US3313589A

US3313589A - Levelling agents for dyeing textile materials

Info

Publication number: US3313589A
Application number: US408418A
Authority: US
Inventors: Landauer Franz; Weckler Gerhard; Reuter Martin
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1963-11-02
Filing date: 1964-11-02
Publication date: 1967-04-11
Anticipated expiration: 1984-04-11
Also published as: BE655185A; FR1415072A; CH420049A; GB1038527A; DE1266271B

Description

United States Patent LEVELLING AGENTS FOR DYEIN G TEXTILE MATERIALS Franz Laudauer and Gerhard Weckler, Frankfurt am Main, and Martin Renter, Kronberg, Taunus, Germany, assignors to Farbwerke Hoechst Aktiengeseiischaft vormals Meister Lucius & Bruning, Frankfurt am Main, Germany, a corporation of Germany No Drawing. Fiied Nov. 2, 1964, Ser. No. 403,418 Claims priority, application Germany, Nov. 2, H63,

7 Claims. (Ci. 8-35) In the dyeing with leuco-sulfuric acid esters of vat dyestuffs difficulties are often caused by the fact that the leuco compounds of quite a number of vat dyestuffs show a great afiinity to cellulose fibers and that unlevelled dyeings are obtained due to the high velocity with which the dyestuffs are, therefore, absorbed by the fibers. In many cases, difliculties of said kind are likewise observed with substantive dyestuffs as well as in the dyeing of nitrogencontaining fibers dyeable with acid dyestuffs, for instance, with wool dyestutfs absorbed by the fibers in a neutral or a weakly acid medium.

It is already known that by adding to the dyebaths cationic compounds on the base of polyalkylene-polyamines the absorption period is increased and the evenness of the dyeings is improved. In many cases, however, this method of operation shows the drawback that the addition compounds formed between the dyestutf and the auxiliary agent are very stable and that in the course of the dyeing process the dyestulf is only insufiiciently liberated, even if the temperature is increased so that considerable amounts of dyestutf are lost for the dyeing process. The known oxethylated alkyl-phenols or the oxethylated fatty alcohols recommended as additional agents for obtaining more even dyeings show similar drawbacks. Likewise with these products the complexes formed in the dyebath between the dyestuft and the auxiliary agent are often of a high stability so that large amounts of dyestufi are lost for the dyeing process and that only pale shades are obtained.

Now we have found that said diificulties could be overcome and that with full exhaustion of the dyebaths more even dyeings were obtained on nitrogen-containing fibers and on cellulose fibers by adding to the dyebaths watersoluble oxazolines carrying in 4-position polyglycol ether chains and in 2-position-directly or by means of a bridge-member-an al'kyl radical containing about 4-20 carbon atoms, or by treating the dyeings additionally with an aqueous bath containing such an oxazoline compound. It is likewise of advantage that the levelling agents according to the invention are active in the same way for dyeings on nitrogen-containing fibers as well as on cellulose fibers, whereas most of the hitherto known levelling agents are suitable for dyeings on either one or the other kind of fibers.

The oxazoline compounds used as levelling agents according to the invention are, above all, those corresponding to the general formula in. which R represents an alkyl radical with 320, preferably 618 carbon atoms,A stands for a methylene group, for oxygen or the sulfur atom, R stands for an alkyl group with.1'4 carbon atoms or the radical 'ice wherein n is an integer of 2 or 3, y=1-3, preferably 1, x=4-100, preferably 960, R represents the radical wherein n, y and x have the meanings given above.

As oxazolines substituted in the above-mentioned way, there are used, for instance, the addition compounds of ethylene oxide and/ or propylene oxide to 2-hexyl-4-methyl 4-hydroxy-methyl-oxazoline, 2,-undecyl-4-ethyl-4-hydroxy-methyl-oxazoline, Z-heptadecyl-4-ethyl-4-hydroxymethyl-oxazolineor Z-undecyl-4,4abis-hydroxy-methyloxazoline. The oxazolines can be prepared according to known methods, for instance, according to US. Patent 2,504,951 from saturated or unsaturated monocarboxylic acids, such, for instance, as tallow oil fatty acid or coconut oil fatty acid, by reaction with alkylol-amines-( 1,2) containir; at least 2 hydroxy groups, such, for instance, as 2 amino-Z-ethyl-propanediol-(1,3), Z-amino-Z-methyl-propanediol-(L3) or the tris-hydroxy-methyl-aminomethane with splitting ofi of 2 mols of water at an elevated temperature and, if desired, under reduced pressure. The hydroxy groups of the substituted oxazolines thus obtained can then be reacted according to known methods, for instance, according to the operating method described in German patent application No. 1,027,672 laid open to public inspection, with epoxides, such, for instance, as ethylene-oxide, or propylene-oxide or mixtures of said epoxides. When operating in this manner, about 4-100 mols of epoxide, preferably 9-60 mols, are used per mol of oxazoline.

In compliance with the dyeing method, the dyestuffs used and the fibrous material to be treated, the oxazoline compounds used as levelling agents according to the inveution are used in varying quantities. The most favorable amount for each treatment can be easily ascertained .by a dyeing test.

Generally, quantities Within a range of about 0.05 and about 8 grams/liter, preferably between 0.1 and 3 grams/ liter of dyebath are used.

The oxazoline compounds claimed are likewise excellently suitable for the additional levelling of unequal dyeings. When operatingin this way, the dyeings are additionally treated at an elevated temperature with an aqueous bath containing the oxazoline compound generally under the same conditions under which the dyeing is carried-outQ v The levelling agents according to the invention can be applied together with the usual dyestuffs, for the levelling of all dyeings realized on nitrogen-containing fibers and cellulose fibers according to known dyeing methods. Nitrogen-containing fibers comprise polyamide fibers, above all protein fibers, such as wool and silk. Most suitable for the dyeing of said nitrogen-containing fibers are, above all, those of the series of the so-called acid dyestulfs. As cellulose fibers there are used native and regenerated cellulose fibers. As dyestuffs which may be used for the dyeing of cellulose fibers there are mentioned, for instance, substantive dyestuifs and vat dyestufis which are used in the form of their sodium-leuco compounds.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto. Unless otherwise stated, the indications in percent are calculated on the weight of the goods to be dyed.

Example 1 Bleached cotton yarn is dyed in the open vat at a goodsto-liquor ratio of 1:20 with 2% of the dyestuff C.I.7O 305 (Cf. Colour Index, 2nd edition (1956)), according to the lN-process for 45 minutes at 5060 C. Per liter of dyebath 16 cc. of sodium hydroxide solution (38 B.) and 3 grams of sodium-dithionite are used. The goods =3 are then achieved in the normal way, i.e. the dyeing is subjected in the usual way to oxidation, acidification and saponification. 5 grams of the cotton yarn thus dyed together with 5 grams of undyed cotton yarn are treated in the same manner as described above with the blank vat IN. A completely unsatisfactory levelling effect is obtained together with a very uneven dyeing of the added yarn. Likewise insufficient levelling effects are obtained by adding in each case 0.1 or 1.5 g./l. of polyglycol of an average molecular weight of 1000 or 0.1 or 1.5 g./l. of the addition compound of mols of ethylene-oxide to 1 mol of dodecyl alcohol. In the same manner levelling effects are realized by simultaneously using in each case 0.1 or 1.5 g./l. of the addition compound of mols of ethylene-oxide to 1 mol of Z-undecyl-4,4-bis-hydroxymethyloxazoline. Already with low starting quantities a distinct levelling effect is observed together with an improved evenness of the dyeing, but no remarkable retardation effect occurs. Only with quantities of 1.5 g./l.

and more a retardation effect can gradually be observed. 7

Example 2 On the same material and in the same Way as described in Example 1 a dyeing is produced with 2% of the dyestulf C.I.6O 010 (cf. Colour Index, 2nd edition (1956)) according to the .IN-process and levelling tests are then carried out as described in Example 1.

Whereas again with the blank vat IN and products such as a polyglycol of a molecular weight of 600 and an addition product of 5 mols of ethylene-oxide to 1 mol of oleyl alcohol in quantities of 0.1 or 1.5 g./l. each, a completely insufficient levelling effect is obtained, very good levelling effects without remarkable retarding action are observed when starting from 0.1 or 0.5 g./l. of the addition compound of 9 mols of ethylene-oxide to 1 mol of 2-undecyl-4,4-bis-hydroxy-methyloxazoline. Similar results are obtained with 0.1 to 0.5 g./l. of the addition product of 53 mols of ethylene-oxide to 1 mol of 2-undecyl-4-ethyl-4-hydroxy-methyl-oxazoline.

Example 3 As described in Example 1, a dyeing is obtained with 2% of the dyestuff C.I.59800 (cf. Colour Index, 2nd edition (1956)) according to the IN-process and levelling tests are likewise carried out as described in Example 1. With the blank IN-vat and compounds such as the addition compound of 15 mols of ethylene-oxide to 1 mol of stearyl alcohol or polyglycol of a molecular weight of 600 in quantities of 0.1 or 1.5 g./l. in each case, a completely unsatisfactory result is obtained, whereas with 0.1

or 0.5 g./l. in each case of the addition compound of 12 mols of ethylene-oxide to 1 mol of 2-undecyl-4-ethyl- 4-hydroxy-methyl-oxazoline a good levelling effect is obtained.

Example 4 10 weight units of a Wool gabardine (20 grams) are divided into a larger piece of 4 Weight units (8 g.) and into 6 smaller pieces of 1 Weight unit (2 grams) each, thoroughly Wetted and then centrifuged in a uniform way. The large piece of 4 weight units is first introduced into the boiling dyebath containing 1% of the wool dyestuif C.I.24 800 (cf. Colour Index, 2nd edition (1956)), 5% of sodium sulfate and 4% of acetic acid. After 2, 4, 8, 16, 32 and 64 minutes each a small piece of a weight-unit of one is added and boiling is continued for a further 56 minutes, after the last piece has been added. Total boiling time: 2 hours. The goods-to-liquor ratio amounts to 1:40 calculated on the total wool material (:800 cc.). Evaporated water is replaced after a boiling time of 1 hour. (Kramrisch test, B. Kramrisch, J. 502. Dyers and Coll., May 1959, pages 242 et seq.)

The above-described combined absorption-levelling test is carried out without as Well as with addition of increasing quantities of the compounds claimed.

Whereas without the addition of the auxiliary agents the dyestuff is nerly completely absorbed prior to the addition of the last pieces of the wool gabardine, a good levelling effect between the Wool pieces added at first to the dyebath and those added at last can be observed, if in each case 0.1 or 2 g./l. of the addition compound of 12 mols of ethylene-oxide to 1 mol of 2-undecyl-4-ethyl- 4-hydroxymethyl-oxazoline are added in low concentrations.

A similar good levelling effect is obtained with the compounds mentioned in Examples -1-3, whereas products such as polyglycols of a molecular weight of 1000 as well as an addition product of 5 mols of ethyleneoxide to 1 mol of oleyl alcohol in quantities of 0.1. or 2 g./l. only show a small levelling effect.

Example 5 A previously cleaned cross-wound bobbin (as described in Example 1) is dyed at a goods-to-liquor ratio of 1:10 in the closed apparatus with 0.2% of the dyestuff C.I.70 035 (cf. Colour Index, 2nd edition (1956)) according to the IN-process in the usual manner for 45 minutes at 50-60 C. Per liter of dyebath 20 cc. of sodium hydroxide solution (38 B.) and 4.5 grams of sodium-dithionite are used. The bobbin is badly dyed through and the dyeing is unlevelled.

In the same manner, but with addition of 0.5 g./l. of the addition compound of 20 mols of ethylene-oxide to 1 mol of 2-undecyl-4,4-bis-hydroxy-methyl-oxazoline a bobbin is dyed. A bobbin is obtained which is well dyed through.

Example 6 10 grams of loose wool are dyed for 1 hour at C. and at a goods-to-liquor ratio of 1:40 with a mixture consisting of 0.3% of the dyestuff C.I.42 655 0.4% of the dyestuff C.I.24 825 0.2% of the dyestuff C.I.18 (cf. Colour Index, 2nd

edition (1956)) while adding 5% of sodium sulfate and 2% of acetic acid of 30% strength.

A completely uneven dyeing is obtained.

In the same manner, but with addition of 0.5% of the addition compound of 12 mols of ethylene-oxide and 1 mol of 2-undecyl-4-ethyl-4-hydroxy-methyl-oxazoline the dyeing shows a considerably increased evenness.

We claim:

1. Process for producing even dyeings on nitrogen containing fibers and on cellulose fibers by adding to the dyebath a levelling agent of the formula wherein R represents an alkyl radical containing 3-20 carbon atoms, A stands for a member seleced from the group consisting of the methylene radical, oxygen and sulfur atom, R stands for a member selected from the group consisting of an alkyl group containing 1-4 carbon atoms and a radical (CH (C H O) H, wherein n is an integer of 2 to 3, y is an integer of 1 to 3 and x is an integer of 4-100, R represents the radical (CH (C I-I ,,O) H, wherein n, y and x have the meanings given above.

2. The process as claimed in claim 1, wherein the levelling agent is added to the dyebath in quantities within the range of 0.05 to 8 grams per liter.

wherein R represents an alkyl radical containing 3-20 carbon atoms, A stands for a member selected from the group consisting of the methylene radical, oxygen and sulfur atom, R stands for a member selected from the group consisting of an :alkyl group containing 1-4 carbon atoms and a radical (CH -(C H O) H, wherein n is an integer of 2 to 3, y is an integer of 1 to 3 and x is an integer of 4-100, R represents the radical (CH (C I-I O) H, wherein n, y and x have the meanings given above.

4. The process as claimed in claim 3, wherein the aqueous solution contains the levelling agent in quantities within the range of 0.05 to 8 grams per liter.

5. A process as claimed in claim 1, wherein the addition compound of 20 mols of ethylene-oxide to 1 mol of Z-undecyl 4,4-bishydroxy methyloxazoline is used as levelling agent.

6. A process as claimed in claim 1, wherein the addition compound of 12 mols of ethylene-oxide and 1 mol of 2-undecyl-4-ethyl-4-hydroxy-methyl-oxazoline is used as levelling agent.

7. In a process for dyeing nitrogen containing fibers and cellulose fibers to obtain even dyeings, the improve- 6 ment comprising: adding to the dyebath a levelling agent of the formula:

/Ra N CRa R,-A-o CH3 0 wherein R is an alkyl radical containing 3 to 20 carbon atoms, A is a member selected from the group consisting of the methylene radical, oxygen and sulfur atoms;

R is a member selected from the group consisting of an alkyl group containing 1 to 4 canbon atoms and a radical (CH (C H O) H, wherein n is an integer of 2 to 3, y is an integer of 1 to 3 and x is an integer of 4 to R is the radical (CH C I-I O) H, wherein n, y

and x have the meanings given above.

References Cited by the Examiner UNITED STATES PATENTS 2,187,823 1/1940 Ulrich et a1 8-88 X 3,096,139 7/1963 Hindle 888 X 3,097,046 7/1963 Walles et al 888 3,223,471 12/1965 Kuth et al 8-88 FOREIGN PATENTS 1,027,672 4/1958 Germany.

OTHER REFERENCES A. M. Schwartz et al.: Surface Active Agents and Detergents, vol. II, 1958, pp. and 111, pub. by Interscience Publishers Inc., New York, NY.

NORMAN G. TORCHIN, Primary Examiner.

J. T. HERBERT, Assistant Examiner.

Claims

1. PROCESS FOR PRODUCING EVEN DYEINGS ON NITROGEN CONTAINING FIBERS AND ON CELLULOSE FIBERS BY ADDING TO THE DYEBATH A LEVELING AGENT OF THE FORMULA