US3307901A - Process for dyeing polyamide textile materials and auxiliaries therefor - Google Patents

Process for dyeing polyamide textile materials and auxiliaries therefor Download PDF

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US3307901A
US3307901A US510063A US51006365A US3307901A US 3307901 A US3307901 A US 3307901A US 510063 A US510063 A US 510063A US 51006365 A US51006365 A US 51006365A US 3307901 A US3307901 A US 3307901A
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parts
dyeing
acid
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Bindler Jakob
Pugin Andre
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Novartis AG
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JR Geigy AG
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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
    • C09B47/24—Obtaining compounds having —COOH or —SO3H radicals, or derivatives thereof, directly bound to the phthalocyanine radical
    • C09B47/26—Amide radicals
    • 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 invention concerns in a first aspect a process for the dyeing of Wool with sulfonated metal phthalocyanines in level, fast turquoise blue to green shades of good color strength.
  • the present invention concerns quaternary ammonium compounds which are suitable as dyeing auxiliaries, and processes for the production thereof.
  • Certain sulfonated or sulfated copper phthalocyanines have attained importance for the dyeing of cellulose in pure, lightfast turquoise shades.
  • Sulfonated pinthalocyanines have also been suggested for the dyeing of wool.
  • the formation of the quaternary compound comprises first the addition of styrene oxide to said amine. It is generally suflicient to react these components by heating at least to 60 C. and preferably to from about C. to 200 C. depending on their composition and reactivity and generally in the presence of a basic catalyst such as sodium or potassium hydroxide, carbonate or alcoholate.
  • a basic catalyst such as sodium or potassium hydroxide, carbonate or alcoholate.
  • the styrene oxide can be incorporated in solutions of the amine and catalysts in inert organic solvents, or in the melts of amine and catalyst, if necessary under pressure. In general, raised temperatures of, for example, 80 C. up to about 200 C. are employed.
  • reaction product of styrene oxide and amine is then, if desired, reacted with from one to two equivalents of propylene oxide, followed by a subsequent reaction with preferably 10 to 30, and optionally with 18 to 22 equivalents of ethylene oxide.
  • the reaction with propylene oxide is not an essential requirement.
  • Said reactions with proplene oxide and ethylene oxide are carried out preferably at a temperature of from about 80 C. to about 200 C. in the presence of a basic catalyst such as sodium or potassium hydroxide, carbonate or alcoholate but in the absence of any solvent.
  • the resulting polyglycol ethers are thereupon quaternized at from about 70 C. to C. with an ester of lower alkanol and strong acid, to form the condensation product usable according to the invention.
  • Preferred intermediates are the products of addition of 1 equivalent of styrene oxide, 1 to 2 equivalents of propylene oxide and about 20 equivalents of ethylene oxide to octadecenylamine or octadecylamine or to technical mixtures thereof alone or with similar higher alkylamines such as technical oleylamine o-r sterylamine.
  • dimethyl sulfate but also diethyl sulfate, methyl or ethyl halides such as methyl iodide, methyl bromide, ethyl iodide, ethyl Ibromide, ethyl chloride, as well as the esters of aromatic sulfonic acids, e.g., the methyl esters of benzene sulfonic acids, toluene sulfonic acids, such as methyl or ethyl p-tosylate, halogenobenzene sulfonic acids and nitrobenzene sulfonic acids or chloro-or bromo-propionic acid methyl or ethyl esters are used as reactive esters of lower alkanols with a strong acid.
  • the reaction is performed by gradually mixing the components, at room temperature or with heating.
  • the alkylation can also be performed in the presence of inert organic solvents and diluents which are again removed on completion of the reaction, e.g., by distilling off, preferably under vacuum.
  • the quaternary ammonium compounds according to the invention are in the form of salts with the anions of the acids from which the alkylating agent used is derived: thus they contain as anion, e.g., one equivalent chlorine ion, bromine ion, iodine ion, benzene sulfonic acid ion, toluene sulfonic acid ion, halogenobenzene sulfonic acid ion, nitrobenzene sulfonic acid ion, ethosulfate ion and, preferably, methosulfate ion.
  • anion e.g., one equivalent chlorine ion, bromine ion, iodine ion, benzene sulfonic acid ion, toluene sulfonic acid ion, halogenobenzene sulfonic acid ion, nitrobenzene sulfonic acid ion, ethos
  • Quaternary ammonium compounds according to the invention form colorless, pasty, water soluble masses.
  • quaternized condensation products advantageously those are used which are derived from primary higher alkyl or aralkyl namely benzyl, or higher alkenyl amines, preferably those containing generally 8 to 19 carbon atoms and, in the case of higher alkyl and alkenylamine, preferably 10 to even as much as 22 carbon atoms, e.g., octylamine, decylamine, dodecylamine, tetradecylamine and mixtures thereof, hexadecylamine, octadecylamine, oleylamine and mixtures thereof, or of dodecylbenzylamine.
  • Particularly advantageous amines are oleylamine, sterylamine, and dodecylamine, especially oleylamine and dodecylamine, but also tetradecylamine, hexadecylamine, docosylamine and preferably, octadecenylamine or octadecylamine, or technical mixtures of such higher alkylamines, particularly those having substantial contents of octadeoenylamine or octadccylamine.
  • condensation products resulting from the above reaction sequence and employed in the process according to this invention are preferably mixtures of quaternary compounds of the probable formulas:
  • R is a higher alkyl, aralkyl or higher alkenyl radical
  • R is a lower alkyl radical, preferably methyl
  • A- is an anion of an acid (monovalent anion or the normal equivalent of a polyvalent anion)
  • the sum of a, b, c and d is a number from O to 4 inclusive (advantageously from 2 to 4 inclusive) while the sum of x, y, z and w is a number from 14 to 60 inclusive.
  • R represents an alkyl or alkenyl radical having 12 to 22 carbon atoms, preferably the oleyl or stearyl radical;
  • R represents a low alkyl radical, preferably the methyl group
  • n O or 1;
  • n and p are each 0, 1 or 2 with the condition that the sum of n and p is at most 2;
  • x and y are whole numbers the sum of which is from 1-0 to 30, preferably 18 to 22;
  • A- is tile equivalent of an anion, preferably the methosulfate ion.
  • the sum of the coefficients x and y represents an average value and mixtures according to the invention contain analogous compounds having polyalkyleneoxy substitutes of various chain lengths, but of the said average value.
  • the quaternary ammonium compounds according to the invention are valuable auxiliaries for the dyeing of polyamide material with anionic dyestuffs, in particular with sulfonated dyestuffs. Their advantageous properties become particularly apparent on dyeing wool with anionic dyestuffs containing more than one sulfonic acid group,
  • the quaternary ammonium compounds according to the invention act as levelling and shade-deepening agents.
  • the dyeing auxiliaries according to the invention are distinguished by their marked shade-strengthening action; compared with analogous compounds not containing the phenethyleneoxy radical and having the same color-strengthening action but which, then, must contain rshortened polyethyleneoxy groups having less than 10 ether oxygen atoms, the dyeing auxiliaries according to the invention are distinguished in that they produce dyeings which are faster to rubbing, and they completely eliminate the troublesome staining of the dyeing apparatus.
  • the sulfonated or sulfated metal phthalocyanines usable according to the invention are nickel or preferably copper phthalocyanines. They must be water soluble. They can be mixtures of different degrees of sulfonation or sulfation respectively. They can contain either sulfonic acid groups or sulfuric acid monoester groups or they can contain both types of these Water solubilizing substituents together.
  • the number of the sulfonic acid groups or of the sulfated sulfonic acid -B- or -y-hydroxyalkylamide groups is preferably 2 to 4.
  • the sulfonic acid groups are bound to the phthalocyanine structure and/ or to external aromatic radicals, in which case principally to .sulfonic acid arylamide or arylester groups.
  • the metal phthalocyanines can contain the usual substituents in phthalocyanine dyestuffs, for example, single halogens and/or single, possibly N-substituted sulfonic acid amide groups in the phthalocyanine structure and, in the external aromatic radicals, for example, possibly substituted alkyl, cycloalkyl, aralkyl, aryl, ether groups, halogens, nitro groups, if desired N-substituted carboxylic acid and sulfonic acid amide groups, acylamino, acyl, arylazo groups of the homocyclic and heterocyclic series.
  • substituents in phthalocyanine dyestuffs for example, single halogens and/or single, possibly N-substituted sulfonic acid amide groups in the phthalocyanine structure and, in the external aromatic radicals, for example, possibly substituted alkyl, cycloalkyl, aralkyl, aryl,
  • sulfonic acid amide groups are present which increase the water solubility, then a single sulfonic acid group is suflicient as salt-forming acid substituent.
  • substituent of the said N-su'bstituted sulfonic acid amide groups can be employed: lower alkyl groups such as methyl, ethyl, propyl, butyl groups; low substituted alkyl groups such as acylaminoethyl, acylaminopropyl, acylaminohexyl, Z-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl groups: in particular sulphated low hydroxyalkyl groups and possibly further substituted aryl groups such as phenyl, sulphophenyl and acylaminophenyl groups.
  • All these dyestuffs are used in the form of their water soluble salts, particularly as alkali metal or ammonium salts.
  • a prefered class of metal phthalocyanines employed according to this invention are those of the formulae:
  • n can be one if the phthalocyanine radical contains a further water solubilizing group as the monosulphonic acid ethanolarnide group
  • P0 is a phthalocyanine radical, i.e., a unsubstituted phthalocyanine radical or a substituted phthalocyanine radical, e.g., dyestuff produced by condensation of copper phthalocyanine tetrasulphonic acid chloride with 1 mol of 2,4-diaminobenzene-1-sulphonic acid, the dyestuff produced by the condensation of a mixture of copper phthalocyanine sulphonic acid chloride which contains on the average of 2 to 3 sulphonic acid chloride groups with 1 mol of 2,5-diarninobenzene-l-sulphonic acid, saponification of the remaining sulphonic acid chloride groups with subsequent diazotisation and coupling with 1-phenyl-3- methylpyrozal-S-one, copper phthalocyanine monosulphonic
  • the quaternised condensation products are used in amounts of about 0.5 gramme (g.) per litre dye liquor.
  • the range of action is to some extent dependent on the amount and type of the dyestuff used on the composition of the auxiliaries, so that the content varies from about 0.1 to 2 g. per litre of dye liquor.
  • the dye liquor can contain the auxiliaries usual in Wool dyeing, e.g., salts such as sodium sulphate, ammonium sulphate, ammonium acetate, acid alkali or ammonium phosphates, esters such as methyl or ethyl lactate or tartrate, or acids such as formic acid, acetic acid, hydrochloric acid, sulphuric acid etc.
  • salts such as sodium sulphate, ammonium sulphate, ammonium acetate, acid alkali or ammonium phosphates, esters such as methyl or ethyl lactate or tartrate
  • acids such as formic acid, acetic acid, hydrochloric acid, sulphuric acid etc.
  • Advantageously dyeing is performed in possibly buffered, weakly acid baths or in dye liquors which contain ammonium salts of difficulty volatile acids, e.g., ammonium sulphate in contents of 3% to 6% of the goods to be dyed,
  • condensation products are obtained by heating a reaction mixture containing a monocarboxylic fatty acid of at least eight carbon atoms and one to three mols of a lower alkanol amine per mol of fatty acid with the simulatneous splitting off of about one mol of Water per mol of alkanol amine, the ratio of fatty acid to alkanol amine in the reaction mixture being such that for each mol of fatty acid in the reaction mixture there is at least three mols of monoalkanol radicals.
  • they are condensation prod- 'ucts of fatty acids having 8 to 14 carbon atoms or mixtures of such acids and 2 mols of dialkanolamine per mol of fatty acid present.
  • the quaternised condensation products simultaneously deepen the shade, and improve the levelling and fastness to perspiration, wet and rubbing. Also, even when highly concentrated dyestuff solutions are used, they prevent staining of both the dyeings as well as the apparatuses.
  • the wet fastness properties of the wool dyeings produced according to the invention by after-treatment of the wool dyeings in the known way with agents which raise the pH such as ammonia or hexamethylenetetramine, at 80l00 C., as well as with wetting agents.
  • the wool dyeings so obtained are distinguished by a full shade, great evenness, excellent wet fastness properties and perfect fastness to rubbing.
  • Example 1 250 parts of woollen worsted yarn wound onto cheeses are treated in a dyeing apparatus for 10 minutes at 50 with a solution of 10 parts of ammonium sulphate and 5 parts of the quaternised nitrogen compound described below in 2800 parts of soft water. After adding a solution of 7 parts of sodium salt of copper phthalocyanine disulphonic acid in 200 parts of soft water, the temperature is raised within 40 minutes to and dyeing is performed for 1 hour at 100. The wool is then rinsed in the apparatus with hot and then with cold water. After drying a pure, level, strongly coloured blue dyeing is obtained which has good perspiration, rubbing and wet fastness properties. No coloured greasy coating has formed in the dyeing apparatus.
  • the quaternised nitrogen compound used in this example is produced as follows:
  • Example 2 0.5 part of the sodium salt of 4, 4, 4", 4" coppe1' phthalocyanine tetrasulphonic acid are dissolved in 250 parts of hot water with the addition 'of 0.4 part of ammonium sulphate and 0.2 part of the quaternary nitrogen compound described below. 10 parts of woollen worsted yarn are entered into this liquor at 40, the liquor is brought to the boil within 45 minutes and dyeing is performed for 1 hour at the boil. The Woollen worsted yarn is then rinsed first with warm and then with cold water. The pure, deep, level, reddish-blue dyeing has very good wet, light and rubbing fastness properties.
  • the quaternary nitrogen compound used in this example is produced as follows:
  • Example 3 0.3 part of the sodium salt of copper phthalocyaninemonosul-phonic acid-monosulphonic acid ethanolamide, produced from copper phthalocyanine-monosulphonic acid-monosulphonic acid chloride and ethanolamine in water, 0.4 part of ammonium sulphate and 0.2 part of the quaternised nitrogen compound described below are dissolved in 250 parts of hot water. parts of woollen worsted yarn are entered into this liquor at 40. The liquor is brought to the boil within 40 minutes and dyeing is performed for 1 hour at the boil. The dyed woollen worsted yarn is then rinsed, first with Warm and afterwards with cold water. The pure, level blue dyeing obtained has very good wet, light, perspiration and rubbing fastness properties.
  • the quaternised nitrogen compound used in this example is produced as follows:
  • Example 4 Dyeing is performed in the same way as described in Example 2 but instead of the copper phthalocyanine tetrasulphonic acid, 0.5 part of the dyestuif (SOsNa)s CnPc
  • Example 5 Dyeing is performed as described in Example 2 but instead of the copper phthalocyanine tetrasulphonic acid, 0.5 part of the dyestuff of the formula (S OaN8.)1-2
  • This dyestulf is produced by condensation of a mixture of copper phthalocyanine sulphonic acid chloride which contains on the average 2 to 3 sulphonic acid chloride groups, with 1 mol of 2,5-diaminobenzene-1- sulphonic acid, saponification of the remaining sulphonic acid chloride groups, diazotisation and coupling with 1- phenyl-3-methylpyrazol-5-one.
  • a level green dyeing is obtained which is fast to perspiration, Wet and rubbing.
  • Example 6 0.4 part of the sodium salt of copper phthalocyanine trisulphonic acid are dissolved hot in 400 parts of water with the addition of 0.4 part of ammonium sulphate, 0.1 part of the quaternary nitrogen compound described in Example 2 and 0.4 part of the condensation product obtained according to U.S. Patent No. 2,089,212 from 1 mol of coconut oil fatty acids and 2 mols of diethanolamine. 10 parts of Wool flannel are introduced into this liquor at 40.
  • the temperature is raised Within 40 minutes to the boil and dyeing is performed for 1 hour at the boil.
  • the dyed wool flannel is then rinsed with Warm and then with cold water.
  • the full, pure, level, bl-ue dyeing obtained has very good wet, light and rubbing fastness properties.
  • Example 7 0.5 part of the sodium salt of the sulphated copper phthalocyanine sulphonic acid-'y-hydroxypropylamide of the schematic formula CUPC 2 3 wheerin Pc is the phthalocyanine moiety, are dissolved hot in 250 parts of soft water with the addition of 0.6 part of 40% acetic acid and 0.2 part of the quaternised nitrogen compound described below. 10 parts of woollen worsted yarn are introduced into this liquor at 40.
  • the bath is raised to the boil within. 45 minutes and dyeing is performed for 1 hour at the boil. 0.4 part of hexamethylenetetramine are then added and boiling is continued for another 30 minutes.
  • the dyed yarn is then rinsed, first with warm and then with cold water. The pure, deep, level, blue dyeing obtained has very good fastness to wet, light and rubbing.
  • a blue dyeing having similar properties is obtained if, instead of the above sulphated copper phthalocyanine sulphonic acid- -hydroxypropylamide, a corresponding number of parts of sulphated copper phthalocyanine sulphonic acid hydroxyethylamide of the schematic formula are used.
  • the dyestuifs are produced as follows:
  • the dyestuff sulphonic acid chloride is then reacted with 105 parts of 1,3-propanolamine, first cold and then at 80, and the dyestuff sulphonic acid 'y-hydroxypropylamide is isolated, dried and esterified with sulphuric acid monohydrate or with chlorosulphonic acid.
  • the quaternary nitrogen compound used in this exampie is produced as follows:
  • Example 8 I 0.5 part of the sodium salt of the sulphated copper phthalocyanine tetrasulphonic acid-fi-hydroxyethylamide of the schematic formula are dissolved in 250 parts of soft water with the addition of 0.6 part of 40% acetic acid and 0.2 part of a surface active quaternary nitrogen compound of the type described below. 10 parts of Woollen worsted yarn are introduced into this solution at 40. The bath is raised to the boil within 45 minutes and the goods are dyed for 1 hour at the boil. The 0.4 part of hexamethylenetetramine are added and the bath is boiled for another 30 minutes. The dyed yarn is then rinsed, first with warm and then with cold water. The pure, full, level, blue dyeing obtained has very good wet, light and rubbing fasteness.
  • the dyestuff is produced as follows:
  • sulphated dyestuff is produced by pouring onto ice, salting out, filtering off, suspending the precipitate and carefully neutralising the suspension. It is in the form of the sodium salt and is precipitated with sodium chloride, filtered off under suction and dried.
  • the quaternary nitrogen compound used in this example is produced as follows:
  • Example 9 0.8 part of the sodium salt of the sulphated copper phthalocyanine tetrasulphonic acid hydroxyethylamide of the schematic formula CUPC 4 (produced as described in Example 8) are dissolved in 250 parts of soft water with the addition of 0.6 part of 40% acetic acid and 0.2 part of the surface active quaternary condensation product described below. Dyeing is performed as described in Example 7 and a full, pure, blue wool dyeing is obtained which is fast to light, wet and rubbing.
  • the surface active quaternary nitrogen compound used in this example is produced as follows:
  • Example 10 Dyeing is performed in the same way as in Example 2 except that instead of copper phthalocyanine tetrasulphonic acid, 0.5 part of the dyestuff CuPc (SOzNHCHzCHzOSOaH):
  • Example 11 1069 parts of the product of addition of 1 equivalent of styrene oxide, 1 equivalent of propylene oxide and 2 0 equivalents of ethylene oxide to 1 equivalent of technical oleylamine are melted at -80 and 102 parts of dimethyl sulfate are added dropwise to this melt within 45 minutes while stirring well.
  • the reaction is slightly exothermic; as soon as the temperature drops, the reaction mixture is stirred for another 30 minutes at -85 salt of the probable formula wherein m is a whole number from to 22, are obtained as a pasty, water soluble mass.
  • the position of the substituents in the polyethyleneoxy chains is probably correct; but isomeric compounds are also possible.
  • the chain length of the individual polyglycol ether radicals is unknown and the sum of the chain members is, as is usual, an average value.
  • the addition product was produced by heating 240 parts of technical oleylamine with 108 parts of styrene oxide and 1.6 parts of sodium ethylate for hours at 110150 cooling to 60, adding 52 parts of propylene oxide within 1 hour, refluxing until the temperature attained 130 and introducing ethylene oxide at this temperature into the melt until the weight increases to 790 parts.
  • the new quaternary, water soluble condensation product makes it possible to attain level, light fast, deep blue dyeings on wool with dioxazine dyestuffs by, for example, the following process:
  • Example 12 '632 parts of the production of addition of 1 equivalent of styrene oxide, 2 equivalents of propylene oxide, 24 equivalents o fethylene oxide to 1 equivalent of stearylamine are melted at 75-80. 51 parts of dimethyl sulphate are added dropwise to the melt within 40 minutes while stirring well. The whole is stirred at 8090 for another 30 minutes and then allowed to cool.
  • the quaternary ammonium salt of the probable formula orrasoi 11.015031 is obtained as solid, soap-like paste which dissolves completely in the usual practical concentration in hot water.
  • the addition product is produced by the method described in the second paragraph of Example 1 from 121 parts of technical stearylamine, 54 parts of styrene oxide and 52 parts of propylene oxide and 475 parts of ethylene oxide.
  • this product also produces level, strongly coloured blue dyeings 0n wool with the dioxazine dyestulf, Remastral Blue FFZGL, sold by Farbwerke Hoechst, in Frankfurt au Main, Germany.
  • Example 13 42 parts of dimethyl sulphate are added dropwise within 45 minutes at 80 while stirring well to 310 parts of the product of addition of 1 equivalent of styrene oxide, 1 equivalent of propylene oxide and 15 equivalents of ethylene oxide to dodecylamine. On completion of the exothermic reaction, the whole is stirred for half an hour while heating at -90". It is then cooled and the quaternary ammonium salt of the probable formula onisoa is obtained as a soap-like semi-solid paste which completely dissolves in hot water.
  • the addition product used is produced from 92.5 parts of technical dodecylamine, 60 parts of styrene oxide, 29 parts of propylene oxide and 330 parts of ethylene oxide by the method described in paragraph 2 of Example 11.
  • Example 14 65 parts of dimethyl sulphate are added dropwise within 40 minutes at 80 while stirring well to 590 parts of the product of addition of 1 equivalent of styrene oxide and 18 equivalents of ethylene oxide to 1 equivalent of oleylamine. As soon as the exothermic reaction has been completed, the whole is heated to 8590 and stirred for another 30 minutes at this temperature. It is then cooled.
  • the soap-like, past, water soluble quaternary salt corresponds to the probable formula wherein m is a whole number from 0 to 18, or it is an isomeric mixture of this composition.
  • the addition product used above is produced by the method described in Example 11 by adding parts of styrene oxide to 267 parts of oleylamine and then adding 792 parts of ethylene oxide.
  • This quaternary salt also produces level, light fast wool dyeings of good colour strength with polysulphonated dioxazine dyestuffs under the dyeing conditions described in the last paragraph of Example 11.
  • Example 11 the product of addition of 1 equivalent of styrene oxide, 2 equivalents of propylene oxide and 16 or 18 or 20 or 22 or 24 equivalents of ethylene oxide to oleylamine is used;
  • Example 12 In Example 12, the product of addition of 1 equivalent of styrene oxide and 16, 18, 20, 22 or 24 equivalents of ethylene oxide to hexadecylamine, octadecylamine, docosylamine is used.
  • Example 13 the product of addition of 1 equivalent of styrene oxide, 2 equivalents of propylene oxide and 12, 14, 16, 18 or 20 equivalents of ethylene oxide to dodecylamine, tetradecylamine or hexadecylamine is used;
  • Example 14 the product of addition of l equivalent of styrene oxide and 18, 20 or 22 equivalents of ethylene oxide to stearylamine is used.
  • the improvement comprising mixing with the aqueous dyebath containing the aforesaid salt a quaternary condensation product of a primary amine selected from the group consisting of a higher alkylamine, a higher alkenylamine and higher alkyl-benzylamine, with, per equavalent of said primary amine from 7-30 equivalents of ethylene oxide, one equivalent of styrene oxide and from to 2 equivalents of propylene oxide quaternized with the ester of a lower alkanol and a strong acid.
  • a primary amine selected from the group consisting of a higher alkylamine, a higher alkenylamine and higher alkyl-benzylamine, with, per equavalent of said primary amine from 7-30 equivalents of ethylene oxide, one equivalent of styrene oxide and from to 2 equivalents of propylene oxide quaternized with the ester of a lower alkanol and a strong acid.
  • the metal is of atomic number from 28 to 29 and said dyebath containing a condensation product obtained by heating a reaction mixture containing a monocarboxylic fatty acid of at least eight carbon atoms and one to three mols of a lower alkanol amine per mol of said fatty acid with the simultaneous splitting off of about one mol of water per mol of alkanolamine, the ratio of fatty acid to allcanolamine in said reaction mixture being such that for each mol of fatty acid in the reaction mixture there are at least three mols of monoalkanol radicals, the improvement which comprises mixing with the aqueous dyebath containing the aforesaid salt a quaternary condensation product of a primary amine selected from the group consisting of a higher alkylamine, a higher alkenylamine and higher alkyl-benzylamine, with, per equivalent of said primary amine, from 7 to 30 equivalents of ethylene oxide one equivalent of sty
  • a quaternary condensation product of oleylamine with, per equivalent thereof, about one equivalent of styrene oxide and with about 10 to 30 equivalents of ethylene oxide, quaternized with dimethyl sulfate.

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CH602061A CH373012A (de) 1961-05-24 1961-05-24 Verfahren zur Erzeugung echter Wollfärbungen mit Kupfer- oder Nickelphthalocyaninen

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3401004A (en) * 1964-03-26 1968-09-10 Geigy Ag J R Process for the dyeing of synthetic polyamide fibers
US3446569A (en) * 1963-05-11 1969-05-27 Hoechst Ag Aqueous solutions of phthalocyanine pigments and process for preparing them
US3529922A (en) * 1965-09-09 1970-09-22 Ciba Ltd Process for dyeing nitrogen-containing textile fibres
US3995997A (en) * 1973-08-16 1976-12-07 Bayer Aktiengesellschaft Concentrated solutions of anionic dyestuffs
WO2007042379A1 (en) * 2005-10-07 2007-04-19 Clariant International Ltd Dyeing of polyamide fibres
CN101278090B (zh) * 2005-10-07 2011-10-19 克莱里安特财务(Bvi)有限公司 羊毛纤维的染色

Citations (3)

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US2763530A (en) * 1951-01-11 1956-09-18 Ciba Ltd Process for dyeing loose wool
US3049392A (en) * 1962-08-14 Process for dyeing nitrogenous mate-

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US2763530A (en) * 1951-01-11 1956-09-18 Ciba Ltd Process for dyeing loose wool
US2759975A (en) * 1952-05-28 1956-08-21 Gen Aniline & Film Corp Mixed alkyl-benzyl-alkylol quaternary ammonium salts

Cited By (6)

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US3446569A (en) * 1963-05-11 1969-05-27 Hoechst Ag Aqueous solutions of phthalocyanine pigments and process for preparing them
US3401004A (en) * 1964-03-26 1968-09-10 Geigy Ag J R Process for the dyeing of synthetic polyamide fibers
US3529922A (en) * 1965-09-09 1970-09-22 Ciba Ltd Process for dyeing nitrogen-containing textile fibres
US3995997A (en) * 1973-08-16 1976-12-07 Bayer Aktiengesellschaft Concentrated solutions of anionic dyestuffs
WO2007042379A1 (en) * 2005-10-07 2007-04-19 Clariant International Ltd Dyeing of polyamide fibres
CN101278090B (zh) * 2005-10-07 2011-10-19 克莱里安特财务(Bvi)有限公司 羊毛纤维的染色

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BE617998A (fr) 1962-11-23
CH373012A (de) 1963-07-31

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