US3619124A - Process for the dyeing or printing of fibrous materials - Google Patents

Abstract

The dyeing or printing of fibrous materials is improved by using a compound of the formula R1-CHX-(CH2-CH2-O)n-R2 in which R1 is alkyl of four to 20 carbon atoms, X is chlorine or bromine, n is a number of three to about 200 and R2 is an aliphatic hydrocarbon radical of up to 20 carbon atoms, alkylphenyl with up to 12 carbon atoms in the alkyl moiety, phenyl, naphthyl, benzyl, the acyl residue of a fatty acid of up to 18 carbon atoms, benzoyl or the group of the formula R1-CHXCH2-CH2, as dispersing, levelling or after treating agent. The improvement consists in the combination of dispersing and levelling properties.

Description

United States Patent Gerhard Weckler Sulzbach. Taunus;

Helmut Diery, Kelkhelm, Tauaus; Lorenz Helb, Hofhelm, Taunus; Franz Schon Frankfurt am Main, all of Germany lnventors PROCESS FOR THE DYEING OR PRINTING OF FlBROUS MATERIALS 5 Claims, No Drawings U.S. Cl 8/173. 8/93 Int. Cl D06p 5/04 Field of Search 8/93, 74, I65, I73

I 56] References Cited UNITED STATES PATENTS 2,878,294 3/1959 Kress 8/93 X 3,085,987 4/1963 Ahashian 8/173 X 3,342,542 9/1967 Morf A. 8/! 73 Primary Examiner-Donald Levy Almmey-Curtis, Morris & Safford ABSTRACT: The dyeing or printing of fibrous materials is improved by using a compound ofthe formula in which R is alkyl of four to 20 carbon atoms, X is chlorine or bromine, n is a number of three to about 200 and R is an aliphatic hydrocarbon radical of up to 20 carbon atoms, alkylphenyl with up to 12 carbon atoms in the alkyl moiety, phenyl, naphthyl, benzyl, the acyl residue of a fatty acid of up to 18 carbon atoms, benzoyl or the group of the formula R,- CHXCH CH as dispersing, levelling or after treating agent. The improvement consists in the combination of dispersing and levelling properties.

PROCESS FOR THE DYEING OR PRINTING F FIBROUS MATERIALS The present invention is concerned with the use of polyalkylene oxide compounds as dispersing, levelling or aftertreating agents in a process for the dyeing or printing of fibrous materials.

In dyeing fibrous materials with dyestuffs insoluble or sparingly soluble in water which have been in the pigment form already initially or pass into insoluble state in the course of the dyeing, difficulties are often encountered. The factors impairing, generally, the quality of the dyeings essentially consist in the impossibility to obtain in the dyebath a fine enough dyestuff dispersion and/or with dyestuff mixtures used, in the unequal affinity to the fiber resulting in unlevelness of the fabric and insufficient fastness of the dyeings, especially an inferior fastness to rubbing.

Such unsatisfactory results are, e.g., experienced in the dyeing of cellulose fibers with vat dyestuffs, their leucosulfuric acid esters, other organic or inorganic pigments or developing dyestuffs, or when synthetic fibers, preferably polyester fibers are dyed with pigment dyestufis, for example, disperse dyestuffs.

Also in the single-bath dyeing of fiber blends, e.g. blends of polyester or polyacrylonitrile with anionic or cationic dyestuffs it must be taken into account that these dyestuffs nearly always precipitate in the dyebath so that unusable dyeings result.

Another problem rendering difficult the dyeing of blends of polyester fibers and wool or cellulose fibers with dispersion dyestuffs consists in that the second fiber is stained and that the dyed fabric thus has inferior fastness properties.

It is known that dyestuffs which are insoluble or sparingly soluble in water can be maintained in the form of fine dispersions during the dyeing process, when additives such as the condensation products of naphthalene-sulfonic acid with formaldehyde or the alkali metal salts thereof, oxethylated fatty alcohols, etc., are used. However, the applicability of these compounds for the production of dyeings is almost always limited to a specific application field so that for different dyestuff classes or different dyeing processes using the same dyestuffs or for aftertreating such dyeings different auxiliaries are required. Moreover, the products mentioned either possess solely dispersing properties or solely levelling properties, so that combination of both actions is achieved almost exclusively with mixtures of various auxiliaries only.

Now, we have found that polyalkyleneoxide compounds having the general formula and n stands for a number of three to about 200, preferably three to about 100, especially seven to about 70, can be used universally as dispersing, levelling or aftertreating agents for dyeing or printing fibrous materials consisting of cellulose, cellulose triacetate, polyamide fibers of natural or synthetic origin or hydrophobic fibers, for example fibers of polyester or polyacrylonitrile or their copolymers or of mixtures of said fibers, with dyestuffs insoluble or sparingly soluble in water.

By using the above-identified polyalkyleneoxide compounds it is henceforth possible to eliminate the factors described hereinbefore which negatively influence the dyeing or printing of fibrous materials, with the dyestuffs concerned or with similar dyestuffs, when no auxiliaries are used.

' ing, increased velocity of flow is ensured.

The polyalkylene oxides of formula I used according to the present invention are symmetrical or unsymmetrical addition products of l or 2 mols of an a-olefin corresponding to the formula R,-CH=CH (II) in which R, is defined as above on I mol of the monoor bishalomethylether of a polyalkylene oxide of formula X-CI-l O(Cl-l ---Cl-l O),,,R (III) in which X is defined as above, m stands for a number of two to 200, generally, preferably, six to I00, R has the meaning of R except for the radical replaced therein by the group CH -X. Said addition compounds are obtained by stirring the two components at temperatures ranging from l0 to C. in the presence of Friedel-Crafts catalysts US. application Ser. No. 841,620, filed July 14, 1969 discloses the synthesis of the above emulsifiers in detail.

Of the polyalkylene oxide compounds of formula I there have proved suitable for the application according to the present invention, for example, in particular the addition products of bis-chloromethyl ether of a polyethylene glycol with a molar weight of about l00 to 2,000 on octene-l, dodecene-l, octadecene-l or on a technical mixture of aolefins containing from about 15 to 18 carbon atoms.

Furthermore, there may be used addition products of the bromomethyl or chloromethyl ether of a methoxy polyethyleneglycol with two to 50 ethoxyl groups on dodecene-l, octadecene-l or on a technical mixture of an aolefin having from 15 to 22 carbon atoms. Such polyethylene glycols may, for example, also contain instead of the methylether group a lauryl-, oleylor octadecylether group or a phenyl-, naphthylor benzylether radical. Moreover, the polyethyleneglycol serving as starting compound may be unilaterally esterified with a carboxylic, preferably, a fatty acid having up to 18 carbon atoms, e.g., acetic or stearic acid, or benzoic acid. Finally, there may likewise be used according to the present invention the additional products of the chloromethylether of an alkylphenoxypolyethylene glycol with no less than two ethoxyl groups on octene-l, octadencene-l or on a technical mixture of a-olefins having up to 22 carbon atoms. The alkyl radical of the alkylphenol serving as starting compound contains up to 12 carbon atoms.

The amount of polyalkyleneoxide compound used ranges in the present process between 0.1 and 5 g., preferably 0.5 to 2 g. per liter of aqueous dye or aftertreating bath. The action of these products is not dependent on a definite temperature or pH value. By dyestuffs insoluble or sparingly soluble in water there are understood those selected from the group consisting of vat dyestuffs, their leucosulfuric acid esters, inorganic or organic pigment dyestuffs, developing dyestuffs or disperse dyestuffs, anionic or cationic dyestuffs, more especially dyestuffs of the azo, indanthrone, anthraquinone, quinophthalone, triphenylmethane or polymethine series.

The following examples illustrate some possible uses of the products of the invention. The parts and percentages are by weight unless otherwise stated.

EXAMPLE 1 Aqueous solutions were prepared each from 2 gjl. of dyestuff Cl 69 826-Solubilized Vat Blue 6 (cf. Color index, 2nd edition (1956), volume 3, page 3,535) and increasing amounts (/O.2/0.4/0.6/0.8/l.0 g./l.) of the addition product of 1 mol of the bis-chloromethylether ofa polyethyleneglycol of a molecular weight of 1,200 and 2 mols ofa technical mixture of a-olefins with 15 to 18 carbon atoms (referred to hereinafter as compound A). Subsequently thereto, the dis solved dyestuff was transformed into its pigment form by oxidizing with sulfuric acid and sodium nitrite. The so-obtained dyestuff dispersions were, after abandoning for half an hour. suction-filtered through a round filter (Schleicher and Schull. No. 1450). The resulting residues of the filter samples showed how the dispersive power rose with the amount of compound A increasing, in the case of the above-mentioned dyestuff class.

Analogous good results could be obtained, when instead of compound A the following compounds were used.

Compound E EXAMPLE 2 One hundred g. of a cotton fabric were treated first for about 45 minutes at 40-50 C. in 2 l. of an aqueous dyebath containing 1.2 g. of the dyestuff of example i, 100 g. of calcined Glaubers salt, 1 g. of calcined soda and 1 g. of compound G. Thereupon, at short intervals, successively, l g. of sodium nitrite, optionally l g. of an auxiliary preventing overoxidation, and ml. of sulfuric acid of 96 percent strength were added to the dyebath and the vat dyestuff was developed on the fiber for about 15 minutes in the bath which had cooled off. The dyeing was then finished by rinsing, neutralizing with soda and soaping at the boil in the manner usual with this class of dyestuffs.

ln testing the fastness properties, especially to wet and to rubbing, distinctly better values were ascertained than with a dyeing produced without compound G.

Also when dyeing was performed according to the two-bath method as is likewise usual with said class of dyestuff the auxiliary being then added to the developing bath. analogous good results were obtained in the test of fastness properties.

Practically the same results were obtained with the remaining polyalkyleneoxide compounds of example 1 used instead of compound G.

EXAMPLE 3 into aqueous solutions of 10 g./l. of dyestuff salt C. l. 37 0l0-Azoic Diazo Component 3 (cf. Color Index, 2nd edition 1956). vol. 3, page 3,317) increasing amounts 20 /0.5/1.0/l.5/2.0/2.5/3.0 g./l.) of compound A were introduced. Subsequently, these solutions were mixed while stirred with 0.6 g./l. of an aqueous solution of coupling component C. l. 37 530Azoic Coupling Component 20 (cf. Color index, 2nd edition (1956), vol. 3, page 3,328) prepared 2 5 as prescribed. The so-obtained dispersion of the developing dyestuff was allowed to stand for about minutes whereupon it was suction-filtered through a round filter (Schleicher and Schiill No. 1450). The resulting residues of the filter samples showed that increased addition of compound A enabled a 30 higher dispersing effect.

Similar good results were obtained also with compounds B-i.

EXAMPLE 4 Practically the same results were achieved with compounds A to 1, when for the preparation of the developing dyestuff dispersion according to the method of example 3 there were used instead of the starting compound mentioned therein the following dyestuff components:

(1956), vol. 3, page 3,329).

EXAMPLE 5 One hundred parts of a cotton fabric were dyed on a jigger at a goods-to-liquor ratio 1:5 by treating in the following aqueous baths:

a. impregnation bath:

5.5 g./l. of coupling component C. l. 37 530-Azoic Coupling Component 20 (cf. Color index, 2nd edition (1956), vol. 3, page 3,328). dissolved in water as prescribed, l0 ml./l. of sodium hydroxide solution of 32.5 percent strength, 1 g./l. of a protective colloid on the basis of a protein degradation product b. developing bath:

25 g./l. of dyestufi' salt C. l. 37 OlO-Azoic Diazo Component 3 (cf. Color Index, 2nd edition (1956), vol. 3, page 3,317), 2 g./l. ofcompound C.

The fabric was first impregnated for 45 minutes in a bath which had cooled off, starting at a temperature of C. and using liquor (a), whereupon it was squeezed off and the dyestufi developed cold for 30 minutes, without intermediate rinsing, by treating with liquor (b). The dyeing was finished according to the method usual with this class of dyestuffs, i.e. soaped twice at 60 C. and at the boil.

In testing the fastness properties of this dyeing it was found that when compound C was used as dispersing agent in the impregnation bath. far better fastness was achieved, especially in regard to rubbing than provided dyeing without said auxiliary.

Similar results could be achieved, when instead of componentC the compounds A, B or D-l were used.

EXAMPLE 6 Four hundred g. of a combed material made from polyethyleneglycolterephthalate fibers were dyed. as closely packed as possible in a high-temperature dyeing machine at l C. over the course of 90 minutes at a goods-to-liquor ratio lz40 with an aqueous liquor containing (referred to the dry weight of the goods) 0.04 I; of the disperse tlycstulf of formula O /l i HO] kl CH L N F 0.027% of the disperse dyestuff of formula 0.02% of the disperse dyestuff of formula EXAMPLE 7 One hundred g. of a mixed fabric consisting in the mixing ratio 55:45 of polyethyleneglycolteraphthalate fibers and wool were dyed for 90 minutes at the boil with an aqueous liquor adjusted to a pH of 5.5 and containing, referred to the dry weight of the goods, 3 percent of the disperse dyestuffC. l. 26 080-Disperse Orange 13 (cf. Color Index, 2nd edition (1956), vol. 3. page 3.206) and 3 g./l. ofa carrier of the type of a phenylphenol. About half the charge of this dyeing was subsequently aftertreated for 20 min. at a temperature of 70 C. at a goods-to-liquor ratio 1:40 in a fresh aqueous bath containing 2 g./l. of compound I and l ml./l. of acetic acid of 30 percent strength. From the different dyeing results obtained in these two cases it was obvious that the strong staining of the wool component by the disperse dyestuff can be removed to a great extent by aftertreating with compound I.

ln testing the fastness properties. especially to rubbing and to wet of the two dyeings. clearly better values were for the aftertreated dyeing.

Similar results were obtained, when instead of compound I the compounds A-H were used.

EXAMPLE 8 To aqueous dyestufi' solutions of 3 g./l. of the anionic dyestuff Acid Blue 213 (cf. Color Index. 2nd edition, Sup lement volume (1963). page 81) and l ml./l. of acetic am of 30 percent strength increasing amounts (/0.2/0 4/0.6 /0.8/l.0 g./l.) of compound A were added. Subsequently, these solutions were mixed each with 3 g./l. of the cationic dyestuff Basic Yellow 21 (cf. Color Index. 2nd edition, Supplement volume (1963). page 15] and heated to about C. at which temperature they were abandoned for about 30 minutes. The the individual samples were suction-filtered using a round filter (Schleicher andSchiill,No. 1450).

The so-obtained residues of the filter samples showed that the precipitates which form with combinations of anionic and cationic dyestuffs can be dispersed the better, the more the amount of compound A is increased.

Similar good results were obtained, when instead of compound A the compounds B-l were used.

We claim:

1. A process for dyeing or printing of fibrous materials consisting of cellulose. cellulose triacetate, natural or synthetic polyamide. polyester or polyacrylonitrile fibers or mixtures thereof with water-insoluble or sparingly soluble dyestuffs, which comprises using as a dyeing auxiliary a compound of the formula in which R is alkyl of four to 20 carbon atoms. X is chlorine or bromine, n is a number of three to about 200 and R is an aliphatic hydrocarbon radical of up to 20 carbon atoms. alkylphenyl with up to 12 carbon atoms in the alkyl moiety, phenyl, naphthyl, benzyl, the acyl residue of a fatty acid of up to 18 carbon atoms. benzoyl or the group of the formula R, CHX-CH CH 2. The process as claimed in claim 1, wherein n is a number ofthree to about [00.

3. The process as claimed in claim 1, wherein nis a number of seven to 70.

4. The process as claimed in claim 1, wherein 10 to 18 carbon atoms.

5. The process as claimed in claim 1. wherein R is lower alkyl.

R is alkyl of

Claims (4)

1. 2. The process as claimed in claim 1, wherein n is a number of three to about 100.
2. 3. The process as claimed in claim 1, wherein n is a number of seven to 70.
3. 4. The process as claimed in claim 1, wherein R1 is alkyl of ten to 18 carbon atoms.
4. 5. The process as claimed in claim 1, wherein R2 is lower alkyl.