US3752649A

US3752649A - Dye levelling on and oligomer removal from polyester fibers and cellulose or polyamide blends with fatty acid diester of butanediol-ethylene oxide condensate

Info

Publication number: US3752649A
Application number: US00199748A
Authority: US
Inventors: O Smerz; G Weckler; A Scharf; W Linke
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1970-11-18
Filing date: 1971-11-17
Publication date: 1973-08-14
Anticipated expiration: 1990-08-14
Also published as: GB1328577A; NL7115574A; BE775507A; AT332350B; ATA988771A; DE2056694B2; DE2056694C3; DE2056694A1; CH551528A; FR2115214B1; CH1662671A4; IT940630B; FR2115214A1

Abstract

IN WHICH R1-CO- AND R2-CO- ARE RADICALS OF STRAIGHT CHAIN OR BRANCHED ALKANE- OR ALKENE-MONOCARBOXYLIC ACIDS HAVING 12 TO 22 CARBON ATOMS, AND N AND M EACH REPRESENT NUMBERS FROM 4 TO 12, OR DYEINGS PRODUCED WITHOUT USING THIS AUXLIARY AGENT ARE AFTERTREATED THEREWITH AND/OR THIS AUXILIARY AGENT IS ADDED AFTER THE DYEING IN THE FOLLOWING REDUCING CLEANING PROCESS.

-O-(C2H4O)M-CO-R2

R1-CO-(OC2H4)N-O-C4H8

PROCESS FOR THE MANUFACTURE OF LEVEL DYEINGS ON FIRBOUS MATERIALS OF LINEAR POLYESTERS AND MIXTURES THEREOF WITH CELLULOSE- OR NITROGEN-CONTAINING FIBERS, WHEREIN THE DYEINGS ARE CARRIED OUT IN THE PRESENCE OF COMPOUNDS OF THE GENERAL FORMULA

Description

United States Patent many No Drawing. Filed Nov. 17, 1971, Ser. No. 199,748 Claims priority, application Germany, Nov. 18, 1970, P 20 56 694.3 Int. Cl. D06p /04 U.S. Cl. 8-469 9 Claims ABSTRACT OF THE DISCLOSURE Process for the manufacture of level dyeings on fibrous materials of linear polyesters and mixtures thereof with celluloseor nitrogen-containing fibers, wherein the dyeings are carried out in the presence of compounds of the general formula in which R --CO-- and R CO are radicals of straight chain or branched alkaneor alkene-monocarboxylic acids having 12 to 22 carbon atoms, and n and m each represent numbers from 4 to 12, or dyeings produced without using this auxiliary agent are aftertreated therewith and/or this auxiliary agent is added after the dyeing in the following reducing cleaning process.

In practice, it is often very difiicult to produce with disperse dyestuffs level dyeings on fibrous materials of linear polyesters, in particular on those having the form of polyester rayon or of endless material such as wound bobbins.

The difficulties are due to the fact that during the manufacture of the high molecular linear polyesters from dicarboxylic acids and polyfunctional alcohols, for example from terephthalic acid an ethylene glycol, not only the long chain macro-molecules are formed which are suitable for the manufacture of filaments, but that also, at the same time, short chain or cyclic reaction products are formed in quantities of up to about 5%. These oligomers in the polyester fiber materials are disturbing, especially in a heating treatment during further processing, for example within the conventional dyeing process. As these oligomers are in general not dyed, for example by disperse dyestuffs, they turn out On the dyed material in the form of a white dust; this White dust appears particularly in spinning mills and weaving and knitting shops, where it deposits on the machine parts which come into contact with the dyed material.

The attempt has been made to remove by rinsing the oligomers which appear after the dyeing and deposit on the dyed polyestermaterial or to convert them with the aid of especially selected dispersing agents in the course of the reducing after-cleaning process into a dispersion and to eliminate them in this manner from the fiber. However, this is possible to a certain extent because merely the oligomers which are slightly adhering to the surface of the fiber can be removed in this manner, but not those oligomers which are partly or for the major part hidden within the fiber and protrude outwards from the surface of the fiber in the form of peaks.

3,752,649 Patented Aug. 14, 1973 It has also been proposed to eliminate the oligomers already during the dyeing process, during which they mainly appear, by immediate formation of a dispersion. As special dispersing agent for this purpose, a condensation product of butane-diol-(l,4)-pentaglycol ether and stearic acid at a molar ratio of 1:1 has been used, which, according to German Pat. 1,184,730, could be used, during dyeing as Well as during the reducin after-treatment of the polyester fibers or filaments which had been dyed without the use of this auxiliary agent. Though the above-mentioned measures using this known auxiliary agent brought some improvements, they did not sufiiciently meet the requirements of practice with a view to eliminating the detrimental influence of the oligomers.

An additional problem, occurring especially in the dyeing of cross-Wound bobbins, is the unlevel absorption of the dyestuffs on the fibrous materials; unlevelled parts within the yarn bobbin are found only during the further processing, and correction or improvement of the dyeing is then no more possible. The above-described difficulties arise not only when dyeing textile materials of linear polyesters, but also in the dyeing from one bath of miX- tures of polyester and wool, especially those having the form of wound bobbins, with disperse, acid, 1:1 or 1:2 metal complex dyestuffs.

A certain improvement was obtained, which, however, was not fully satisfying, by increase of the dyeing temperature, extension of the dyeing time and/ or addition of certain auxiliary agents to the dyebath, auxiliaries as those encompassed by the term carriers which have a colour intensifying elfect in the dyeing of polyester fibers with disperse dyestulfs, furthermore alkylation products of fatty acids, fatty acid esters or fatty amines, or of the condensation product of butanediol-(l,4)-pentaglycol ether which has been esterified in a molar ratio with stearic acid and is described in German Pat. 1,184,730.

Finally, the dyeing of piece goods of synthetic fibers or of mixtures thereof With cellulose fibers, especially of closely woven fabrics or delicate knittings on winch becks often implies the risk of the formation of creases resulting in unlevel dyeings.

Now, we have found that in the dyeing of fibrous materials of linear polyesters and their mixtures with cellulose or nitrogen-containing fibers with disperse dyestuffs the above-described difiiculties can be avoided and level dyeings which are free from running creases can be produced by carrying out the dyeing in the presence of compounds of the general formula in which R -CO- and R CO-- represent radicals of straight chain or branched alkaneor alkene-monocarboxylic acids having 12 to 22 carbon atoms, and n and In each represent numbersfrom 4 to 12, or by aftertreating dyeings produced without the use of this auxiliary agent with these compounds and/or adding this auxiliary agent after the dyeing during the following reducing cleaning process.

The compounds of the Formula I used according to the invention ma be prepared, for example, by esterification of 1 mol of an addition product of 8-24 mols of ethylene oxide and 1 mol of butanediol-(l,4) with 2 mols of a straight chain or branched alkaneor alkene-monocarboxylic acid having 12 to 22 carbon atoms. For the esterification, mixtures of the mentioned carboxylic acids may also be used.

The use of the compounds of the Formula I, in accordance with the methods for carrying out the present invention, unexpectedly increases essentially the effects obtained with the butanediol-(1,4)-pentaglycol ether monostearic acid ester known from German Pat. 1,184,- 730, so that the oligomers deposited on the surface of the fibers can be eliminated in the form of extremely fine dispersions, which are easy to remove by rinsing processes, whereby the detrimental effects on the outer appearance of the goods are avoided. In addition, the soiling of the dyeing apparatuses by these undesired by-products is prevented to such an extent which permits the labor expenditure for cleaning these plants to be reduced by up to 70% Furthermore, the condensation products of the Formula I are distinguished by their essentially simpler application and, in many cases, by an improved dispersing action for the disperse dyestuffs used for the dyeing of polyester materials, which is also maintained when the dyeing process is carried out at high temperature conditions (120130 C.).

In the known process described in German Pat. 1,184,- 730 using the monostearic acid ester of butanediol-(1,4)- pentaglycol ether, it was in most cases necessary to add during the Whole dyeing process dispersing agents on the basis of reaction products of naphthalene-sulfonic acids and formaldehyde or N-oleyl-N-methyl-tauride to the dyebath in order to avoid precipitations, especially when the dyeing process was carried out under the above-mentioned economically important high temperature conditions.

The quantity of the compounds of the Formula I to be added according to the invention for obtaining level dyeings varies between 0.25 and g., in particular between 1 and 3 g., per liter of dyebath; the concentration of the auxiliary agent depends on the depth of the dyeing and on the disperse dyestuffs to be levelled. The use of the mentioned condensation products in dyeing according to the invention is not bound to a determined temperature; in general, the temperatures used are within the range of from about 98 C. to about 140 C. and the dyeing is effected according to the exhaust method in the usual manner, optionally in the presence of carriers.

Dyeings produced without the use of the compounds of the Formula I and which are unlevel, can be levelled by an after-treatment with the said auxiliary agent. For this purpose, the compounds are used in quantities of 4 to 5 g. per liter of after-treating bath during a treatment time of 1 to 3 hours at boiling temperature or under high temperature conditions.

In addition to the levelling action of the products of the Formula I and to their preventing action against the formation of creases when dyeing polyester fibers or the mentioned fiber mixtures, they improve the fastness to rubbing of the dyeings produced according to the invention.

As disperse dyestuffs, there may be used in the process according to the invention the products known for the dyeing of polyester materials, for example those of the series of azo and anthraquinone dyestuffs.

The following examples illustrate the invention:

EXAMPLE 1 100 kg. of a combed material of polyethylene glycol terephthalate fibers, packed as closely as possible, were dyed at 120 C. for 90 minutes, in a high temperature dyeing apparatus, at a goods-to-liquor ratio of 1:15, with an aqueous bath containing, referred to the dry weight of the goods,

0.2% of the disperse dyestulf of the formula 4 0.12% of the disperse dyestuff of the formula 0 NH; II

0.22% of the disperse dyestuff of the formula 0.05 cc./l. of sulfuric acid (96% strength) and 2 g./l. of butane-diol-(1,4)-pentadecaglycol ether dioleyl ester.

The dyeing so obtained was then further treated with a reducing after-treatment usual for this fiber type and dyestuif class. I

An excellently level dyeing was obtained, whereas a dyeing produced for comparison without the auxiliary agent showed high unlevelness and was, therefore, unutilizable.

EXAMPLE 2 A fabric having the tendency to crease formation and a weight of about g./m.'-, in linen weave pattern from yarns having the size Nm 48/2, consisting of polyethylene glycol terephthalate staple fibers of 3.3 d. tex 60 mm. cutting length, a density of the weft of 130 yarns per 10 cm. and a number of warp yarns of 1700 yarns over a web width of 130 cm., was dyed, after the prewashing and thermofixation usual for this kind of goods, for 30 seconds at C. on a winch beck, at a goods-toliquor ratio of 1:30, in the following manner:

The fabric was entered into the bath which contained, per liter of water, 2 g. of butanediol-(1,4)-pentadecaglycolether dioleyl ester and 3 g. of a carrier on the basis of methyl-naphthalene, and which had been adjusted to pH 5.5 by means of sulfuric acid and had a temperature of 60 C., and the fabric was allowed to run through the bath for 15 minutes. 7

Then, 0.3% of the disperse dyestuif of the formula and 0.2% of the disperse dyestuff of the formula I l OA o-om-cm-on ll OH referred to the dry Weight of the goods,

EXAMPLE 3 50 kg. of texturated polyester rayon, which had been dyed for 1 hour at 125 C. in a high temperature apparatus, at a goods-to-liquor ratio of 1: 15, in an aqueous bath with disperse dyestuffs, were subjected, after completion of the dyeing, without cooling the goods and without intermediate rinsing, to the following reducing cleaning process:

A bath was prepared which contained per liter of water, in addition to cc. of sodium hydroxide solution of 36 B. and 2 g. of hydrosulfite, 3 g. of a condensation product of butane-diol-(1,4)-pentadecaglycol ether and oleic acid in a molar ratio of 1:2. This bath was heated to 90 C. and pumped into the dyeing apparatus in which the dyeing had been carried out under high temperature conditions and which contained the not cooled material of polyester rayon. The bath was cycled for minutes at 90 C. and the dyeing was then rinsed with water under overflow until it was free from alkalies.

The polyester rayon so treated showed practically no oligomer deposits, neither in the form of dust nor in the form of solid particles which could have formed by auxiliary agents in combination with the oligomers.

We claim:

1. In a process for dyeing, with a disperse dyestufi, fibrous materials of linear polyesters and blends thereof with cellulose or polyamide fibers, the improvement which comprises applying to the material a levelling compound of the formula in which R -CO- and R2-c0 are radicals of straight chain or branched alkaneor alkene-monocarboxylic acids of 12 to 22 carbon atoms, and n and m each represent numbers from 4 to 12.

2. A process as defined in claim 1, wherein the levelling compound is applied to the material with the dyestuff.

3. A process as defined in claim 1, wherein the levelling compound is applied to the material after application of the dyestulf.

4. A process as defined in claim 1, wherein the levelling compound is applied to the material after application of the dyestufi and in a reducing after-treatment.

5. A process as defined in claim 1, wherein the dyeing operation is carried out at a temperature within the range of from about 98 to about 140 C. according to th exhaustion method.

6. A process as defined in claim 1, wherein the levelling compound is applied in a concentration of between 0.25-5 g. liter of dyebath.

7. A process as defined in claim 4, wherein the aftertreating operation is carried out at a temperature within the range of from about 98 to about 140 C.

8. A process as defined in claim 7, wherein the levelling compound is applied in a concentration of between 4 and 5 g. per liter of after-treating liquor.

9. A process as defined in claim 1 wherein the levelling compound is butanediol-(1,4)-pentadecaglycol dioleyl ester.

References Cited UNITED STATES PATENTS 3,003,843 10/1961 Amick 8-93 FOREIGN PATENTS 2,037,217 11/1970 Germany 260- R DONALD LEVY, Primary Examiner US. Cl. X.R.