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Publication numberUS3713768 A
Publication typeGrant
Publication dateJan 30, 1973
Filing dateNov 12, 1970
Priority dateNov 12, 1970
Publication numberUS 3713768 A, US 3713768A, US-A-3713768, US3713768 A, US3713768A
InventorsKeller K, Wegmuller H
Original AssigneeCiba Geigy Ag
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Long chain alkane or alkene amido benzene sulfonate assisted dyeing of synthetic linear polyamides
US 3713768 A
Abstract
A process for the even, non-streaky dyeing of fiber material made from synthetic polyamide of differing dyestuff-affinity, such as textured polyamide fiber material, is disclosed, which comprises pre-treating said fiber material, at a pH-value of from 2 to 7 and at temperatures of from 30 to 100 DEG C, with a liquor containing, as essential component, an alkane- or alkene-amido-benzene-sulphonic acid salt having from 10 to 19 carbon atoms in the alkane- or alkene-amido radical, as anion-active auxiliary, such as the sodium or ammonium salts of 1-octadecanamido-benzene-3-sulphonic acid, 1-octadec-9-enamido-benzene-3-sulphonic acid and especially 1-octadec-9-enamido-benzene-3-ammonium sulphonate, thereafter adding the solution of at least one anionic dyestuff at temperatures of from 40 to 100 DEG C and completing the dyeing at temperatures of from 95 to 140 DEG C. By this process, even on synthetic polyamide fiber material tending to exhibit streakiness upon dyeing and with poorly levelling dyestuffs, even and non-streaky dyeings are obtained with a single anion-active auxiliary, said auxiliary being moreover suitable for the levelling of streaky and uneven dyeings by means of an after-treatment.
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United States Patent [191 Wegmuller et ab [11] 3,713,768 A 1' Jan. 30, 1973 [75] Inventors: Hans Wegmuller; Karlheinz Keller,

both of Riehen, Switzerland [73] Assignee: Ciba-Geigy AG, Basel, Switzerland [22] .Filed: Nov. 12, 1970 [21] Appl. No.: 88,986

[52] U.S. Cl. ..8/172, 8/l73, 8/15 [51]' Int. Cl. ..D06p /04 [58] Field of Search ..8/87, 172

[56] Y References Cited UNITED STATES PATENTS 2,310,074 2 1943 Gotte ..s ss

Primary ExaminerDonald Levy AttorneyWenderoth, Lind 8L Ponack 57 ABSTRACT A process for the even, non-streaky dyeing of fiber material made from synthetic polyamide of differing dyestuff-affinity, such as textured polyamide fiber' material, is disclosed, which comprises pre-treating said fiber material, at a pH-value of from 2 to 7 and at temperatures of from to 100 C, with a liquor containing, as essential component, an alkaneor alkeneamido-benzene-sulphonic acid salt having from 10 to 19 carbon atoms in the alk-aneor alkene-amido radical, as anion-active auxiliary, such as the sodium or ammonium salts of l-octadecanamido-benzene-3- sulphonic acid, l-octadec-9-enamido-benzene-3- sulphonic acid and especially l-octadec-9-enamidobenzene-S-ammonium sulphonate, thereafter adding the solution of at least one anionic dyestuff at temperatures of from to C and completing the dyeing at temperatures of from 95 to C. By this process, even on synthetic polyamide fiber material tending to exhibit streakiness upon dyeing and with poorly levelling dyestuffs, even and ru m-streakydyeings are'obtained with a single anion-active auxiliary, said auxiliary being moreover suitable for the levelling of streaky and uneven dyeings by means of an aftertreatment.

6 Claims, No Drawings LONG CHAIN ALKANE R ALKENE AMIDO BENZENE SULFONATE ASSISTED DYEING 0F SYNTHETIC LINEAR POLYAMIDES The present invention relates to a process for the even, non-streaky dyeing of fiber material made from synthetic polyamide, particularly synthetic polyamide of differing dyestuff-affinity, as well as to the fiber material dyed using this process.

In many instances, the even, non-streaky dyeing of fiber material made from synthetic polyamide represents a very serious problem for the dyeing expert. Various suggestions have already been made to overcome these difficulties. For instance, the simultaneous use of condensation products of naphthalene-2- sulphonic acid and formaldehyde and a weakly cationactive auxiliary has been recommended. Use of dibutylnaphthalene-sulphonic acid in admixture with certain cation-active polyglycol ethers is also known.

Often, however, the levelling power of these mixtures of auxiliaries has proved insufficient; thus, the results achieved by this process are unsatisfactory.

It has now been found that fiber material made from synthetic polyamide can be dyed evenly and nonstreakily, by pre-treating the fiber material, at a pH value of from 2 to 7 and at temperatures of from 30 to 100 C, with a liquor which contains an anion-active auxiliary of Formula I wherein R represents an aliphatic hydrocarbon radical having from 10 to 19 carbon atoms,

R represents hydrogen, an alkyl group having from one to four carbon atoms, an alkoxy group having from one to four carbon atoms or a halogen atom, and

M represents a monovalent cation, then adding the solution of at least one anionic dyestuff at temperatures of from 40 to 100 C and completing the dyeing at temperatures of from 95 to 140 C.

In compounds of the general Formula I R, in the meaning of an aliphatic hydrocarbon radical having from ID to 19 carbon atoms, represents a straightchained alkyl or alkenyl group, such as the dec-9-enyl, undecyl, tridecyl, pentadecyl, pentadec-B-enyl, heptadecyl, heptadec-S-enyl or nonadecyl group. Preferably, R represents a heptadecyl or, more particularly, a heptadec8-enyl group.

R in the meaning of an alkyl or alkoxy group having from one to four carbon atoms, represents, e.g., a methyl, ethyl, isopropyl'or n-butyl group or a methoxy, ethoxy, isopropoxy or n-butoxy group; R in the meaning of a halogen atom is, e.g. chlorine or bromine. The group corresponding to R can be in 0-, mor p-position with respect to the alkaneor alkene-amido radical. Preferably, R represents hydrogen.

M in the meaning of a monovalent cation represent, e.g., an alkali metal cation, or an alkylammonium or hydroxylakyl-ammonium cation having from two to four carbon atoms, such as the ethylammonium, n-butylammonium, B-hydroxyethylammonium, di-B- hydroxyethylammonium, tri-B-hydroxyethylammonisoa m (I) um, B-hyroxypropylammonium or a-hydroxypropylammonium cation. Advantageously, however, M

represents a sodium cation and more particularly the ammonium ion.

The sulphonic acid group can be in 0-, mor p-position with respect to the alkaneor alkene-amido radical. Preferably, the sulphonic acid group is in m-position. Examples of such anion-active compounds of Formula I, usable according to the invention, are: l-undec- 10-enamido-benzene-3-sodium sulphonate, dodecanamido-benzene-3-sodium-sulphonate, l-hexadecanamido-4-methyl-benzene-2-sodium sulphonate, l-ocatdecanamido-benzene-4-ammonium sulphonate, l-octadecanamido-2-propoxy-benzene-5 -potassium sulphonate, 1-0ctadecanamido-4-butyl-benzene-3- sodium sulphonate, 1-octadecanamido-4-ethoxybenzene-Z-ammonium sulphonate, l-octadec-9- enamido-benzene-Z- or -4-sodium sulphonate, l-octadec-9-enamido-4-methoxy-benzene-Z-sodium sulphonate, 1-ocataec-9-enamido-4-methyl-benzene-3- sodium sulphonate, l-octadec-9-enamido-4-chloroor -4-bromo-benzene-3-sodium sulphonate, l-octadec-9- enamido-benzene-4-ethyl-ammonium sulphonate, the B-hydroxyethylammonium, di-B-hydroxyethylammonium and tri-B-hydroxyethyl-ammonium salts of l-octadec-9-enamido-benzene-3-sulphonic acid, l-octadec- 9-enamido-4-butoxy-benzene-3-a-hydroxypropylammonium sulphonate or l-eicosanamido-2-methoxybenzene-4-sodium sulphonate.

As anion-active auxiliaries, preferably compounds of Formula II R-C O-NHQ wherein R represents an aliphatic hydrocarbon radical having 17 carbon atoms, and.

M represents a monovalent cation are used, particularly the sodium or ammonium salts of l-octadecanamido-benzene-3-sulphonic acid or I-octadec-9-enamido-benzene-3-sulphonic acid, more particularly, however, l-octadec-9-enamido-benzene-3- ammonium sulphonate.

The anion-active compounds of the general Formula I can be prepared by methods known per se, for instance by condensation of the corresponding fatty acid halides with the amino-benzene-sulphonic acids in the presence of acid-binding agents, such as sodium hydroxide, ammonium hydroxide, sodium carbonate, potassium hydrogen carbonate, sodium acetate, ethanolamine, diethanolamine or triethanolamine.

Anionic dyestuffs suitable for the process according to the invention can'belong to very diverse classes of dyestuffs. These can be, for example, the classes of the azo, anthraquinone, quinophthalone, phthalocyanine, triphenylmethane, nitro or formazane dyestuffs which optionally can contain complex-bound metals, such as copper, nickel, chromium or cobalt. Suitable azo dyestuffs are, principally, monoazo dyestuffs, for instance those of the phenylazobenzene, phenylazonaphthalene, phenylazohydroxyor -aminopyrozole, phenylazo-acyloacetylarylamide type or those of the analogous naphthylazo series, whereby the aromatic nuclei can be suitably substituted. Also suitable are disand polyazo dyestuffs. Metallised azo or formazane dyestuffs principally contain chromium or cobalt, one or two molecules of dyestuff per metal atom participating in the complex. The anionic character of said dyestuffs can be due to the metal complex formation alone and/or acid, salt-forming substituents, such as carboxylic acid groups, acid sulphuric acid-ester and phosphoric acid-ester groups, phosphoric acid groups or sulphonic acid groups. Non-metallised acid wool dyestuffs having one sulphonic acid group are preferred.

Advantageously, the pH-value of the pre-treatment liquor is adjusted to the desired value by the addition of an acid, such as acetic acid, formic acid or sulphuric acid, or a suitablepl-l-regulating salt, such as ammonium sulphate. The pre-treatment of the fiber material at 30 C, preferably at 40 C to 100 C, in the liquor containing the auxiliaries as defined, preferably lasts from 5 to 45 minutes;

After the pre-treatment the acidity of the liquor can be reduced by the addition of an acid-binding agent, such as ammonium hydroxide, di-sodiumor di-potassi um-hydrogen phosphate, sodiumor potassium-acetate as well as hexamethylene-tetramine.

According to a particularly advantageous embodiment of the process of the invention the pre-treatment is carried out'at boiling temperature, the pre-dissolved dyestuff being then added and the dyeing completed at the same temperature. After the dyeing, the dyed material is advantageously rinsed in the usual manner, if necessary given an after-treatment for improving the fastnesses to wet processing, and dried.

Usually, the anion-active auxiliaries are employed in amounts of from 0.2 to 5 per cent by weight, referred to the fiber material to be treated, preferably in amounts of from 1 to 3 per cent by weight.

It has proved particularly advantageous to employ the anion-active auxiliaries, usable according to the invention, in the form of solutions stable on storing. Suitable solvents are, e.g., water, mixtures of water and monovalent or divalent lower aliphatic alcohols, such as ethanol, propanol, isopropanol or ethylene glycol, or ethers of lower divalent alcohols, such as ethyleneglycol monomethyl ether or ethyleneglycol monethyl ether. By lower alcohols those having from one to four carbon atoms are meant. For the preparation of such solutions of auxiliaries stable on storing, especially the corresponding ammonium sulphonates of compounds of the general Formula I have proved useful. A particularly preferred composition contains from to 60 per cent by weight of l-octadec-9- enamido-benzene-3-ammonium sulphonate in a mixture of isopropanol and water, in a volume ratio of from about 1:4 to 4:1, especially in a ratio of from about 1:4 to 1:1.

The pre-treatment liquor and the dye liquor, respectively, canalso contain further auxiliaries usual in dyeing, for example electrolytes, urea, thiourea, thiodiethylene glycol or hydrophilic compounds which are only partly soluble in water, such as butyl alcohol'or benzyl alcohol. 1

Examples of fiber material made from synthetic polyamide which can be dyed by the process according to the invention, are: linear synthetic polyamides such as condensation products from hexamethylene diamine and adipic acid (Polyamide 6.6) or sebacic acid (Polyamide 6.10) or mixed condensation products, e.g., from hexamethylene diamine, adipic acid and e-caprolactam (Polyamide 6.6/6), also the polymerization products from a -caprolactam, known under the tradenames Nylon Perlon, Grilon or Enkalon, or those from w-aminoundecanoic acid (Polyamide 11 and Rilsan). These fibers can be employed in any desired form, thus, for example, in the form of threads, yarns, knitted goods or fabrics.

By the process according to the invention, synthetic polyamide fiber material can be dyed non-streakily and evenly. Surprisingly, it is possible to achieve compensation of differencies in affinity due to the substrate, together with a compensation of differencies in levelness due to the dyestuff, using one anion-active auxiliary only. It is especially unexpected that the migration power of the dyestuffs, which is desirable for attaining.

level dyeings, very often can be remarkably increased by the addition of the anion-active auxiliaries usable according to the invention. Therefore, these auxiliaries are also suitable, e.g., for the levelling of streaky and uneven dyeings by means of an after-treatment.

In the following Examples the temperatures are given in degrees Centigrade.

EXAMPLE 1 To 400 ml of water of about 40 0.2 g of ammonium sulphate and 0.15 g ofa compound of the Formula v climbed-Nag ]N 039 are added. 10 g of knitted fabric made from texture Polyamide 6 yarn are treated for l0 minutes at 40 with this liquor. Then a solution of 0.05 g of the dyestuff of the Formula 0 NH! i 1 CH; CH;

oQwm-bwm $113 $113 0 111B -CH3 -S0;Na

Ha J

in 10 ml of water is added to the liquor.

Within 45 minutes the temperature of the dye bath is raised to the boiling point while continuously moving the textile material, and dyeing is continued with slight boiling during a further 60 minutessThereafter, the dyed material is rinsed with warm and cold water and dried.

in this manner, a non-streaky and even violet dyeing is obtained.

The compound used in this Example as anion-active auxiliary can be prepared, e.g., as follows:

52 g of metanilic acid are dispersed in 250 ml of water and dissolved therein by the addition of 27.3 ml of 30 percent sodium hydroxide solution. Thereafter, the solution is diluted with 300 ml of methylethyl ketone.

To this solution, simultaneously 90 g of oleic acid chloride and 27.3 ml of 30 percent sodium hydroxide solution are added dropwise at to within about 2 hours, the pH-value of the reaction mixture being kept between 6 and 7. Then 50 g of sodium chloride are added to the reaction mixture, whereupon phase formation occurs. The organic phase containing the desired product in dissolved state is separated and evaporated to dryness in vacuo at 60 to 70. 140 g of a white powdery crude product are obtained, the composition of which substantially corresponds to the Formula ms-o O-NHQ I OaNa TABLE 1 Example N0. Sulphonic acid salt 01111350 ONII JNHGB $0.

01.11230 0NH- :|Na

[011113.30 o NII-S o gal I m LII - EXAMPLE i) To 400 ml of softened water 0.2 g of ammonium sulphate and 0.5 ml of a 35 percent solution of the compound of the Formula CnHasCONHQ ]NH469 in a mixture of isopropanol and water in ratio of about 4:7, are added.

10 g of knitted fabric made from textured Polyamide 6.6 yarn are pre-treated in this liquor for 15 minutes at 45. Then a solution of 0.05 g of the dyestuff of the Formula S OzNa (C.l. 23635) in 10 ml of water is added to the liquor. While continuously moving the fiber material, the temperature of the dye bath is increased within 45 minutes to the boiling point and dyeing is continued with slight boiling for another 60 minutes. The dyed material is then rinsed with warm and cold water and dried.

In this manner, a level and non-streaky red dyeing is obtained.

The solution of the compound of the Formula C iTHuCONHQ ]NH4 in isopropanol/water in a ratio of about 4:7, used as auxiliary in this Example, is obtained, e.g., as follows:

35 g Ofmetanilic acid are slurried in 83 ml of water and 66 ml of isopropanol and dissolved by the addition of 16 ml of aqueous 24 percent ammonium hydroxide solution. Then, simultaneously 60 g of oleic acid chloride and 17.5 ml of aqueous 24 percent ammonium hydroxide solution are added dropwise at 0 to 5 to this solution, so that the pH-value of the reaction mixture remains between 4.5 and 5.

In this manner 258 g of a slightly red-brown colored solution of the compound of the above formula are obtained.

If, in Example 17 the dyestuff employed is replaced by the same amount of the dyestuff used in Example l, the procedure being otherwise as indicated in Example 17, an even, non-streaky violet dyeing is obtained.

EXAMPLE 18 0.2 ml of 40 percent acetic acid and 0.1 g of the compound of the Formula are added to 400 ml of softened water. In the obtained liquor g of knitted fabric made from texture Polyamide 6.6 yarn are pre-treated for minutes at 40. Then, a solution of 0.055 g of the dyestuff of the Formula M-..

described in U. S. Pat. No. 3,136,752). 0.038 g of the dyestuff of the Formula and 0.05 g of the dyestuff of the Formula (described in U. S. Pat. No. 2,714,103)

is obtained.

EXAMPLE l9 0.2 g of ammonium sulphate and 0.15 g of the auxiliary described in Example I are added to 400 ml of water of about 40. 10 g of tricot made from texture S OaNa c H. Gama-00G C Ha (described in U. S. Pat. No. 3,320,287) in 10 ml of water is added to the liquor and then dyeing is performed for 60 minutes at boiling temperature. The dyed material is then rinsed with warm and cold water and dried. Maintaining the above conditions a level, non-streaky blue dyeing is obtained, while the dye bath is exhausted to a large extent.

If in this Example 19 the dyeing conditions are altered in that dyeing, instead of for 60 minutes at boiling temperature, is performed only for 45 minutes, but at in a closed dyeing system under pressure, a nonstreaky, level blue dyeing is also obtained.

If in this Example 19 the 10 g of tricot made from textured POlyamide 6.6 yarn are replaced by 10 g of a knitted fabric made from non-textured Polyamide 6.6 yarn and dyeing is performed in a closed system at a temperature of the dyeing time can be reduced to 30 minutes. A non-Streaky, even blue dyeing is obtained.

EXAMPLE 20 1.5 ml of the 35 percent solution of the auxiliary of the Formula [CHHIICONHQ jlNIL (may be produced according to U. S. Pat. No. 2,933,489) in ml of water is added to the liquor, and the liquor is heated to boiling temperature within about minutes. While continuously moving the textile material, dyeing is then continued for an hour at boiling temperature and the dyed material is finally rinsed and dried as usual.

The resulting brown dyeing is essentially smoother than a dyeing obtained without addition of the auxiliary given above.

EXAMPLE 21 Muffs made from textured Polyamide 6 yarn are in troduced in an open dyeing apparatus (packing apparatus). Separately, a liquor having a temperature of about 40 is prepared (goodszliquor ratio about 1:5) which, referred to the weight of the textile material,

contains 5 percent of the 35 percent solution of the auxiliary of the Formula If the auxiliary used in this Example is replaced by a corresponding amount of one of the auxiliaries given in Examples 1 to 16, the procedure being otherwise as described in Example 21, then dyeings of similar quality are obtained.

EXAMPLE 22 400 ml of a warm dye liquor are prepared which contains 0.06 g of the dyestuff of the Formula 0.03 g. of the dyestuff of the formula Naozs /CHzCHaOH Q- CHICHzOH 0.035 g. of the dyestuflt' of the formula.

0 NH; I I SO;Na

I I OH; omNH-o 0Q NHC;

0.3 percent of the dyestuff of the Formula CHzCHrOH and 0.35 percent of the dyestuff of the Formula l SOaNa jam CHzNHCO-Q P) I I H/ CH:4

(all percentages being calculated on the weight of the material to be dyed), pre-dissolved in 10 times the amount of water, are added and dyeing is continued for another 60 minutes at boiling temperature. Thereafter, the dark-brown dyed material is rinsed with warm and cold water and dried.

A knitted fabric prepared from the thus colored yarn is very even in shade and not streaky.

and 0.2 g of ammonium sulphate, then 10 g of Polyamide 6.6 tricot made from textured yarn of differing affinity, are introduced, the temperature of the bath is raised within 45 minutes to the boiling point and dyeing is performed at this temperature for 60 minutes while continuously moving the textile material. The textile material is then rinsed and dried. A streaky dyeing isobtained which can be levelled as follows:

0.5 ml of a 35 percent solution of the auxiliary of the Formula and 0.02 g of ammonium sulphate are added to 400 ml of a 40 warm liquor. The material already dyed is introduced into this liquor, the bath temperature is raised quickly to the boiling point and the material is treated at this temperature for 60 minutes while being continuously moved. Then the treated material is rinsed with warm and cold water and dried.

By this after-treatment the dark-brown dyeing becomes substantially non-streaky and even.

What we claim is:

l. A process for the even, non-Streaky dyeing of linear synthetic polyamide fiber material which comprises I. applying to said fiber material before dyeing, at a pl-I-value of from 2 to 7 and at temperatures of from 30 to 100 C, with a liquor containing, as essential component, an anion-active auxiliary of the formula represents an aliphatic hydrocarbon radical having from 10 to 19 carbon atoms,

represents hydrogen, an alkyl group having from 1 to '4 carbon atoms, an alkoxy group having from 1 to 4 carbon atomsor a halogen atom, and M represents a monovalent cation, and ll. adding the solution of at least one anionic dyestuff at temperatures of from 40 to 100 C and completn he dy ing, atte turesv 95 r m 9 1, 4 C.

wherein 2. A process as defined in claim 1, employing a liquor containing a compound of the formula CnHag-C ONHQ wherein R represents an aliphatic hydrocarbon radical having 17 carbon atoms, and M represents a monovalent cation, as anion-active auxiliary; 3. A process as defined in claim 1, employing a liquor containing the compound of the Formula am n/r

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2310074 *May 4, 1939Feb 2, 1943Unichem Chemikalien Handels ATreatment bath
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3925016 *Dec 12, 1972Dec 9, 1975Ciba Geigy AgPolyarcrylonitrile basic dyeing process with anionic assistant
US3961881 *Jul 22, 1974Jun 8, 1976Imperial Chemical Industries LimitedPolyamide textiles, tanning agent, disperse dyestuff
US4030880 *Oct 9, 1975Jun 21, 1977E. I. Du Pont De Nemours And CompanyOf polyamides, melt-spinning, drawing, dye leveling agents
US4445905 *Apr 5, 1983May 1, 1984Harry SchaetzerProcess for trichromatic dyeing or printing of polyamide
US4537598 *May 24, 1984Aug 27, 1985Ciba-Geigy CorporationProcess for trichromatic dyeing or printing of polyamide
USB314489 *Dec 12, 1972Jan 28, 1975Ciba Geigy AgTitle not available
EP0092512A1 *Mar 31, 1983Oct 26, 1983Ciba-Geigy AgProcess for trichromatic dyeing or printing
EP0127579A1 *May 21, 1984Dec 5, 1984Ciba-Geigy AgTrichromatic dyeing or printing process
Classifications
U.S. Classification8/586, 8/589
International ClassificationD06P1/44, D06P1/62, D06P3/24
Cooperative ClassificationD06P1/628, D06P3/241
European ClassificationD06P3/24A, D06P1/62D