DYEING AIDS

20094î4 PATENT Case D 8450 CA i0 DYEING AIDS Background of the Invention Field of the Invention:

This invention relates to dyeing aids and to a process for the single-bath, single-stage dyeing of textile fibers.

Discussion of Related Art:

Cotton contains natural impurities, for example waxes, waxlike substances, proteins, seed shells, fruit husks and pectins and also impurities which are applied as foreign substances in the course of processing, for example paraffins and/or mineral oils. The impurities in wool, regenerated fibers, such as viscose rayon, and synthetic fibers, such as polyester and polyamide, emanate from the treatment of these materials with finish compositions (Chwala/Anger: "Handbuch der Textilhilfsmittel", pages 526 - 528, 537, 558 et seq., Verlag Chemie Weinheim, 1977). To obtain uniformly dyed textile fibers, particularly cellulose-containing textile fibers, the textile material is normally subjected to a pretreatment. The object of the pretreatment is to remove the impurities mentioned by way of example above as completely as possible from the fibers in order thus to provide the fibers with the relatively high degree of hydrophilicity and absorbency required for the subsequent finishing processes. In dyeing processes above all, inadequate hydrophilic properties and inadequate absorbency of the textile material result as early as the dye absorption phase in uneven dyeing which is very difficult or impossible to correct.

However, the pretreatment is attended by the disadvantage that it has to be carried out in several stages. Accordingly, to shorten the processes involved in the dyeing of textiles, processes have recently been developed which eliminate the need for the separate pretreatment step (Chwala/Anger: "Handbuch der Textilhilfsmittel", pages 528 - 529, Verlag Chemie Weinheim, 1977). Single-bath, single-stage dyeing is one such process.

i0 3o Z009414 in this process, the textile material is pretreated and dyed in a single stage. The baths contain the chemicals required for the pretreatment, such as wetting agents, detergents, dispersants, leveling agents and/or alkalis, and also dyes. The singlebath/single-stage dyeing process described in German 36 43 752 for mixtures of polyester fibers and cellulose fibers dyeable in the absence of carriers is carried out in the presence of dispersion and reactive dyes and, optionally, auxiliaries at pH values of 6 to 8.5 and at temperatures of from 90 to I05°C.

However, the stringent requirements in regard to level dyeing, depth of color and fastness of the textile material often cannot be satisfactorily met by the known single-bath, singlestage dyeing processes. Accordingly, an object of the present invention is to develop dyeing aids which, when used in singlebath single-stage dyeing processes, produce uniform and brilliant colors on the textile material. In addition, the performance characteristics of the dyed fibers, such as fastness to light, fastness to rubbing and wet fastness values, are not adversely affected by the use of such aids.

DESCRIPTION OF THE INVENTION Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term "about".

It has now surprisingly been found that the stringent requirements which the dyeing properties of textile fibers and, in particular, cellulose-containing textile fibers have to meet, are satisfied by mixtures containing (i) C8 .24 alkyl or alkenyl alcohol sulfates or C14 .18 alkane sulfonates or Ci0 .i4 alkyl benzene sulfonates, (2) castor oil containing 20 to 50 mols ethylene oxide or alkoxylated C8 .24 alkyl or alkenyl alcohols or alkoxylated C8 .12 alkylphenols, (3) sulfatized hydroxyalkyl alkylpolyalkylene glycol ethers, and (4) C2 .12 alkyl alcohols in specific quantities and ratios by weight.

Accordingly, the present invention relates to dyeing aids containing anionic and nonionic surfactants, comprising:

1 to 60% by weight surfactants selected from the group consisting i0 4o of Z009414 a) C8 .24 alkyl or alkenyl alcohol sulfates, C14.18 alkane sulfonatesg and CI0 .14 alkyl benzene sulfonates in the form of their alkali metal, ammonium or amine salts, and b) castor oil containing 20 to 50 mols ethylene oxide, alkoxylated C8.24 alkyl or alkenyl alcohols, and alkoxylated C8 .12 alkylphenols; 1 to 25% by weight sulfatized hydroxyalkyl alkylpolyalkylene glycol ethers corresponding to general formula I SO3M R -- O--- CnH2 nO) ---CH2 -- CH -- R1 (I) in which R is a CI.6 alkyl radical, RI is a C6 .

IS alkyl radical, M is an alkali metal or ammonium cation, n = 2 or 3 and x is a number of 2 to i0; and 1 to 30% by weight C2 .12 alkyl alcohols, with the proviso that the ratio by weight of surfactants a) to surfactants b) is from 5:1 to 1:5, the ratio by weight of surfactants a) and b) to sulfatized hydroxyalkyl alkylpolyalkylene glycol ethers is from i:I to 4:1, and the ratio by weight of surfactants a) and b) and sulfatized hydroxyalkyl alkylpolyalkylene glycol ethers to alkyl alcohols is from i:I to 5:1.

The dyeing aids according to the invention preferably contain 1 to 40% by weight surfactants a) and b), 1 to 20% by weight sulfatized hydroxyalkyl alkylpolyalkylene glycol ethers corresponding to general formula I and 1 to 30% by weight C2 .12 alkyl alcohols.

The alkyl or alkenyl alcohol sulfates are produced in the form of their alkali metal, ammonium and/or amine salts in known manner by sulfatization of the corresponding alkyl or alkenyl alcohols with chlorosulfonic acid or sulfur trioxide. The i0 resulting sulfuric acid semiesters of the alcohols are then neutralized with, for example, alkali metal hydroxide, such as sodium hydroxide, ammonia or alkanolamines, such as monoethanolamine or triethanolamine (Winnacker-Küchler in "Chemische Technologie", Vol. 7, pages 120 - 123, Carl Hanser Verlag, München-Wien (1986)). The educts alkyl or alkenyl alcohols may be linear or branched, of natural or synthetic origin and contain 8 to 24 carbon atoms and preferably 12 to 18 carbon atoms. Examples of suitable alkyl or alkenyl alcohols are octyl, decyl, lauryl, myristyl, cetyl, stearyl, oleyl, behenyl alcohol and mixtures of these alcohols. Lauryl, myristyl, cetyl or stearyl alcohol, mixtures of these alcohols or alcohol mixtures with predominantly C12 .18 alkyl or C12 .1 a alkenyl alcohols, for example coconut oil fatty alcohol or tallow fatty alcohol, are preferably used.

On an industrial scale, alkali metal, ammonia or amine salts of C14 .18 alkanesulfonates may be obtained by reaction of linear paraffins with, for example, SO2 and oxygen in the presence of radical formers, such as ozone, organic peroxides or UV light (Winnacker-Küchler in "Chemische Technologie", 4th Edition, Vol.

7, pages 114 - 116, Carl Hanser Verlag, München-Wien (1986)).

CI0.14 alkyl benzene sulfonates in the form of their alkali metal, ammonium or amine salts may be produced by reaction of Ci0 .

14 alkyl benzenes with sulfonating agents, such as S03 /air mixtures, SO3 /nitrogen mixtures, sulfuric acid or oleum, using known industrial processes "Winnacker-Küchler in Chemische Technologie", 4th Edition, Vol. 7, pages iii - 114, Carl Hander Verlag, München-Wien (1986)).

Castor oil containing 20 to 50 mols ethylene oxide, alkoxylated C8 .24 alkyl or alkenyl alcohols and alkoxylated C8 .12 alkylphenols are produced by alkoxylation of castor oil or linear or branched alkyl or alkenyl alcohols of natural or synthetic origin or alkylphenols with ethylene oxide or propylene oxide using known industrial processes (see for example "Chemische Technologie", Vol. 7, pages 131 - 132, Carl Hanser Verlag, München-Wien (1986)). The average degree of alkoxylation of the alkoxylates obtained, which corresponds to the molar quantity of Z009414 IO uhe added alkylene oxides, is preferably from 30 to 50 in the case of castor oil, preferably from 3 to i0 and more preferably from 4 to 8 in the case of alkyl or alkenyl alcohols and preferably from 1 to 20 in the case of the alkylphenols.

Suitable alkyl or alkenyl alcohols containing 8 to 24 and preferably 12 to 18 carbon atoms are the alcohols and alcohol mixtures mentioned above.

Sulfatized hydroxyalkyl alkylpolyalkylene glycol ethers may be obtained in accordance with European Patent 299,370 by sulfatization of hydroxyalkyl alkylpolyalkylene glycol ethers corresponding to general formula II OH I R -- O--- CnH2 nO) ----CH2 -- CH -- R1 (Il) with chlorosulfonic acid or SO3 /inert gas mixtures and subsequent neutralization, for example with alkali metal hydroxides, such as sodium hydroxide, ammonia or amines, such as CI.4 alkylamines or triethanolamine. The ethers corresponding to general formula II may be obtained in accordance with EP 299 370 by reaction of epoxides corresponding to general formula III RI -- CH -- CH o (III) with alkoxylated linear or branched alkyl alcohols corresponding to general formula IV R -- 0 CCnH2 nO)--H-" x (IV) in the presence of catalysts, for example sodium methylate, at temperatures in the range from I00 to 180°C and preferably at temperatures in the range from 150 to 160°C. Sulfatized hydroxyalkyl alkylpolyalkylene glycol ethers corresponding to general formula I, in which R is a linear or branched Ca.5 alkyl radical, RI is a linear or branched C8 .16 alkyl radical, M is an alkali metal cation, n = 2 and x is a number of 2 to 5, are i0 2o 3o 4o 003414 preferably used.

The fourth component of the mixtures according to the invention, namely the C2 .12 alkyl alcohols, may be linear or branched and of natural or synthetic origin. C6 .10 alkyl alcohols, for example 2-ethyl hexanol, n-octanol or n-decanol, are preferably used.

The present invention also relates to a process for the single-bath, single-stage dyeing of textile fibers in the presence of anionic or nonionic surfactants, wherein the textile fibers are treated at temperatures of 20 to 95°C with aqueous dye liquors containing per liter liquor 0.i to 2.0 g of surfactants selected from the group consisting of a) C8 .z4 alkyl or alkenyl alcohol sulfates, C14_18 alkane sulfonates, and CI0 .14 alkyl benzene sulfonates in the form of their alkali metal, ammonium or amine salts, and b) castor oil containing 20 to 50 mols ethylene oxide, alkoxylated C8.24 alkyl, or alkenyl alcohols, and alkoxylated C8 .12 alkylphenols; 0.05 to 1.0 g of sulfatizedhydroxyalkyl alkylpolyalkylene glycol ethers corresponding to general formula I 0.i to 2.0 g SO3M R -- 0 (CnH2 nO) ----CH2 - CH -- R1 (1) in which R is a CI.6 alkyl radical, RI is a CO" 18 alkyl radical, M is an alkali metal or ammonium cation, n = 2 or 3 and x is a number of 2 to I0, and of C2 .12 alkyl alcohols, the ratio by weight of surfactants a) to surfactants b) being from 5:1 to 1:5, the ratio by weight of surfactants a) and b) to sulfatized hydroxi0 20094OE4 yalkyl alkylpolyalkylene glycol ethers being from I:i to 4:1 and the ratio by weight of surfactants a) and b) and sulfatized hydroxyalkyl alkylpolyalkylene glycol ethers to alkyl alcohols being from i:i to 5:1, and on completion of dyeing are aftertreated in known manner at temperatures in the range from 80 to 100°C.

Preferably, from 0.3 to 1.2 g surfactants from groups a) and b), from 0.l to 0.6 g sulfatized hydroxyalkyl alkylpolyalkylene glycol ethers and from 0.2 to 0.6 g C2 .12 alkyl alcohols are used per liter of dye liquor.

In addition to the mixtures according to the invention, the aqueous dye liquors contain from 0.5 to 5.0% by weight of dyes, based on the weight of the textile material. Reactive dyes, substantive dyes, vat dyes, dispersion dyes, diazo dyes, sulfur dyes, acid dyes or metal complex dyes or pigments are used as dyes, depending on the textile fibers to be treated. The aqueous dye liquors contain aliphatic CB.24 carboxylic acids, such as hydrogenated tallow fatty acid or coconut oil fatty acid, C8 .24 alkylamines, such as tallow amine, foam inhibitors, for example based on mineral oil or silicone, as optional constituents in a total quantity of 0.01 to 1.0 g per liter dye liquor. Textile fibers, for example of cotton, viscose, wool, cotton/polyester blends or cotton/polyamide blends, which are present for example as woven fabrics, knitted fabrics or yarns, are dyed by the extraction process in which the textile material is contacted with the aqueous dye liquors at temperatures in the range from to 45°C. The liquor ratio is between 1:5 and 1:30 and preferably between i:10 and 1:20. Electrolytes, for example Glauber's salt or sodium chloride in quantities of 30 to 80 g per liter of liquor and sodium carbonate or NaOH in quantities of 2 to 20 g per liter of liquor, are then added to the dye liquors, preferably in severa! portions, at the same temperature or at higher temperatures. After dyeing, the textile fibers are aftertreated in known manner at temperatures of 25 to 98°C to improve their performance characteristics, the aftertreatment i0 comprising adding aftertreatment preparations, such as Locanit(R)B, a product of Henkel KGaA, detergents or cationic post-setting agents to the aqueous liquors in quantities of 0.5 to 1.5 g per liter. After rinsing with water, the fibers are dried at temperatures of 50 to 150°C.

The mixtures according to the invention, which are used in aqueous dye liquors, show good electrolyte compatibility and produce excellent depth and level of color on cellulosecontaining textile fibers combined with good performance characteristics, such as fastness to light or wet fastness values.

Example 1 In a jet dyer of the type made by Mathis, Switzerland, raw cotton knitted fabric (average fat content: 0.45% by weight) was treated at 45°C with an aqueous dye liquor containing 1% by weight C.I. Reactive Blue 71 (Prociontürkis H-A, a product of ICI), based on the weight of the raw cotton knitted fabric, and 1 g of the mixture according to the invention per liter liquor.

The liquor ratio was 1:17, based on the weight of the fabric.

The temperature was then increased and quantities of 25 g/l sodium chloride were added at 50°C, 60°C and 70°C. I0 g/l soda was added twice at 85°C. The fabric was then aftertreated with new liquor containing 1 g/l liquor Locanit(R)B, a product of Henkel KGaA, at a temperature of 95°C. After rinsing with water and tumble-drying at 60°C, the fastness of the dyed knitted cotton fabric obtained to rubbing was determined in accordance with DIN 54 021 and its residual fat content was determined by extraction with petroleum ether in accordance with DIN 54 278, Part i. The evenness of dyeing was visually evaluated by three people on a piece of fabric measuring approx. 2 m2 (i = very good, 6 = very poor). The results are shown in Table i.

Table 1 Mixture used ) Residual fat content in % by weight Evenness of dyeing Fastness to rubbing (DIN 54 021) Dry wet Mixture according to the invention 0.02 1-2 Comparison mixture 1 0.31 0.06 0.37 5-6 5 3 6 5 2-3 4-5 5 2-3 ±) Composition of the mixtures used:

Z8 S414 Mixture according to the invention:

23.25% by weight C12 .18 fatty alcohol sulfate, sodium salt (35% by weight aqueous solution) 23.25% by weight castor oil 40 EO 23.25% by weight sulfatized hydroxyalkyl alkylpolyethylene glycol ether of general formula I (R = nbutyl, RI = n-dodecyl, x = 2.5; 48% by weight i0 aqueous solution) 23.25% by weight 2-ethyl hexanol 7 % by weight F0 amaster(R)340 (mineral oil foam inhibitor, Henkel KGaA) Comparison mixture i:

corresponds to the mixture according to the invention without the sulfatized hydroxyalkyl alkylpolyethylene glycol ether: 7% by weight Foamaster( )340 and 31% by weight of each of the other components Comparison mixture 2:

93 % by weight sulfatized hydroxyalkyl 7 % by weight alkylpolyethylene glycol ether of general formula I (R = nbutyl, RI = n-dodecyl, x = 2.5; 48% by weight aqueous solution) Foamaster(R)340 Comparison mixture 3:

without surfactants, sulfatized hydroxyalkyl alkylpolyethylene glycol ether, alcohol and foam inhibitor.

Example 2 In the same jet dyer as in Example i, knitted cotton fabric (average fat content: 0.45% by weight), partly soiled with Parffinum durum (softening point 62°C; partial paraffin coating:

1.2 g distributed over i0 stains each with an area of approx, i0 cmz) was treated at 40°C with an aqueous dye liquor containing 2% 0094OE4 by weight C.I. Reactive Blue 114 (Levafixbrilliantblau E-BRA, a product of Bayer AG), based on the weight of the fabric, and 1 g/l of the mixture according to the invention. The liquor ratio was 1:15. 50 g/l Glauber's salt in two portions and 15 g/l calcined soda in two portions were then added to the aqueous dye liquor. After dyeing for 40 minutes, the fabric was aftertreated at 95°C by addition of 1 g/l Locanit(R)B to the aqueous dye liquor. After rinsing and tumble-drying at 60°C, the dye finish was evaluated in the same way as in Example I. The results are i0 shown in Table 2.

il Table 2 Mixture used2) Residual fat content in % by weight Evenness of dyeing Fastness to rubbing (DIN 54 021) Dry wet Mixture according to the invention 0.15 2-3 3-4 Comparison mixture 1 0.23 0.19 0.39 3-4 2) Composition of the mixtures used:

O0S4OE4 Mixture according to the invention:

23.25% by weight C12 .18 fatty alcohol sulfate, sodium salt (35% by weight aqueous solution) 23.25% by weight C16 .I8 fatty alcohol 6 EO 23.25% by weight sulfatized hydroxyalkyl alkylpolyethylene glycol ether of general formula I (R = nbutyl, RI = n-dodecyl, x = 2.5; 48% by weight i0 aqueous solution) 23.25% by weight 2-ethyl hexanol 7 % by weight Foamaster(R)340 Comparison mixture i:

corresponds to the mixture according to the invention without the sulfatized hydroxyalkyl alkylpolyethylene glycol ether: 7% by weight Foamaster(R)340 and 31% by weight of each of the other components Comparison mixture 2:

93 % by weight sulfatized 7 % by weight hydroxyalkyl alkylpolyethylene glycol ether of general formula I (R = nbutyl, RI = n-dodecyl, x = 2.5; 48% by weight aqueous solution) Foamaster(R)340 Comparison mixture 3:

without surfaotants, sulfatized hydroxyalkyl alkylpolyethylene glycol ether, alcohol and foam inhíbitor.

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS: OO i4 1, 2 • A dyeing aid composition containing anionic and nonionic surfactants, comprising from about 1 to about 60% by weight of surfactants selected from the group consisting of a) Cs.24 alkyl or C8 .z4 alkenyl alcohol sulfates, C14 .18 alkane sulfonates and Ci0 .

14 alkyl benzene sulfonates in the form of their alkali metal, ammonium or amine salts, and b) castor oil containing about 20 to about mols of ethylene oxide, alkoxylated C 24 alkyl or alkenyl alcohols, and alkoxylated C8 .1 z alkylphenols; from about 1 to about 25% by weight of sulfatized hydroxyalkyl alkylpolya!kylene glycol ether corresponding to formula I SO3M R -- O CnH2 nO) ---CH2 -- CH -- R1 (I) in which R is a CI.6 alkyl radical, RI is a C6 IS alkyl radical, M is an alkali metal or ammonium cation, n = 2 or 3 and x is a number of about 2 to about i0; and from about 1 to about 30% by weight of Cz.12 alkyl alcohol; with the proviso that the ratio by weight of surfactants a) to surfactants b) is from about 5:1 to about 1:5, the ratio by weight of surfactants a) and b) to sulfatized hydroxyalkyl alkylpolyalkylene glycol ether is from about i:i to about 4:1 and the ratio by weight of surfactants a) and b) and sulfatized hydroxyalkyl polyalkylene glycol ether to alkyl alcohol is from about i:i to about 5:1.

A dyeing aid composition as in claim 1 comprising from about 1 to about 40% by weight of said surfactants a) and b), from about 1 to about 20% by weight of said sulfatized hydroxyalkyl alkylpolyalkylene glycol ether, and from about 1 to about 30% by weight of said Cz.12 alkyl alcohol.

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