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Publication numberUS3684426 A
Publication typeGrant
Publication dateAug 15, 1972
Filing dateMar 2, 1970
Priority dateMar 24, 1969
Also published asDE1919120A1
Publication numberUS 3684426 A, US 3684426A, US-A-3684426, US3684426 A, US3684426A
InventorsJakob Bindler, Rudolf Keller
Original AssigneeJakob Bindler, Rudolf Keller
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Levelling polyamide fiber dyeing with sulfonated long chain alkyl diphenyl ether and quaternized long chain alkyl ammonium alkylene oxide condensate
US 3684426 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent Int. Cl. D06p 3/06 U.S. Cl. 8-15 8 Claims ABSTRACT OF THE DISCLOSURE A process for the even, non-streaky dyeing of fibre material made from synthetic polyamide of ditfering dyestuif-afiinity, such as textured polyamide fibre material, is disclosed, which comprises pre-treating said fibre material, at a pH-value of from 2 to 7 and at temperatures of from 30 to 130 C., with aqueous solution of a mixture of auxiliaries consisting of at least one monoor di-sulphonated higher-alkyl-diphenylether as anion-active compound and at least one cation-active, non-quaternated or quatemated compound containing at least one basic nitrogen atom to which are bound at least one polyglycol ether chain and at least one aliphatic radical having from to 18 carbon atoms, the molecule containing from 8 to 20 di-alkylene-oxy groupings, and, optionally, further auxiliaries normally used in dyeing, adding then, at temperatures of from 30 to 100 C., pre-dissolved anionic dyestufi, and completing the dyeing in the heat. By this process, even on polyamide fibre material tending to exhibit streakiness upon dyeing, even and non-Streaky dyeings are obtained with, in themselves, poorly levelling dyestuffs, with extensive exhaustion of the dye bath.

DETAILED DISCLOSURE The present invention relates to a process for the even, non-streaky dyeing of fibre material made from synthetic polyamide of differing dyestulT-afiinity, as Well as to the fibre material dyed using this process.

It has been found that fibre material made from synthetic polyamide having differing dyestuff-aflinity, such as textured polyamide fibre material, e.g. Banlon, can be dyed very evenly and non-streakily by pro-treating this fibre material, at a pH-value of from 2 to 7 and at temperatures of from 30 to 130 C., preferably at 40 to 95 C., with the aqueous solution of a mixture of auxiliaries, consisting of (a) at least one anion-active compound of Formula I,

wherein R represents an alkyl radical having from 8 to 18 carbon atoms,

X represents a cation and n represents a number from 1 to 2,

"iota.--

l I (II) as well as, optionally,

3,684,426 Patented Aug. 15, 1972 Ice (c) further auxiliaries normally used in dyeing, adding then, at temperatures of from 30 to C., pre-dissolved anionic dyestuif and completing the dyeing in the heat, preferably at boiling temperature or at temperatures above 100 C., under pressure.

Anion-active compounds of Formula I are known per se and can be produced, e.g. by the methods described in British Pats. Nos. 912,340 and 1,043,043, by reacting correspondingly substituted diphenyl ethers together with a sulphonating agent, such as sulphur trioxide or chlorosulphonic acid, in the solution of a poly-chlorinated aliphatic hydrocarbon, or by dissolving the diphenyl ether compound in a saturated aliphatic hydrocarbon and then bringing it into contact with the sulphonating agent.

Anion-active compounds of Formula I which have proved particularly valuable, in the process according to the invention, are those wherein R represents an alkyl radical having from 9 to 12 carbon atoms, X represents an alkali metal ion, such as the lithium or potassium ion, preferably, however, the sodium ion, or the ammonium ion and n represents the number 2. Disulphonated compounds of Formula I, which are obtained by sulphonating the 4-dodecyldiphenyl ether, are especially preferred.

The cation-active, non-quaternated or quaternated compounds (b), usable in the process according to the invention, are likewise known per se and can be produced in a manner known per se, e.g. by reaction of the corresponding aliphatic amines, especially long-chain primary alkylmono-, -dior -tri-arnines, the alkyl or alkenyl radical of which contains from 10 to 18 carbon atoms, such as dodecyl-, octadecylor octadecenylamine, dodecylpropylenediamine, octadecylethylenediamine and octadecyldiethylenetriamine, with alkylene oxides, e.g. with propylene oxide, but particularly with ethylene oxide, and, optionally, subsequent reaction with usual quaternating agents such as methyl-, ethylor benzylhalides, diethyl sulphate and, in particular, dimethyl sulphate. Suitable cationactive compounds (b), usable according to the invention, are also products obtained by reaction of the above mentioned alkylamines with from 1 to 2 equivalents of styrene oxide, from 0 to 2 equivalents of propylene oxide and from 1 to 19 equivalents of ethylene oxide as well as, optionally, subsequent quaternisation.

Cation-active compounds of Formula III are preferred,

Y Y; (III) wherein R represents an alkyl or alkenyl radical having from 10 to 18 carbon atoms, especially the octadecenyl or the octadecyl radical,

R represents a lower alkyl radical having from 1 to 4 carbon atoms, particularly the methyl group,

of Y and Y one Y represents hydrogen and the other Y represents hydrogen or the phenyl radical,

m represents 0 or 1,

n and p represent whole numbers, the sum of which is from 6 to 20, especially from 11 to 18, and

A represents an anion, particularly the methosulphate ion.

The sum of the coeflicients n and p represents a mean value, and there are present mixtures of analogous compounds with polyalkyleneoxy substituents of varying chain-length.

Anionic dyestuffs, suitable for the process according to the invention, can belong to very diverse classes of dyestuffs. These can be, for example, the commercially important dyestulf classes of the azo, anthraquinone, phthalocyanine, nitro or formazane dyestuffs which can also contain metals bound in complex linkage such as copper, nickel, chromium or cobalt. Suitable azo dyestuffs are, principally, monoazo dyestuffs, e.g. of the type phenylazobenzene, phenylazonaphthaiene, phenylazohydroxyor -aminopyrazole, phenylazoacyloacetylarylamide, or those of the analogous naphthylazo series, whereby the aromatic nuclei can be suitably substituted. Also suitable are disand polyazo dyestuffs. The 2120 dyestuffs, to which also belong the formazane dyestutfs, can be metallised, principally by chromium or cobalt, but also by cop per or nickel, whereby 1 or 2 dyestufi molecules per metal ion participate in the complex.

The pH-value of the dye bath is adjusted to the desired value by the addition of an acid, such as acetic acid, formic acid or sulphuric acid. The preliminary treatment of the fibre material in the dye bath containing the auxiliaries as defined, preferably lasts 5 to 30 minutes. The weight ratio of anion-active to cation-active compound is thereby advantageously from 1:1 to :1.

After the preliminary treatment, the acidity of the dye liquor can be reduced by the addition of an acid-binding agent, such as an alkali metal hydroxide, -carbonate or -hydrogen carbonate, by the addition of ammonium hydroxide, disodium or dipotassium phosphate, sodium or potassium acetate, as well as by the addition of hexamethylenetetramine.

An advantageous embodiment of the process, according to the invention, consists in carrying out the preliminary treatment at boiling temperature, then adding the predissolved dyestufi and completing the dyeing at the same temperature. After the dyeing is completed, the dyed material is advantageously rinsed in the usual manner, if necessary given an aftertreatment to improve the fastness to wet processing, and dried.

In general, the anion-active compounds are used in amounts of from 0.1 to 5% by weight, relative to the fibre material to be treated, preferably in amounts of from 0.2 to 2% by weight. The cation-active compounds are, in general, used in amounts of from 0.01 to 2% by weight, preferably in amounts of from 0.05 to 0.5% by weight.

As auxiliaries which are normally used in dyeing, the dye bath can contain, e.g. urea, thiourea, thiodiethylene glycol or hydrophilic compounds having limited Watersolubility such as, e.g. butyl alcohol or benzyl alcohol.

Further additives are textile-protective agents having afiinity to the fibres and which protect the textile ma terial to be dyed.

Suitable fibre materials made from synthetic polyamide, which can be dyed using the process according to the invention, are, e.g. condensation products from hexamethylenediamineand adipic acid (Polyamide 6.6) or sebacic acid (Polyamide 6.10) or mixed condensation products, e.g. from hexamethylenediamine, adipic acid and e-caprolactam (Polyamide 6.6/6), also the polymerisation products from e-caprolactam, known under the trade names of Polyamide 6, Perlon, Grilon or Enkalon, or from w-aminoundecanoic acid (Polyarnide 11 or Rilsan). These fibres can be used at any stage of processing, that is to say, e.g. in the form of threads, yarns, knitted goods and fabrics.

The process, according to the invention, is distinguished in that, even on polyamide fibre material tending to exhibit streakiness upon dyeing, even and non-Streaky dyeings are obtained with, in themselves, poorly levelling dyestufis, with extensive exhaustion of the dye bath.

The temperatures are given in degrees centigrade in the following examples.

EXAMPLE 1 To 200 ml. of softened water are added 0.1 ml. of 40% acetic acid and 0.1 g. of a mixture, consisting of 0.076 g. of a 45% aqueous solution of the disodium salt of the dodecyldiphenyl ether disulphonic acid, 0.0075 g. of a compoundof the formula CH3 (CHgCH2O) H C1aH 5 OH2ICHO(CHZCHZO)pH 3043113 and 0.0165 g. of water.

5 g. of knitted fabric made from textured polyamide-6 yarn are treated in the obtained auxiliary liquor for 10 minutes at 40. To the liquor is then added a solution of 0.025 g. of the dyestuif of the formula and 0.007 g. of the dyestulf of the formula i IhH-Q-NH-IJO on,

S C ble in 10 g. of water.

While continuously moving the textile material, the temperature of the dye bath is raisedwithin-45 minutes to the boiling point and, as the dye liquor gently boils, dyeing is continued for a further 45 minutes. The dyed material is then rinsed Warm and afterwards cold and finally dried.

In this manner is obtained a non-streaky and even brown dyeing.

If, in this example, the 0.076 g. of 45% aqueous solution of the sodium salt of the dodecyldiphenyl ether disulphonic acid are replaced by the same amount of one of the anion-active compounds which are listed in the second column of the following Table I, with the procedure otherwise as described in Example 1, then similarly good dyeings are obtained on the stated material.

TAB-LE 1 EXAMPLE 5 To 400 ml. of water at ca. 40 are added 0.075 ml. of 40% acetic acid and 0.2 g. of a mixture consisting of 0.152 g. of a 45% aqueous solution of the disodium salt of the dodecyldiphenyl ether disulphonic acid, 0.015 g. of a compound of the formula and 0.033 g. of water.

To the obtained auxiliary liquor are added g. of knitted fabric made from textured polyamide-6.=6 yarn, the temperature of the liquor is rapidly raised, with continuous movement of the textile material, up to the boiling point and boiling is maintained for minutes. To the liquor are then added 0.050 g. of the dyestuff of the formula,

N-SO3N& I l I Cl CH3 0.018 g. of the dyestuff of the formula some (Synthesized in US. Pat. 2,714,103.)

and 0.014 g. of the' dyestuff of the formula (Synthesized in Belgium Pat. 674,050.)

pre-dissolved in 20 g. of water. Boiling proceeds for a further 60 minutes until the dyestuff has drawn onto the textile material. The material is afterwards rinsed warm and then cold, and dried. The resulting brown dyeing is smooth and level and differences in afiinity, caused by the material, are extremely well equalised.

Without the addition of the above mixture of auxiliaries, applying otherwise the same procedure, an uneven and very streaky dyeing is obtained.

If, in the above example, the 0.015 g. of the compound of the formula CH3 (CH CHzOhH ee ofingonzonowmomo n SOICHS are replaced by the same amount of one of the cationactive compounds listed in the second column of the following Table II the procedure being otherwise as de scribed in the above example, then similarly level and non-streaky dyeings are obtained on knitted fabric made from textured polyamide-6.6 yarn.

TABLE II Ex. No. Cation-active compound 6.--.. CHxCHrOhH um's-N (CH CHgObH (CH2CH2O)|1H CHHZPN on; s 0,

(CHzCHzOhH H;

a..." (omcmmnn CiaHs1 (CH1CH20)pH V C4H0 n+p=20 EXAMPLE 13 Muffs made from polyamide-6 textured yarn are introduced into an open dyeing apparatus (packing machine). An about 40 warm auxiliary liquor is prepared separately which contains, relative to the weight of the textile material, 2.0% of 40% acetic acid and 3.0% of the mixture of auxiliaries used in Example 1 (ratio of goods to liquor ca. 1:15).

This auxiliary liquor is pumped into the dyeing apparatus. The temperature of the auxiliary liquor is then rapidly raised to 96 and the material to be dyed is treated at this temperature for 30 minutes. The pH-value of the dye bath is thereupon raised to 6.0 by the addition of aqueous ammonia solution, After the auxiliary liquor has been thoroughly mixed, an addition is made, relative to 7 the weight of textile material, of 0.5% of the dyestuif of the formula which is pre-dissolved in ten times the amount of water, and dyeing proceeds for a further 60- minutes at 96. The red dyed material is then rinsed warm and afterwards cold, and dried.

A knitted fabric, produced from the thus dyed yarn, is free of streaks and is uniform.

EXAMPLE 14 To 300 ml. of water at 70 are added 0.5 g. of the mixture of auxiliaries, used in Example 5, and 0.2 ml. of 85% formic acid. g. of tricot made from polyamide- 6.6 textured yarn are pre-treated at 70 for 15 minutes in the obtained auxiliary liquor. To the auxiliary liquor are then added 0.04 g. of the dyestutf of the formula --N=N OH; i o] N l/ N C o o i 554,509). dissolved in 4 ml. of water, and

the dye liquor is heated to boiling within 20 minutes. Whilst continuous movement I,

of the material being dyed is maintained, dyeing proceeds during one hour at the boiling temperature, after which the obtained brown dyeing is rinsed and dried.

The resulting dyeing is appreciably more level than a dyeing obtained without addition of the above-mentioned 1 mixture of auxiliaries.

Whatwe claim is: v 1. A process for the even, non-streaky dyeing of fibre material made from synthetic polyamide of differing dyestuff-aflinity, which comprises (I) applying to said fibre material, at a pH-value of I from 2 to 7 and at temperatures of from 30 to 130 C., with the aqueous solution of a mixture of auxiliaries comprising a (a) at least one anion-active compound of Formula I l so X R L .l a h (I) wherein I R represents an alkyl radical having to 18 carbon atoms, X represents a cation, and I n represents a number from 1 to 2, an

from 8 l 8 (b) at least one cation-active compound of the formula l some (0.1. 23635) (Y1 Y3 R1\$/ hnhn-o m-(oHQ-oHPmn-H /N\ A n, orr t zn ocm-onz-o g-n Y; Y,

wherein R represents an alkyl or alkenyl radical having from 10 to 18 carbon atoms, R represents a lower alkyl radical having from 1 to 4 carbon atoms, of Y and Y one Y represents hydrogen and the other. Y represents hydrogen or the phenyl radical, m represents 0 or 1 n and p represents whole numbers, the sum of which is from 6 to 20, and A represents. an anion; and (II) adding, at temperatures of from 30 to 100 C., predissolved anionic dyestufi and completing the dyeing at the temperature of 30 to 100 C.

2. A process as claimed in claim 1 wherein the aque ous solution contains further dyeing auxiliaries.

3. A process as claimed in claim 1 wherein in the anion-active compounds R represents an alkyl radical having from 9 to 12 carbon atoms, X represents an alkali metal ion or the ammonium ion, and n represents the number 2.

4. A process as claimed in claim 1 employing a weight ratio of anion-active to cation-active compounds of from 1:1 to 10:1.

5. A process as claimed in claim 1 wherein the preliminary treatment is carried out at a temperature of between 40 and C. p

6. A process as claimed in claim 1 wherein the dyeing is performed at boiling temperature.

7. A process as claimed in claim 1 wherein the dyeing is performed at temperatures above C. under pressure.

8. A process as claimed in claim 1 wherein the preliminary treatment is carried out at boiling temperature,

the pre-dissolved dyestulf then added and the dyeing then completed at the same temperature.

References Cited UNITED STATES PATENTS Brooks: Defensive Publication of application S.N, 661,- 820, 895 O.G. 41.

Schmidlin: Preparation and Dyeing of Synthetic Fibers, pp. 172-173, pub.by Chapman & Hall Ltd., London, 1963.

DONALD LEVY, Primary Examiner v US. (:1. X.R. a r-172,173, 42 B, 39.

UNTTEn STATES PATENT @FFICE CERTIFICATE OF CGREC'HUN Patent No. 3 ,684,426 Dated August 15 1972 Inventor(s) Jakob Bindler and Rudolph Keller It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 2 under the title, after "Switzerland", please insert:

assignors to Ciba-Geigy AG, Basel, Switerland columnl, between lines 3 and 4, under the title, please insert: claims priority, application Switzerland, March 24 1969 Serial No. 4381 Column 5 plaese change the first formula from the bottom to read as follows: instead of as C H II 1 II printed. 18 35 37 Column 6, Table II, Example No. 10, please change "n+ +Z +Z =2O" to n+p+Z +Z =l8 column 6 third line from the bottom, please change "dye" to auxiliary Signed and sealed this 19th day of February 1974;

(SEAL) Attest:

EDWARD M.FLETCHER,JR. C M I Attesting Officer 2 ARSHALL NN Commissioner of Patents FORM PO-105O (10-69) USCOMM'DC 6376-P69 U.S. GOVERNMENT PRINTING OFFICE: 1969 0-366-334.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4030880 *Oct 9, 1975Jun 21, 1977E. I. Du Pont De Nemours And CompanyProcess for improving dyeability
US4217103 *Sep 22, 1978Aug 12, 1980Bayer AktiengesellschaftDyestuff formulations containing salts of diaryl ether sulfonic acids
US4444563 *Sep 2, 1982Apr 24, 1984Ciba-Geigy CorporationDyeing assistant and use thereof in dyeing or printing synthetic polyamide fibre materials
US4563190 *Aug 31, 1983Jan 7, 1986Ciba-Geigy CorporationDyeing assistant and use thereof for dyeing or printing synthetic polyamide fibre material
US4563192 *Sep 14, 1984Jan 7, 1986Ciba-Geigy CorporationProcess for dyeing fibre material made of synthetic polyamides with anionic dyes and an auxiliary mixture
US5460632 *Dec 29, 1994Oct 24, 1995Olin CorporationLow-foaming, enhanced wetting dye-leveling agent
US5762650 *Aug 23, 1996Jun 9, 1998Olin CorporationBiocide plus surfactant for protecting carpets
Classifications
U.S. Classification8/480, 8/676, 8/686, 8/606, 8/930, 8/900, 8/924, 8/589
International ClassificationD06P3/24, D06P1/607, D06P1/62
Cooperative ClassificationD06P3/24, Y10S8/93, Y10S8/90, Y10S8/924, D06P1/621, D06P1/6076, D06P3/241, D06P1/625
European ClassificationD06P1/62B, D06P3/24A, D06P3/24, D06P1/62B2D, D06P1/607D