fibers with cationic dyes. The process is characterized in that this material is dyed in the presence of the auxiliary mixture according to the invention. Components (A) and (B) can also be added separately to the dyebath.
Die Einsatzmengen, in denen das erfindungsgemässe Hilfsmittelgemisch dem Färbebad zugesetzt wird, bewegen sich vorteilhafterweise zwischen 0,1 bis 5 Gewichtsprozent, vorzugsweise 0,5 bis 3 Gewichtsprozent, bezogen auf das Gewicht des Färbegutes.The amounts used in which the auxiliary mixture according to the invention is added to the dyebath, advantageously range between 0.1 to 5 percent by weight, preferably 0.5 to 3 percent by weight, based on the weight of the material to be dyed.
Als kationische Farbstoffe können sowohl migrierende als auch nicht-migrierende Farbstoffe eingesetzt werden.Both migrating and non-migrating dyes can be used as cationic dyes.
Als migrierende kationische Farbstoffe sind insbesondere solche mit einer mehr oder weniger delokalisierten positiven Ladung geeignet, deren Kationgewicht kleiner als 310, deren Parachor kleiner als 750 und deren log P kleiner als 3,2 ist. Der Parachor wird gemäss dem Artikel von O.R. Quayle [Chem. Rev. 53, 439 (1953)] berechnet und log P bedeutet die relative Lipophilie, deren Berechnung von C. Hanach et al [J.Med.Chem. 16, 1207 (1973)] beschrieben wurde. Dabei wurde der Einfluss der Ladung der Farbstoffkationen nicht berücksichtigt, was um 6 log Einheiten höhere log P-Werte ergibt. Bevorzugt migrierende kationische Farbstoffe sind solche, deren Kationgewicht kleiner als 275, deren Parachor kleiner als 680 und deren log P kleiner als 2,8 ist,Particularly suitable as migrating cationic dyes are those with a more or less delocalized positive charge, the cation weight of which is less than 310, the parachor of which is less than 750 and the log P of which is less than 3.2. The Parachor is according to the article by O.R. Quayle [Chem. Rev. 53, 439 (1953)] and log P means the relative lipophilicity, the calculation of which by C. Hanach et al [J.Med.Chem. 16, 1207 (1973)]. The influence of the charge of the dye cations was not taken into account, which results in 6 log units higher log P values. Preferred migrating cationic dyes are those whose cation weight is less than 275, whose parachor is less than 680 and whose log P is less than 2.8,
Nicht-migrierende kationische Farbstoffe sind insbesondere diejenigen, deren Kationgewicht grösser als 310 und deren Parachor grösser als 750 ist.Non-migrating cationic dyes are, in particular, those whose cation weight is greater than 310 and whose parachor is greater than 750.
Die kationischen, migrierenden und nichtmigrierenden Farbstoffe können verschiedenen Farbstoffklassen angehören. Insbesondere handelt es sich um Salze, beispielsweise Chloride, Sulfate oder Metallhalogenide, beispielsweise Zinkchloriddoppelsalze von Azofarbstoffen, wie Monoazofarbstoffen oder Hydrazonfarbstoffen, Anthrachinon-, Diphenylmethan-, Triphenylmethan-, Methin-, Azomethin-, Cumarin-, Ketonimin-, Cyanin-, Xanthen-, Azin-, Oxazin- oder Thiazinfarbstoffen.The cationic, migrating and non-migrating dyes can belong to different classes of dyes. In particular, they are salts, for example chlorides, sulfates or metal halides, for example zinc chloride double salts of azo dyes, such as monoazo dyes or hydrazone dyes, anthraquinone, diphenylmethane, triphenylmethane, methine, azomethine, coumarin, ketonimine, cyanine, xanthene , Azine, oxazine or thiazine dyes.
Es können auch Mischungen der kationischen Farbstoffe eingesetzt werden. Besonders bevorzugt sind Farbstoffkombinationen von mindestens 2 oder vorzugsweise 3 migrierenden oder nicht-migrierenden kationischen Farbstoffen zur Herstellung egaler Dichromie- oder Trichromiefärbungen, wobei auch Gemische aus migrierenden und nicht- migrierenden kationischen Farbstoffen verwendet werden können.Mixtures of the cationic dyes can also be used will. Dye combinations of at least 2 or preferably 3 migrating or non-migrating cationic dyes are particularly preferred for producing level dichromia or trichromatic dyeings, it also being possible to use mixtures of migrating and non-migrating cationic dyes.
Die Menge der der Flotte zugesetzten Farbstoffe richtet sich nach der gewünschten Farbtiefe. Im allgemeinen haben sich Farbstoffmengen von 0,01 bis 5, vorzugsweise 0,05 bis 2 Gewichtsprozent, bezogen auf das Gewicht des Färbegutes, als vorteilhaft erwiesen.The amount of dyes added to the liquor depends on the desired depth of color. In general, amounts of dye of 0.01 to 5, preferably 0.05 to 2 percent by weight, based on the weight of the material to be dyed, have proven to be advantageous.
Die Färbeflotte kann auch Elektrolyte, insbesondere anorganische, wie Alkalimetallsalze, zweckmässig Natriumsalze, wie z.B. Natriumchlorid oder Natriumsulfat, Kaliumsalze, wie z.B. Kaliumchlorid oder Kaliumsulfat, Ammoniumsalze, wie z.B. Ammoniumchlorid oder Ammoniumsulfat enthalten. Diese Elektrolyte können in Mengen von 1 bis 20, vorzugsweise 5 bis 10 Gewichtsprozent, bezogen auf das zu färbende Material, eingesetzt werden.The dye liquor can also electrolytes, especially inorganic, such as alkali metal salts, expediently sodium salts, such as e.g. Sodium chloride or sodium sulfate, potassium salts such as e.g. Potassium chloride or potassium sulfate, ammonium salts such as e.g. Contain ammonium chloride or ammonium sulfate. These electrolytes can be used in amounts of 1 to 20, preferably 5 to 10 percent by weight, based on the material to be colored.
Daneben können die Färbeflotten Säuren, z.B. Mineralsäuren, wie Schwefelsäure oder Phosphorsäure oder organische Säuren, zweckmässig niedere aliphatische Carbonsäuren, wie Ameisen-, Essig- oder Oxalsäure, enthalten. Diese Säuren dienen vor allem der Einstellung des pH-Wertes der erfindungsgemäss verwendeten Flotten, der in der Regel 2 bis 8, vorzugsweise 3 bis 6, beträgt. Zur Stabilisierung eines bestimmten pH-Wertes können auch Alkalimetallacetat, z.B. Natriumacetat oder Ammoniumacetat, -citrat oder -phosphat in der Färbeflotte vorhanden sein.The dye liquors can also contain acids, e.g. Mineral acids, such as sulfuric acid or phosphoric acid or organic acids, suitably contain lower aliphatic carboxylic acids, such as formic, acetic or oxalic acid. These acids are used primarily to adjust the pH of the liquors used according to the invention, which is generally 2 to 8, preferably 3 to 6. To stabilize a certain pH, alkali metal acetate, e.g. Sodium acetate or ammonium acetate, citrate or phosphate may be present in the dye liquor.
Die Färbungen erfolgen mit Vorteil aus wässeriger Flotte nach dem Ausziehverfahren. Das Flottenverhältnis ist von den apparativen Gegebenheiten, vom Substrat und der Aufmachungsform sowie von der Packungsdichte abhängig. Es kann jedoch innerhalb eines weiten Bereiches gewählt werden, z.B. 1:4 bis 1:100, liegt aber meistens zwischen 1:5 bis 1:40.The dyeings are advantageously carried out from an aqueous liquor using the exhaust process. The liquor ratio depends on the equipment, the substrate and the packaging, and the packing density. However, it can be chosen within a wide range, e.g. 1: 4 to 1: 100, but is usually between 1: 5 to 1:40.
Die Temperatur, bei der gefärbt wird, beträgt mindestens 70°C und in der Regel ist sie nicht höher als 106°C. Vorzugsweise liegt sie im Bereich von 80 bis 103°C.The temperature at which dyeing is carried out is at least 70 ° C and generally it is not higher than 106 ° C. It is preferably in the range from 80 to 103 ° C.
Das Verfahren kann so durchgeführt werden, dass man das Färbegut entweder zuerst mit dem erfindungsgemässen Hilfsmittelgemisch kurz behandelt und anschliessend färbt, oder vorzugsweise gleichzeitig mit dem Hilfsmittelgemisch und dem Farbstoff behandelt. Vorzugsweise lässt man das Färbegut bei 70-90°C im Bad, das auf einen pH-Wert von 3 bis 5 eingestellt ist, vorlaufen, setzt dann das Hilfsmittelgemisch und den Farbstoff zu und steigert die Temperatur innerhalb von 15 bis 45 Minuten auf 98°C und färbt während 30 bis 60 Minuten bei dieser Temperatur, oder man geht bei Kochtemperatur in die Färbeflotte ein und färbt während 30 bis 60 Minuten bei dieser Temperatur. Es ist aber auch möglich, dass man die Färbeflotte im Verlauf von 15 bis 30 Minuten auf eine Temperatur von 105°C erhitzt (Hochtemperaturfärbung) und dann 15 bis 45 Minuten bei dieser Temperatur belässt.The process can be carried out in such a way that the material to be dyed is either first briefly treated with the auxiliary mixture according to the invention and then dyed, or preferably treated simultaneously with the auxiliary mixture and the dye. The material to be dyed is preferably allowed to advance at 70-90 ° C. in the bath, which is adjusted to a pH of 3 to 5, then the auxiliary mixture and the dye are added and the temperature is raised to 98 ° within 15 to 45 minutes C and dyeing at this temperature for 30 to 60 minutes, or one goes into the dyeing liquor at boiling temperature and dyeing at this temperature for 30 to 60 minutes. However, it is also possible for the dyeing liquor to be heated to a temperature of 105 ° C. in the course of 15 to 30 minutes (high-temperature dyeing) and then to be left at this temperature for 15 to 45 minutes.
Am Schluss der Färbung wird die Färbeflotte langsam abgekühlt und die Ausfärbungen mit Wasser gespült und getrocknet.At the end of the dyeing, the dyeing liquor is slowly cooled and the dyeings are rinsed with water and dried.
Zu den Acrylfasern, die nach dem erfindungsgemässen Verfahren gefärbt werden können, gehören die handelsüblichen Typen von polymerem oder mischpolymerem Acrylnitril. Im Falle der Acrylnitrilmischpolymerisate beträgt der Mengenanteil Acrylnitril zweckmässig mindestens 80 Gew.Z, bezogen auf das Gewicht des Mischpolymerisats. In der Regel bestehen Polyacrylnitrilfasern aus ca. 85 Gew.% Acrylnitrilanteil und ca. 15% Copolymeranteil.The acrylic fibers which can be dyed by the process according to the invention include the commercially available types of polymeric or mixed-polymer acrylonitrile. In the case of the acrylonitrile copolymers, the proportion of acrylonitrile is expediently at least 80% by weight, based on the weight of the copolymer. As a rule, polyacrylonitrile fibers consist of approximately 85% by weight of acrylonitrile and approximately 15% of copolymer.
Die Polyacrylnitrilfasern können von unterschiedlichem Ziehvermögen sein, d.h. das erfindungsgemässe Verfahren lässt sich auf alle Faserarten von Polyacrylnitril anwenden und zwar auf sogenannte schnellziehende, normalziehende und langsamziehende Polyacrylnitrilfasern. Das zu färbende Fasermaterial kann sich in verschiedenen Aufmachungsformen befinden. Beispielsweise kommen in Betracht: loses Material, Kammzug, Kabel, Garn, Kreuzspulen, Kettbaum, Muffs, Wickelkörper, Maschenware, Gewebe, Teppich. Die Fasermaterialien können auch als Mischgewebe unter sich oder mit anderen Fasern, z.B. Mischungen aus Polyacrylnitril/Baumwolle, Polyacrylnitril/Polyester oder Polyacrylnitril/Wolle, eingesetzt werden.The polyacrylonitrile fibers can have different draw properties, ie the process according to the invention can be applied to all types of polyacrylonitrile fibers, namely to so-called fast-pulling, normal-pulling and slow-pulling polyacrylonitrile fibers. The fiber material to be dyed can be in various forms. Examples include: loose material, sliver, cable, yarn, cross-wound bobbins, warp beams, muffs, wound packages, knitted fabrics, fabrics, carpets. The fiber materials can also be used as blended fabrics with one another or with other fibers, for example mixtures of polyacrylonitrile / cotton, polyacrylonitrile / polyester or polyacrylonitrile / wool.
Wie bereits erwähnt, werden gemäss dem erfindungsgemässen Verfahren egale Einzel- und insbesondere Mischtonfärbungen bei üblichen Färbetemperaturen und bei Verwendung nicht- oder migrierender Farbstoffe erzielt. Unabhängig vom zu färbenden Polyacrylnitrilfasertyp können ebenfalls Stellen des Substrates, die hydrophobe Verunreinigungen und daher unerwünschte Luftblasen aufweisen, egal gefärbt werden, da das erfindungsgemässe Hilfsmittelgemisch gleichzeitig als Entlüftungs-und Retardiermittel wirkt. Zudem ermöglicht das erfindungsgemässe Verfahren ein allfälliges Ueberfärben unegal anfallender Färbungen in Schwarz. Ferner erlaubt es das Nuancieren bei Kochtemperatur.As already mentioned, level individual and in particular mixed tone dyeings are achieved at the usual dyeing temperatures and when using non-migrating or migrating dyes. Irrespective of the type of polyacrylonitrile fiber to be dyed, areas of the substrate which have hydrophobic impurities and therefore undesirable air bubbles can also be dyed in any way, since the auxiliary mixture according to the invention acts simultaneously as a deaerating and retarding agent. In addition, the method according to the invention enables any over-dyeing of irregular dyeings in black. It also allows nuances at cooking temperature.
Die erhaltenen Färbungen sind ausgezeichnet durch gute Echtheiten, insbesondere Nassechtheiten wie Wasch-, Wasser-, Schweiss- und Dekaturechtheit. Die anderen Echtheiten der Färbungen, z.B. Lichtechtheit und Reibechtheit, werden durch den Einsatz der erfindungsgemässen Hilfsmittelgemische nicht beeinflusst.The dyeings obtained are distinguished by good fastness properties, in particular wet fastness properties such as fastness to washing, water, sweat and decorative. The other fastnesses of the dyeings, e.g. Lightfastness and fastness to rubbing are not influenced by the use of the auxiliary mixtures according to the invention.
In den folgenden Beispielen beziehen sich die Prozentsätze, wenn nichts anderes angegeben ist, auf das Gewicht. Die Mengen beziehen sich bei den Farbstoffen auf handelsübliche, d.h. coupierte Ware und bei den quaternären Ammoniumverbindungen und Aminoxiden auf Reinsubstanz. Bei den Farbstoffen und den quaternären Ammoniumsalzen bedeuten: K Kationgewicht, Pa Parachor und log P relative Lipophilie.In the following examples, the percentages are by weight unless otherwise specified. The amounts of the dyes relate to commercial, i.e. Coupé goods and with quaternary ammonium compounds and amine oxides on pure substance. For the dyes and the quaternary ammonium salts mean: K cation weight, Pa Parachor and log P relative lipophilicity.
Beispiel 1: 2 kg eines vorgeschrumpften Garnes aus schnellziehenden Polyacrylnitrilfasern werden in einem Färbeapparat mit 34 Liter einer wässerigen Flotte, die 200 g kalziniertes Natriumsulfat enthält, und mit 80%iger Essigsäure auf einen pH-Wert von 4 eingestellt ist, 5 Minuten bei 80°C behandelt. Alsdann werden der Flotte
- 45 g der Hilfsmittelzubereitung (1), bestehend aus 35% einer quaternären Ammonium-Verbindung der Formel
- 45 g of the auxiliary preparation (1), consisting of 35% of a quaternary ammonium compound of the formula
Kationgewicht: 330 Parachor: 814 log P: 4,15 0,45 g des roten Farbstoffs der Formel
Kationgewicht: 321 Parachor: 764 log P: 3,22 1,20 g des blauen Farbstoffes der Formel
Kationgewicht: 371 Parachor: 817 log P: 3,84 zugesetzt. Danach lässt man die Flotte weitere 5 Minuten bei 70°C zirkulieren und erhöht die Temperatur im Verlaufe von 60 Minuten auf 98°C, worauf das Garn während 60 Minuten bei dieser Temperatur gefärbt wird.Cation weight: 371 Parachor: 817 log P: 3.84 added. The liquor is then left to circulate at 70 ° C. for a further 5 minutes and the temperature is raised to 98 ° C. in the course of 60 minutes, after which the yarn is dyed at this temperature for 60 minutes.
Man kühlt anschliessend die Färbeflotte langsam auf 60°C ab und spült und trocknet das Garn.The dyeing liquor is then slowly cooled to 60 ° C. and the yarn is rinsed and dried.
Man erhält ein gut durchgefärbtes Garn mit einer egalen grauen Färbung von guten Nass-, Licht- und Reibechtheiten. Die Färbung ist viel ruhiger als die Färbung, die man erhält, wenn die quaternäre Ammonium- verbindung ohne die Mitverwendung des Aminoxides eingesetzt wird.A well-dyed yarn with a level gray coloration of good wet, light and rub fastness properties is obtained. The color is much quieter than the color obtained when the quaternary ammonium compound is used without the amine oxide being used.
Beispiel 2: Auf ein Gewebe aus normalziehenden Polyacrylnitilfasern wird von Hand Paraffin partiell aufgebracht und bei 60°C fixiert.Example 2: Paraffin is partially applied by hand to a fabric made of normal-pulling polyacrylonitrile fibers and fixed at 60 ° C.
5 g des mit Paraffin verunreinigten Gewebes werden in einem Färbeapparat mit 200 ml einer wässerigen Flotte, die 0,5 g kalziniertes Natriumsulfat enthält und mit 80%iger Essigsäure auf einen pH-Wert von 4 eingestellt ist, 5 Minuten bei 70°C behandelt. Alsdann werden der Flotte
- 0,08 g der Hilfsmittelzubereitung (1) und eine Farbstoffmischung bestehend aus
- 0,04 g des gelben Farbstoffes der Formel (101)
- 0,01 g des roten Farbstoffes der Formel (102) und
- 0,03 g des blauen Farbstoffes der Formel (103)
- zugesetzt. Hernach wird die Temperatur der Flotte im Verlaufe von 30 Minuten auf 98°C erhöht und dann das Gewebe während 30 Minuten bei dieser Temperatur gefärbt. Man kühlt anschliessend die Färbeflotte langsam auf 60°C ab und spült und trocknet das Gewebe.
- 0.08 g of the auxiliary preparation (1) and a dye mixture consisting of
- 0.04 g of the yellow dye of the formula (101)
- 0.01 g of the red dye of the formula (102) and
- 0.03 g of the blue dye of the formula (103)
- added. The temperature of the liquor is then raised to 98 ° C. in the course of 30 minutes and then the tissue in 30 minutes colored at this temperature. The dyeing liquor is then slowly cooled to 60 ° C. and the fabric is rinsed and dried.
Man erhält ein gut durchgefärbtes Gewebe, das keine Markierung des Paraffinauftrages zeigt.A well-dyed fabric is obtained which shows no marking of the paraffin application.
Beispiel 3: 2000 g schnellziehendes Polyacrylnitrilgarn (als Muff) werden in einem Zirkulationsapparat mit 34 Liter einer wässerigen Färbeflotte, die 200 g kalziniertes Natriumsulfat und 40 ml 80Zige Essigsäure enthält, 5 Minuten bei 70°C behandelt.Example 3: 2000 g of fast-pulling polyacrylonitrile yarn (as muff) are treated in a circulation apparatus with 34 liters of an aqueous dyeing liquor containing 200 g of calcined sodium sulfate and 40 ml of 80% acetic acid for 5 minutes at 70 ° C.
Danach werden der FärbeflotteThen the dye liquor
45 g der Hilfsmittelzubereitung (1)45 g of the auxiliary preparation (1)
4 g des gelben Farbstoffes der Formel -
Kationgewicht: 317 Parachor: 734 log P: 6,5Cation weight: 317 Parachor: 734 log P: 6.5
zugesetzt. Hiernach lässt man die Flotte weitere 5 Minuten bei 70°C zirkulieren, erhöht dann die Temperatur im Verlaufe von 30 Minuten auf 98°C und färbt 15 Minuten bei dieser Temperatur.added. The liquor is then allowed to circulate at 70 ° C. for a further 5 minutes, the temperature is then increased to 98 ° C. in the course of 30 minutes and dyeing is carried out at this temperature for 15 minutes.
Um zu nuancieren werden der Färbeflotte, ohne abzukühlen, 22,5 g der Hilfsmittelzubereitung (1) zugesetzt. Nach weiteren 5 Minuten werdenTo shade, 22.5 g of the auxiliary preparation (1) are added to the dye liquor without cooling. After another 5 minutes
0,4 g des blauen Farbstoffes der Formel (103)0.4 g of the blue dye of the formula (103)
beigefügt und weitere 40 Minuten bei 98°C gefärbt. Anschliessend wird die Flotte langsam auf 60°C abgekühlt, das Substrat gespült und getrocknet.added and dyed for a further 40 minutes at 98 ° C. The liquor is then slowly cooled to 60 ° C., the substrate is rinsed and dried.
Um etwaige Unegalitäten zu sehen, wird das Garn so verstrickt, dass der innere und äussere Teil nebeneinanderliegen. Das Strickgut zeichnet sich durch eine hervorragende Egalität aus, wobei die guten Nass-, Licht- und Reibechtheiten erhalten bleiben.In order to see any irregularities, the yarn is knitted so that the inner and outer part lie side by side. The knitwear is characterized by excellent levelness, while maintaining good wet, light and rub fastness.
Beispiel 4: 2 kg eines vorgeschrumpften Garnes aus schnellziehenden Polyacrylnitrilfasern werden in einem Zirkulationsapparat mit 34 Litern einer wässerigen Flotte, die 200 g kalziniertes Natriumsulfat und 40 ml 80%ige Essigsäure enthält, 5 Minuten bei 70°C behandelt.Example 4: 2 kg of a pre-shrunk yarn made of fast-drawing polyacrylonitrile fibers are treated in a circulation apparatus with 34 liters of an aqueous liquor which contains 200 g of calcined sodium sulfate and 40 ml of 80% acetic acid for 5 minutes at 70 ° C.
Danach werden der FlotteAfter that, the fleet
45 g der Hilfsmittelzubereitung (1)45 g of the auxiliary preparation (1)
1 g des gelben Farbstoffes der Formel1 g of the yellow dye of the formula
1 g des roten Farbstoffes der Formel
Kationgewicht: 230 Parachor: 574 log P: 0,92Cation weight: 230 Parachor: 574 log P: 0.92
2 g des blauen Frabstoffes der Formel
Kationgewicht: 270 Parachor: 577 log P: 1,97Cation weight: 270 Parachor: 577 log P: 1.97
zugesetzt.added.
Hiernach lässt man die Flotte weitere 5 Minuten bei 70°C zirkulieren, erhöht die Temperatur im Verlaufe von 30 Minuten auf 98°C und färbt das Fasergut während 60 Minuten bei dieser Temperatur.The liquor is then left to circulate at 70 ° C. for a further 5 minutes, the temperature is raised to 98 ° C. in the course of 30 minutes and the fiber material is dyed at this temperature for 60 minutes.
Anschliessend wird die Flotte langsam auf 60°C abgekühlt, das Substrat gespült und getrocknet.The liquor is then slowly cooled to 60 ° C., the substrate is rinsed and dried.
Man erhält so eine egale blaugraue Färbung mit guten Nass-, Licht-und Reibechtheiten.This gives a level blue-gray coloration with good wet, light and rub fastness properties.
Beispiel 5: 100 g eines Möbelpolsterstoffes, bestehend aus Polyacrylnitrilfasern und Baumwolle (65:35) werden in einem Färbeapparat mit 4000 ml einer wässerigen Flotte, die 5 g kalziniertes Natriumsulfat enthält und mit 80 %iger Essigsäure auf einen pH-Wert von 5 eingestellt ist, 5 Minuten bei 70° C behandelt. Hiernach werden der FlotteExample 5: 100 g of a furniture upholstery fabric consisting of polyacrylonitrile fibers and cotton (65:35) are mixed in a dyeing machine with 4000 ml of an aqueous liquor which contains 5 g of calcined sodium sulfate and is adjusted to a pH of 5 with 80% acetic acid , 5 minutes at 70 ° C treated. After that, the fleet
2 g der Hilfsmittelzubereitung (2), bestehend aus2 g of the auxiliary preparation (2) consisting of
35 % einer quaternären Ammoniumverbindung der Formel35% of a quaternary ammonium compound of the formula
55 % Wasser55% water
0,42 g des gelben Farbstoffes der Formel (101) und0.42 g of the yellow dye of the formula (101) and
0,38 g des roten Farbstoffes der Formel (102)0.38 g of the red dye of the formula (102)
gelöst zugesetzt. Danach wird das Substrat weitere 5 Minuten bei 70°C behandelt und anschliessend das Bad im Verlaufe von 30 Minuten auf 98°C erwärmt, worauf die Ware 30 Minuten bei dieser Temperatur gefärbt wird. Man kühlt dann die Färbeflotte langsam auf 60°C ab. Hierauf wird die Ware in ein zweites Färbebad eingebracht, welches 30 g kalziniertes Natriumsulfat in 4000 ml Wasser enthält.added dissolved. The substrate is then treated for a further 5 minutes at 70 ° C. and the bath is then heated to 98 ° C. in the course of 30 minutes, after which the goods are dyed at this temperature for 30 minutes. The dyeing liquor is then slowly cooled to 60 ° C. The goods are then placed in a second dyebath which contains 30 g of calcined sodium sulfate in 4000 ml of water.
Danach werden der FlotteAfter that, the fleet
2 g des Farbstoffes der Formel
Man färbt 45 Minuten bei 40° C, gibt dann 1 g Natriumcarbonat und nach 5 Minuten 2 ml einer 30 %igen wässerigen Natriumhydroxidlösung zu und behandelt das Substrat weitere 40 Minuten. Das Substrat wird schliesslich gespült, geseift und getrocknet.It is dyed for 45 minutes at 40 ° C., then 1 g of sodium carbonate and after 5 minutes 2 ml of a 30% aqueous sodium hydroxide solution are added and the substrate is treated for a further 40 minutes. Finally, the substrate is rinsed, soaped and dried.
Man erhält eine brillante rote Färbung des Möbelpolsterstoffes mit guten Echtheiten.A brilliant red coloring of the upholstery fabric with good fastness properties is obtained.
Beispiel 6: 10 g eines Mischgewebes, bestehend aus Polyacrylnitrilfasern und Wolle (50:50) werden in einem Färbeapparat mit einer wässerigen Flotte, die 0,3 g Ammoniumsulfat, 0,5 g kalziniertes Natriumsulfat , 0,05 g eines Gemisches aus einem quaternisierten Anlagerungsprodukt von 30 MolEthylenoxid an 1 Mol C20-C22-Fettamin und dem sauren Ester des Anlagerungsprodukts von 16 Mol Ethylenoxid an 1 Mol Talgfettsäureamid (1:2) und mit 80 %iger Essigsäure auf einen pH-Wert von 5 gestellt ist, 5 Minuten bei 50° C behandelt. Hiernach werdenExample 6: 10 g of a mixed fabric consisting of polyacrylonitrile fibers and wool (50:50) are in a dyeing machine with an aqueous liquor containing 0.3 g of ammonium sulfate, 0.5 g of calcined sodium sulfate, 0.05 g of a mixture of a quaternized Addition product of 30 mol ethylene oxide to 1 mol C 20 -C 22 fatty amine and the acidic ester of the adduct 16 mol ethylene oxide to 1 mol tallow fatty acid amide (1: 2) and adjusted to pH 5 with 80% acetic acid, 5 Treated minutes at 50 ° C. After that
0,012 g des Farbstoffs der Formel
0,0025 g des Farbstoffes der Formel
0,001 g des Farbstoffes der Formel
Man fügt nun der FarbflotteNow add the paint fleet
0,05 g der Hilfsmittelzubereitung (3) bestehend aus 35 % einer quaternären Ammoniumverbindung der Formel (22), 10 % N-Myristyl-N,N-dimethyl-aminoxid und 55 % Wasser,0.05 g of the auxiliary preparation (3) consisting of 35% of a quaternary ammonium compound of the formula (22), 10% of N-myristyl-N, N-dimethylamine oxide and 55% of water,
0,014 g des Farbstoffes der Formel (105),0.014 g of the dye of the formula (105),
0,004 g des Farbstoffes der Formel (106) und0.004 g of the dye of formula (106) and
0,0014 g des Farbstoffes der Formel (107)0.0014 g of the dye of the formula (107)
hinzu und färbt 45 Minuten bei 98°C. Hiernach wird die Färbeflotte in Verlauf von 10 Minuten abgekühlt, das Substrat gespült und getrocknet.add and dye for 45 minutes at 98 ° C. The dye liquor is then cooled in the course of 10 minutes, the substrate is rinsed and dried.
Man erhält so eine egale hellbraune Färbung mit guten Echtheiten.This gives a level, light brown color with good fastness properties.
Claims (16)
enthält.1. dyeing aid, characterized in that it is at least
contains.
bedeuten.2, dyeing aid according to claim 1, characterized in that component (A) is a quaternary ammonium compound of the formula
mean.
bedeuten.5. dyeing aid according to claim 1, characterized in that component (A) is a quaternary ammonium compound of the formula
mean.
enthält.10. dyeing aid according to claim 1, characterized in that it, based on the total mixture
contains.
enthält, färbt.12. A method for dyeing polyacrylonitrile fiber material with cationic dyes, characterized in that this material in the presence of an auxiliary which at least
contains, colors.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH5681/82 | 1982-09-27 | ||
CH568182 | 1982-09-27 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0105034A1 true EP0105034A1 (en) | 1984-04-04 |
EP0105034B1 EP0105034B1 (en) | 1986-04-23 |
Family
ID=4297609
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19830810418 Expired EP0105034B1 (en) | 1982-09-27 | 1983-09-21 | Dyeing aid and process for dyeing of polyacrylonitrile fibre material |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0105034B1 (en) |
JP (1) | JPS5976981A (en) |
DE (1) | DE3363184D1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0149116A2 (en) * | 1983-12-20 | 1985-07-24 | Bayer Ag | Process for dyeing fibrous materials from polyacrylonitrile or acrylonitrile copolymers and an auxiliary agent containing a retarder |
EP0790348A1 (en) * | 1996-02-15 | 1997-08-20 | DyStar Textilfarben GmbH & Co. Deutschland KG | Process for washing-off textile printed fabrics from aminated cotton or regenerated cellulose and silk fibers |
WO1997034041A1 (en) * | 1996-03-11 | 1997-09-18 | High Point Chemical Corporation | Biodegradable dye leveler compounds for acrylic fibers |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1134221A (en) * | 1965-01-29 | 1968-11-20 | Courtaulds Ltd | Improvements in and relating to the dyeing of pile fabrics |
DE1769172A1 (en) * | 1968-04-17 | 1971-09-02 | Bayer Ag | Process for dyeing or printing fiber materials containing NH groups |
DE2304548A1 (en) * | 1973-01-31 | 1974-08-01 | Bayer Ag | DYE PREPARATIONS |
DE2355808A1 (en) * | 1973-11-08 | 1975-05-22 | Basf Ag | PRINT PASTE FOR FIBER MATERIAL |
DE2548009A1 (en) * | 1974-10-29 | 1976-05-06 | Ciba Geigy Ag | PROCESS FOR LEVELING INTO COLORING OF SLOW, NORMAL AND FAST DRAWING POLYACRYLNITRILE MATERIALS |
DE2943750A1 (en) * | 1978-11-02 | 1980-05-14 | Ciba Geigy Ag | METHOD FOR COLORING POLYACRYLNITRILE FIBERS |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5529647B2 (en) * | 1972-08-16 | 1980-08-05 |
-
1983
- 1983-09-21 EP EP19830810418 patent/EP0105034B1/en not_active Expired
- 1983-09-21 DE DE8383810418T patent/DE3363184D1/en not_active Expired
- 1983-09-27 JP JP58177191A patent/JPS5976981A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1134221A (en) * | 1965-01-29 | 1968-11-20 | Courtaulds Ltd | Improvements in and relating to the dyeing of pile fabrics |
DE1769172A1 (en) * | 1968-04-17 | 1971-09-02 | Bayer Ag | Process for dyeing or printing fiber materials containing NH groups |
DE2304548A1 (en) * | 1973-01-31 | 1974-08-01 | Bayer Ag | DYE PREPARATIONS |
DE2355808A1 (en) * | 1973-11-08 | 1975-05-22 | Basf Ag | PRINT PASTE FOR FIBER MATERIAL |
DE2548009A1 (en) * | 1974-10-29 | 1976-05-06 | Ciba Geigy Ag | PROCESS FOR LEVELING INTO COLORING OF SLOW, NORMAL AND FAST DRAWING POLYACRYLNITRILE MATERIALS |
DE2943750A1 (en) * | 1978-11-02 | 1980-05-14 | Ciba Geigy Ag | METHOD FOR COLORING POLYACRYLNITRILE FIBERS |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0149116A2 (en) * | 1983-12-20 | 1985-07-24 | Bayer Ag | Process for dyeing fibrous materials from polyacrylonitrile or acrylonitrile copolymers and an auxiliary agent containing a retarder |
EP0149116A3 (en) * | 1983-12-20 | 1985-08-14 | Bayer Ag | Process for dyeing fibrous materials from polyacrylonitrile or acrylonitrile copolymers and an auxiliary agent containing a retarder |
EP0790348A1 (en) * | 1996-02-15 | 1997-08-20 | DyStar Textilfarben GmbH & Co. Deutschland KG | Process for washing-off textile printed fabrics from aminated cotton or regenerated cellulose and silk fibers |
WO1997034041A1 (en) * | 1996-03-11 | 1997-09-18 | High Point Chemical Corporation | Biodegradable dye leveler compounds for acrylic fibers |
AU722753B2 (en) * | 1996-03-11 | 2000-08-10 | High Point Chemical Corporation | Biodegradable dye leveler compounds for acrylic fibers |
Also Published As
Publication number | Publication date |
---|---|
EP0105034B1 (en) | 1986-04-23 |
DE3363184D1 (en) | 1986-05-28 |
JPS5976981A (en) | 1984-05-02 |
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