US3467486A

US3467486A - Dyeing and printing on polyamide fibers

Info

Publication number: US3467486A
Application number: US637309A
Authority: US
Inventors: Charles Soiron; Hans Rafael; Walter Stockar
Original assignee: JR Geigy AG
Current assignee: Novartis AG
Priority date: 1962-07-31
Filing date: 1967-05-09
Publication date: 1969-09-16
Anticipated expiration: 1986-09-16
Also published as: GB1002330A; SE309768B; DE1283801B; NL6811161A; USRE27386E; CH375692A; USRE27333E

Description

United States Patent US. Cl. 8-74 12 Claims ABSTRACT OF THE DISCLOSURE In the process of dyeing and printing polyamide fibers with reactive dyestuffs, there is provided an after-treatment of the dyed fibers for the purpose of fixing still unreacted residual dyestulf on the fibers, which after-treatment does not injure the fibers and permits the drying of the after-treated fibers directly without further intermediate treatments.

This application is a continuation of application Ser. No. 515,774, filed Oct. 22, 1965, and abandoned since the filing of the instant application, which application is in turn a division of application Ser. No. 296,392, filed July 19, 1963, and now abandoned.

This invention relates to improvements in dyeing and printing on polyamide fibers as well as, as industrial products, the dyed and printed polyamide fibers treated according to the invention.

Hitherto, wool and other polyamide fibers including nylon and the like synthetic polyamide fibers which had been dyed with reactive dyestuffs containing per molecule at least one substituent which can be split off as an anion during the dyeing and/or after treatment of the dyed fibers, had to be subjected to an after-treatment in an aqueous basic medium of a pH of preferably about 7.5 or higher which contains, for example, sodium hydroxide, sodium carbonate, or preferably ammonia or hexamethylenetetramine as the basic agent.

This known alkaline after-treatment, which serves to fix on the fibers still unreacted reactive dyestuff present in the dyed goods, suffers from the drawback that the polyamide fibers can be injured by the alkaline medium and particularly by a subsequent drying step if the same is carried out directly on the after-treatment fibers.

Therefore, in the known dyeing methods, the after-treatment with an alkaline medium is followed usually by a further treatment in an acid medium prior to final drying of the dyed or printed fibers.

Another drawback of the after-treatment with alkaline agents such as ammonia or hexamethylenetetramine resides in the tendency of the alkaline bath to remove at least part of the still unreacted dyestuff from the fibers, whereby an exact control of the shade of the fixed dyeing or prints is made very difiicult.

It is, therefore, an object of the present invention to provide, in a process of dyeing or printing polyamide fibers with reactive dyestuffs of the type described, as after-treatment of the dyed fibers for the purpose of fixing still unreacted residual dyestuff on the fibers, which after-treatment does not injure the fibers, permits of drying the aftertreated fibers directly without further intermediate treatments, and allows for a more exact control in producing a desired shade.

Patented Sept. 16, 1969 These objects are attained by the treatment according to the invention, which comprises, as an after-treatment in dyeing and printing processes for producing colored polyamide fibers by heating and thereby reacting said fibers together with reactive dyestuff which contains at least one mobile substituent capable of being split off as anion, in an aqueous acid medium, preferably at a pH of about 4.5 to 5, and, preferably, with subsequent rinsing of the colored fibers in water of a temperature of about 10 to preferably 60, and not more than C., and drying,

(I) Introducing the freshly colored, and preferably immediately subsequently rinsed, fibers, directly thereafter and prior to drying, into an aqueous solution of a condensation product of (a) A naphthalene sulfonic acid, in particular a monoto trisulfonic acid, and preferably naphtha1ene-2-rnonosulfonic acid, or a 1,2,3,4-tetrahydronaphthalene sulfonic acid,

(b) From about 0.5 to 1.5, and preferably from 0.8 to 1.2 parts by weight, per part by weight of (a), of a compound of the formula HO-phenylene-SO -phenyIene-OH, preferably 4,4-dihydroxy-diphenylsulfone, and

(c) From about 0.1 to 0.2, and preferably 0.1 part by weight, per part by weight of (a), of formaldehyde, in aqueous, preferably about 30%-solution.

(II) If necessary, adjusting the pH of the aqueous solution to about 4 to 5.5, and preferably to 4.5 to 5, by the addition of acid, such as acetic or formic acid, and preferably of acetic acid, and

(III) Heating the said aqueous solution and the colored fibers therein for a short time, about 10 to 60, and preferably 15 to 30 minutes, at a temperature of about 20 to 100, and preferably 60 to C.

According to another mode of carrying out the treatment according to the invention is practice, the condensation product used as the fixing agent in the aqueous acid solution of steps (I) to (III) described supra, is produced by condensation of (a) a 0:,w-di0hl010- or a,w-dibromoalkane of from 2 to 7 carbon atoms, or w,w'-dichloro-dialkylether with a total of from 4 to 8 carbon atoms, with (b) a tertiary saturated aliphatic amine with a total of from 6 to 24 carbon atoms and from two to four amino nitrogen atoms, in such molar ratio of (a):(b) that approximately one halogen atom is present in the condensation reaction for every amino nitrogen atom.

According to yet another mode of carrying out the treatment according to the invention in practice, there is used in the aqueous solution of steps I to III supra, in lieu of the above-mentioned condensation products, a product produced by the condensation of (a) Dicyanodiamide, (b) At least one mole, per mole of (a), or an excess thereover, of an ammonia donator which is either urea or an ammonium salt of a mineral acid capable of splitting off ammonia, and (0) At least two moles, per mole of (a), or an excess thereover, of formaldehyde in aqueous, preferably 30% by weight, solution. A concentration of about 0.5 gram of condensation product per liter of solution is the minimum.

In the second and third modes of the treatment according to the invention described above, the addition of acid to the solution in accordance with step II, supra, is mandatory.

As polyamide fibers, those of natural origin, above all wool and silk, but also synthetic polyamide fibers such as the various kinds of nylon e.g. nylon 6, nylon 66, and nylon 11 (Rilsan), are suitable for the after-treatment according to the invention.

These polyamide fibers are dyed by known methods in a dyestuif solution which, in addition to the dyestuffs mentioned, can also contain the auxiliaries usual in woo-l dyeing, e.g. salts such as sodium sulfate or ammonium sulfate and/or dilute acids, e.g. acetic or formic acid, and/ or wetting agents, e.g. condensation products of fatty acids having at least 8 carbon atoms and lower alkanolamines such as are described in US. Patent 2,089,212.

The aforesaid fibers are printed by known processes in neutral or acid medium in the presence of thickeners and, optionally, urea.

The after-treatment according to the invention with the solution of the condensation products is preferably performed in a solution which contains these products in a concentration of about 0.5 to 3 g. per liter, furthermore, optionally, other additives usual in textile dyeing, and

finally, acid, e.g. acetic or formic acid, as mentionedabove.

The aforesaid condensation products suitable for use in the first above-described mode of carrying out the invention in practice are produced as described in German Patent 611,671, issued April 5, 1935; those suitable for use in the second mode of practicing the invention described above, are produced as described in German Patent 894,237, issued October 22, 1953. This class of condensation products is obtained by reacting the components mentioned above at a raised temperature, about 50 to 140 C., possibly in the presence of diluents, e.g. butyl alcohol, ethylene glycol or diethylene glycol. Among the saturated aliphatic tertiary polyamines defined above, there are:

Di-, triand tetra-amines such as N .N-tetramethylhexamethylenediamine and homologues, N,N',N"-pentamethyl-di-ethylenetriamine, N,N',N",N'-hexamethyl-triethylenetetramine as well as industrial mixtures thereof also.

Examples of :,w-dih21l0g6n alkanes are 1,2-dichloroor 1,2-dibromo-ethane, 1,3-dichloro-propane, 1,4dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane; w,w-di halogen ethers are, e.g., ,8,B-dichlorodiethyl ether, ethylene glycol-di-B-chloroethyl ether, p,e-di-(2-ch1oroethoxy)-di-ethyl ether, 'y,y-dichloropropyl ether as well as glycerin dichlorohydrin. The reaction products are most effective when the ratio of the reaction components is so chosen that there is about one halogen atom per N atom, so that, for example, on using a triamine, two mols of amine are quaternized with three mols of a,w-dihalogen alkane. Particularly good results are obtained with the condensation product of 2 mols of N,N,N"-pentamethy1- diethylenetriamine and 3 mols of fi,/3-dichlorodiethyl ether.

The condensation products usable in the third mode of carrying out the treatment according to the invention are produced from dicyanodiamide and the ammonium salt of a strong mineral acid or urea, and formaldehyde, as described in German Patent 929,642 issued Oct. 22, 1953. Best results are obtained with compounds from this class which are produced in accordance with Example 2 of German Patent 929,642.

The reactive dyestuffs used according to the invention can be of the most varied classes of dyestuffs. Preferably they are nitro, azo, anthraquinone or phthalocyanine dyestuffs, which classes excel in stability. They contain watersolubilizing, acid, salt-forming groups, mainly sulfonic acid groups, possibly also carboxyl groups or sulfamyl groups, in the latter case, among others, also acylated sulfamyl groups, e.g. disulfimide and carbonyl sulfimide groups.

The advantages attained according to the invention are particularly impressive when the reactive dyestufis conventionally used for the fast dyeing of cellulose are used which contain sulfonic acid groups, e.g. 2 to 4, per dyestuff molecule. Thus, examples of dyestuffs, dyeings of which are especially suitable for use in the treatment according to the invention are nitrodiarylamine sulfonic acids, metal-free monoand poly-azo dyestuffs, heavy metal-containing, e.g. chromium or cobalt-containing, o,o'-dihydroxy-, o-hydroxy-o-carboxyand o-hydroxyo'-amino-mono-azo and dis-azo dyestufi s, copper-containing formazane dyestuffs, l-amino-4-phenylamino anthraquinone dyestuffs, and copper phthalocyanines with substituted sulfamyl groups, all of which preferably contain at least two sulfonic acid groups.

Mobile substituents which can be split ofli as anion are mainly: radicals of strong acids, in particular halogen atoms, of these preferably chlorine, or bromine or fluorine, the mobility of which is due, for example, to the bond at fi-carbon atoms in negatively substituted organic radicals, at S0 groups in the case of fluorine, at carbon atoms adjacent to teritary ring nitrogen in nitrogen heterocycles of aromatic character, in this case preferably 6-membered heterocycles having at least two tertiary ring nitrogen atoms; aromatically bound halogen atoms in oand/or p-position to one (or more) electrophilic gronp(s), in particular fluorine or chlorine atoms; further, for example, the radical of sulfuric acid in sulfated fl-hydroxyalkyl compounds, e.g. in sulfated ,B-hydroxy-alkyl sulfonyl and sulfamyl groups; or the radical of hydroxyaryl compounds in O-aryl urethane groups.

Dyestuffs usable according to the invention contain the substituent which can be split off as anion, for example, in the form of fl-chloroor fl-bromo-fatty acid amide groups, in which case fl-chlorocrotonic acid amide or fl-bromopropionic acid amide groups are preferred; or the said substituent is in the form of fluoroor chloronitrobenzoylamino groups or fluoroor chloro-nitrobenzene sulfonylamino groups in which the fluorine or chlorine atoms are in the oand/or p-position to the nitro groups or groups; or, preferably, it is in the form of chloroor bromo-diazinylamino triazinylamino groups, in which case it is in particular in the form of monochloroor dichloro-s-triazinylamino groups, and preferably, dior tri-chloropyrimidylamino groups. Dyestuffs with at least one dior tri-halogen pyrimidylamino group and at least 2 sulfonic acid groups are preferred in the dyeing and printing processes comprising the after-treatment according to the invention.

An advantage of the treatment according to the invention over the known processes is the elimination of an alkaline aftertreatment with, for example ammonia or hexamethylenetetramine. This advantage becomes most apparent in the dyeing and printing of wool which is sensitive to alkali, as the danger of injury to the fibers inherent in the alkaline after-treatment is avoided.

Moreover, the control of producing the desired shade more exactly is facilitated since changes in shade due to shifting of the pH of the dyeing medium from acid to alkaline and possibly back to acid are avoided.

Dyeings or prints on polyamide fibers attained according to the invention are distinguished by pure, strong and even shades and good fastness properties. In particular, they have remarkable wet fastness properties, for example fastness to water, washing, milling and perspiration, and particularly to sea-water.

The following non-limitative examples illustrate the invention. Where not otherwise stated, parts and percentages are given by weight. The relationship of parts by weight to parts by volume is as that of grams to cubic centimeters. The temperatures are given in degrees centigrade.

Example 1 parts of wool are dyed in 4000 parts of a dye liquor which contains the following agents:

4 parts of a dyestuif of the formula ('31 (El C-C s 17111-0 /N N=C -N=N-- S0311 HOsS SO3H 0.5 part of a condensation product of 1 mol of oleic acid and 2 mols of diethanolamine (Example 5 of US. Patent No. 2,089,212),and

4 parts of 80% acetic acid.

The goods are introduced into the liquor at 50, dyeing is performed for minutes at this temperature, the bath is brought to the boil within minutes and dyeing is continued at the boil for minutes.

After dyeing, the goods are well rinsed and treated in a fresh bath for 20 minutes at -80 which contains 0.75 g. per liter of a condensation product of formaldehyde with dihydroxydiphenyl sulfone and naphthalene sulfonic acids, the production .of which condensation product is described below, as well as 0.25 g. per liter of acetic acid.

Valuable red dyeings are obtained in this way which are very wet fast.

The condensation product mentioned is obtained as follows:

parts of the sulfonating mixture, obtained by heating for several hours at -160", 520 parts of naphthalene and 5 60 parts of concentrated sulfuric acid until water solubility is attained, are heated for about 1 hour at 105110 with 100 parts of a dihydroxydiphenyl sulfone, 50 parts of water and 45 parts of formaldehyde (30%). The dihydroxydiphenyl sulfone is obtained by heating 540 parts of phenol and 180 parts of 60% oleum for 3 hours at -180 and distilling 01f excess phenol.

By using, instead of the dyestufl? given in Example 1, the dyestuffs listed in column 2 of the following table, and otherwise following the procedure described in said example, wool dyeings of the shade given in column 3 and of good fastness to washing, perspiration and sea water are obtained.

TABLE I No. Dyestufi Shade on wool 1 CH Greenish-yellow.

o1 SOH 3 a I c N:

L 11038 NH-C (J H a 1 CH C] 2 n Reddish-yellow.

l l N=N-C NH-i1 o o1 CH3 3 (31 Red.

N N H A i k N 01 N=N SOaH SO;H 80 11 4 1TH; Blue.

SOaH

b NH-Qsom son! Cl S 03150 Scarlet.

N-O SOsH NH-C N TABLE 1Contlnued No. Dyestuff Shade on wool 13.. Ho NlEllz Blue-black.

HOaS-OCH2CH2S Oz-N= N=NC S 0zCH2CH2O-SOaH H035 -S0aH 14..." /Ol Blue.

HOHS c Cu(|) lTIH-O N I N=C NH- -S0:H

' HO S- SO H Example 2 Example 4 W001 is printed with a printing paste of the following Nylon is printed with a printing paste of the following composition: composition:

30 parts of the dyestutf of the formula parts of the dyestutf of the formula 01 e1 CH3 C1 JJJJ so H 3 HO NH--O N I I 1103s NH- .'-o1

01 l 0 SOaH 11033 $0311 50 parts f urea 250 parts of boiling water, 100 parts of urea, 5 p r s f phenol, 10 parts of the sodium salt of m-nitrobenzene sulfomc 30 parts of throdiethylene glycol, acid 450 parts of 5% sodium alginate solution, and

450 parts of 5% sodium alginate solution, and 1 5 parts of water. 410 parts of water. The goods are then dried and steamed and rinsed, first The goods are then dried, steamed and well rinsed with 4 w1th cold and then with 60 warm water.

cold water.

The rinsed wool is then treated for 20 minutes at 60- 80 in a fresh bath which contains 0.75 g. per liter of the formaldehyde/dihydroxydiphenylsulfone/naphthalene sulfonic acids condensation product used in Example 1, supra, as well as 0.5 g. per liter of aqueous 80% acetic acid.

In this way, valuable red prints are obtained which have very good wet fastness properties.

Example 3 and 1 part of 80% acetic acid.

The goods are entered into the liquor at 40, dyeing is performed for 10 minutes at this temperature, the bath is brought to the boil within 30 minutes and dyeing is continued for minutes at the boil.

After dyeing, the goods are well rinsed and treated for 20 minutes at 6080 in a fresh bath which contains 0.75 g. per liter of the formaldehyde/dihydroxydiphenylsulfone/naphthalene sulfonic acids condensation product mentioned in paragraph 3 of Example 1 and 0.25 g. per liter of 80% acetic acid.

In this way, valuable greenish yellow dyeings which have very good wet fastness properties are obtained.

The rinsed goods are after-treated in a fresh bath in the manner described in the previous Example 3.

In this way, valuable greenish yellow prints are obtained, which have very good wet fastness properties.

Example 5 100 parts of wool are dyed in 4000 parts of a dye liquor which contains the following agents:

4 parts of a dyestutf of the formula no NH--C/ 1 N N N=o soar: HOaS- S0311 0.5 part of a condensation product of 1 mol of oleic acid and 2 mols of diethanolamine (Example 5 of US. Patent No. 2,089,212) and t 4 parts of acetic acid.

These goods are introduced at dyeing is performed for 10 minutes at this temperature, the bath is brought to the boil within 10 minutes and dyeing is performed at the boil for 45 minutes.

After dyeing, the dyed goods are rinsed and treated for 1 mentioned, a nitrogen-containing condensation product of 34 parts of dicyanodiamide with 5.5 parts of ammonium chloride, 18 parts of urea and 80 parts formaldehyde is used in the after-treatment liquor and otherwise the same procedure is followed.

If, instead of the dyestuff mentioned in the example, those given in column 2 of the following table are used and otherwise the procedure described in the example is followed, then corresponding wool dyeings as given in 5 column 3 are obtained.

TABLE II No. Dyestufi Shade on wool 1 (I311: 1 Greenish-yellow.

HO S

N N N H I HOaS-- NH-C C 0 01 H Cl 2 (I31 Reddish-yellow.

C SlOaH II N=N- -NHC\ o Cl CHa 3 (31 Red.

ll 5 HO NH-C C "SOZH S0311 $0311 4 (H) IIIHz Blue.

SOQH

S|O H -fi I G N N i 01 5..-... (IHI $10 11 Scarlet;

C1 SO3H SOSH I NH-C N i 9 C1 C1 6 (|)II NH-OO-CH=CCH Orange.

SOJH SOaH 7...... C1 C1 Turquoise blue.

(HSO;);-{Cu-1hto.}SOz-NH- I) NH--C\ /N (wherein CuPhto. is the copper phthaloeyaniue radical) 15 Example 6 W001 is printed with a printing paste of the following composition:

30 parts of the dyestuff of the formula 31 Cl HO NHC N SOaH H 8 $0311 100 parts of urea,

110 parts of the sodium salt of m-nitrobenzene sulfonic acr 450 parts of 5% sodium alginate solution, and

410 parts of water.

The goods are then dried, steamed and well rinsed with cold water.

The rinsed wool is after-treated as described in Example 1. In this way, valuable, vivid bluish red prints are obtained which have very good wet fasteness properties.

Similar results are obtained if, instead of the reaction products as described in Example 1, a nitrogen-containing condensation product of 34 parts of dicyanodiamide with 12 parts of ammonium chloride, 12 parts urea and 80 parts of formaldehyde are used.

Example 7 100 parts of nylon are dyed in 4000 parts of a dye liquor which contains 1.5 parts of a dyestufi of the formula and 1 part of 80% acetic acid.

The goods are introduced at 40, dyeing is performed for 10 minutes at this temperature, the bath is brought to the boil within minutes and dyeing is continued for minutes at boiling temperature.

After dyeing, the goods are well rinsed and then treated in a fresh bath for 20 minutes at 80 which contains 0.75 g. per liter of the reaction product of 2 mols of N,N,N"-pentamethyl diethylene-triamine and 3 mols of p,f3'-dichlorodiethyl ether, and also 0.5 g. per liter of 40% acetic acid. In this way, valuable greenish yellow dyeing which have very good wet fastness properties are obtained.

Similarly good dyeings are obtained if, in the above example, a nitrogen-containing condensation product of 34 parts of dicyanodiamide with 11 parts of ammonium chloride, 12 parts of urea and 80 parts of formaldehyde is used in the after-treatment bath instead of the reaction product mentioned and otherwise the same procedure is followed.

Example 8 Nylon is printed with a printing paste of the following composition:

@ HOS NHE 50 parts of urea,

250 parts of boiling water,

45 parts of phenol,

30 parts of thiodiethylene glycol,

450 parts of 5% sodium alginate solution and 145 parts of water.

The goods are then dried, steamed and rinsed first with cold and then with 60 warm water.

The rinsed goods are after-treated as described in Example 3. In this way, valuable greenish yellow prints which have very good wet fastness properties are obtained.

Similar results are further obtained if, instead of the reaction product as described in Example 3, a reaction product obtained from corresponding amounts of N,N- tetramethyl ethylene diamine and 'y,'y-dichloropropylether or 1,4-dibromobutane or corresponding amounts of N,N tetramethyl tetramethylene-diamine and glycoldichlorohydrin is used.

We claim:

1. In dyeing and printing processes for producing colored polyarnide fibers by heating and thereby reacting said fibers together with reactive dyestutf which contains at least one mobile substituent capable of being split off as anion, in an aqueous acid medium, and then drying the colored fibers, the improvement comprising (1) introducing polyamide fibers freshly colored with reactive dyestuff, after coloration and prior to drying, into an aqueous solution of a condensation product of (a) a member selected from the group consisting of a naphthalene sulfonic acid and a 1,2,3,4- tetrahydronaphthalene sulfonic acid, (b) from about 0.5 to 1.5 parts by weight of a compound of the formula HO-phenylene-SO -phenylene-OH per part by weight of (a), and

(c) from about 0.1 to 0.2 part by weight of formaldehyde per part by weight of (a), in aqueous solution,

(H) adjusting the pH of the aqueous solution to about 4 to 5.5 by the addition of acid, and

(III) heating the said aqueous solution and the colored fibers therein for about 10 to 60 minutes at a temperature of about 20 to 100 C.

2. The improvement described in claim 1, wherein the member (a) is a naphthalene-monosulfonic acid.

3. The improvement described in claim 1, wherein the member (a) is naphthalene-Z-sulfonic acid.

4. The improvement described in claim 1, wherein the compound under (b) is 4,4-dihydro-diphenylsulfone.

5. The improvement described in claim 1, wherein the compound under (b) enters into the condensation product at a ratio of 0.8 to 1.2 part by weight per part by weight of (a).

6. The improvement described in claim 1, wherein the heating under step HI is carried out for about 15 to 30 minutes.

' 7. The improvement described in claim 1, wherein the aqueous acid solution and fibers therein are heated in step III at a temperature of about 60 to C.

8. The improvement described in claim 1, wherein the acid added in step II is a member selected from the group consisting of acetic acid and formic acid.

9. The improvement described in claim 1, wherein, in step II, the pH is adjusted to about 4.5 to 5.

17 18 10. The improvement described in claim 1, further References Cited comprising the step of rinsing the colored fibers, after UNITED STATES PATENTS removal from the dyeing medium and prior to introduction into the aqueous solution containing the condensa- $298,774 1/1967 Solron et a1 874 2,623,806 12/1952 Fuchs 821 tion product, with water having a temperature of about 5 10 to 70 C., but not higher.

11. The im rovement described in claim 1, wherein said reactive dfiestuff contains a halogen-substituted pyrim- GEORGE LESMES Pnmary Exammel' idylamino reactive dyestuff radical and from 2 t0 3 sul- T. J. HERBERT, JR., Assistant Examiner fonic acid groups. 10

12. The improvement described in claim 1, wherein U.S. C1.X.R. said polyamide fibers are wool. 85 4, 55

3,118,723 1/1964 Harding.