US3512915A

US3512915A - Dyeing textile with a dye solution containing a copolymer of an alkyl siloxane and a polyaminoalkylsiloxane having at least 3 carbons in the alkyl chain

Info

Publication number: US3512915A
Application number: US28851A
Authority: US
Inventors: John L Speier
Original assignee: Dow Corning Corp
Current assignee: Dow Silicones Corp
Priority date: 1960-05-13
Filing date: 1960-05-13
Publication date: 1970-05-19
Anticipated expiration: 1987-05-19
Also published as: DE1419555A1

Description

United States Patent 3,512,915 DYEING TEXTILE WITH A DYE SOLUTION CONTAINING A COPOLYMER OF AN ALKYL SILOXANE AND A POLYAMINOALKYLSILOX- ANE HAVING AT LEAST 3 CARBONS IN THE ALKYL CHAIN John L. Speier, Midland, Mich., assignor to Dow Corning Corporation, Midland, Mich., a corporation of Michrgan No Drawing. Continuation-impart of applications Ser. No. 753,115 and Ser. No. 753,153, both filed Aug. 4, 1958. This application May 13, 1960, Ser. No. 28,851

Int. Cl. D06p /08 US. Cl. 88 8 Claims ABSTRACT OF THE DISCLOSURE Cotton, linen, wood, wool, silk, and glass, acrylic, polyester, nylon, Vinyon, polyolefin, metallic, plastic coated metallic and metallic coated plastic yarns are dyed with any dye in a dyebath containing a copolymer of a polyaminopropylsiloxane and an alkylsiloxane.

The present invention relates to an improved process for coloring textile fibers.

This application is a continuation-in-part of copending applications Ser. Nos. 753,115 and 753,153, both filed Aug. 4, 1958 (both now abandoned after refiling the combined subject matter thereof as Ser. No. 176,797, filed Mar. 1, 1962). The former is a continuation-in-part of copending application Ser. No. 723,991, filed Mar. 26, 1958 (issued as Pat. No. 2,971,864 on Feb. 14, 1961) which is in turn a continuation-in-part of the then copending application Ser. No. 704,343, filed Dec. 23, 1957 (now abandoned).

The textile dyeing art is a highly developed one, but there is a great need for improvement in the resistance of dyed textiles to fading from light, washing, dry clean ing, the atmosphere, or other color destroying agents. The crocking of dyed fabrics (i.e., the undesirable property by which coloring matter rubs oii from a fabric onto another material) has also been an age-old problem.

Although special dyes and/or special techniques for particular textiles have been developed which go a long way toward solving some of the above problems for some types of fabrics, many deficiencies have remained. The problems have been particularly acute in regard to the coloring of glass fibers and synthetic textile fibers, especially those which are relatively hydrophobic and which are thus resistant to swelling in the aqueous dyebaths normally employed. Dyestufis have been forced into the latter types of fibers by the use of chemical swelling agents or carriers, or by the use of high temperatures and pressures in the dyeing process. These expedients have not furnished satisfactory answers to the problems, however. Chemical agents have been expensive and are often toxic, difficult to remove, or damage the fiber in either their application or removal. High temperature dyeing generally requires very expensive equipment in order to operate above atmospheric pressure.

The process of the present invention provides improved dyed textile products and can be carried out with a minimum of the difliculties discussed above. The invention can be particularly described as a process for coloring textile fibers which comprises contacting said fibers with (I) an aqueous dispersion of an organosiloxane copolymer selected from the group consisting of (A) water miscible copolymers conssiting essentially of polymeric units 3 ,5 l 2 ,9 l 5 Patented May 19, 1970 "ice (1) of the formula R," z.,1 u)siY,0

where R is an aliphatic hydrocarbon radical containing a number of carbon atoms selected from the group consisting of 1 and more than 2 carbon atoms and having a valence of n+1 where n is an integer of at least 1, Z is a monovalent radical attached to R by a carbon-nitrogen bond and is composed of carbon, nitrogen and hydrogen atoms and contains at least 2 amine 1 groups, the ratio of carbon atoms to nitrogen atoms in g the substituent --RZ being less than 6:1, each R" is a monovalent hydrocarbon radical free of aliphatic unsaturation, Y is selected from the group consisting of (OH) and (OR) radicals where R is an alkyl radical of less than 4 carbon atoms, x is an integer of from 0 to 2 inclusive, z is an integer of from 0 to 2 inclusive, and the sum of x+z has a value of from 0 to 2 inclusive, and polymeric units.

(2) of the formula II R, 's1Y...o

where each R' is selected from the group consisting of monovalent hydrocarbon radicals and halogenated aryl radicals, Y is as above defined, y is an integer of from 0 to 3 inclusive, m is an integer of from 0 to 2 inclusive, and the sum of y+m has a value of from 1 to 3 inclusive, there being at least 5 percent by weight of the (1) units present in the copolymer and the copolymer having an average degree of substitution of at least 1 organic group attached directly to silicon by carbon-silicon bonding per silicon atom and said copolymer having an amine nitrogen content of at least 0.5 percent by weight, and

(B) Water dispersible acid salts of (A), and (II) a textile dyestuff.

The described process is applicable to all textile fibers, both natural and synthetic. Natural cellulosic fibers such as cotton, linen, and wood, as well as natural protein fibers such as wool and silk, present fewer dyeing problems than do the synthetics, however, and thus generally will not be as greatly benefited as the latter. Nevertheless, cellulosic fibers do not take well to acid dyes because they contain only OH groups as dye sites, and treatment with the defined organosilicon compounds does permit the use of acid dyes on such fibers, thus leading to greater versatility in dyeing processes.

The greatest benefits from the practice of the present invention are derived in the coloring of glass fibers and the hydrophobic synthetic organic textile fibers. The term hydrophobic is not necessarily used here in the limited sense that some special chemical treatment has been given to the fibers to render them unusually water repellant, although the invention is of great benefit in any such case. The term is used here in a broader sense with reference to those fibers which have a relatively greater negative surface potential when immersed in distilled water than do the pure natural cellulosic fibers [see J. Soc. Dyers Colourists, 71, 102 (1955)], and/or which have very small interstitial canals, either of which results in little or no swelling in aqueous media.

Typical examples of hydrophobic synthetic fibers include such well known fibers as glass, acrylic (at least 85 acrylonitrile units), modacrylic (at least 35% but less than 85% acrylonitrile units), polyester (at least 85% an ester of a dihydric alcohol and terephthalic acid), acetate (cellulose acetate and triacetate), Saran (at least vinylidene chloride units), nytril (at least long chain polymer or vinylidene dinitrile), nylon (long chain polyamide with recurring amide groups in the chain), Vinyon (at least 85% vinyl chloride units), and olefin (at least 85% ethylene, propylene, or other olefin unit). The generic names and definitions of these fibers have been adopted by the Federal Trade Commission under the authority of the Textile Fiber Products Identification Act approved Sept. 2, 1958, and are abstracted in Textile World, vol. 109, No. 7, at page 44 (July 1959). Examples of these well known types of fibers are commercially available under such names as Orlon, Zefran, Acrilan, Dacron (Terylene), Darvan, Dynel, and Arnel, as well as under the generic names themselves in many instances, as for example nylon 6 or 66, and Saran.

Some of the above synthetic polymers are also available in the form of films or sheets as well as in the form of fibers. Mylar, for example, is essentially Dacron in a film form. Obviously the process of this invention is applicable to the dyeing of such films. It will also be obvious that the invention is applicable to the above fibers regardless of any mechanical processing to which they may have been subjected, i.e., the twisted, crimped, or stretched forms of yarns and the knitted, woven, plaited, braided, or felt fabrics can be treated in that form.

Other hydrophobic textiles to which the invention is applicable include the metallic yarns such as lam, Lurex, and Metlon, and the various combinations of metallic and organic fibers or yarns. The metallic yarns can be of metal, plastic-coated metal, or metal-coated plastic. Any metal used in the commercial metallic yarns is suitable here, but aluminum is preferred.

Any textile dyestufi can be used in the present invention. The term dyestufi is used herein to include all textile coloring agents, i.e. both the true dyes and those coloring agents classified separately by some authorities as pigments or lakes. Dyestuffs are conventionally classified by several different systems, for example according to color, origin (e.g. natural, such as madder and indigo, or synthetic, coal tar, etc.), chemical class (azo, anthraquinone, triphenylmethane, etc.), method of application or dyers class (acid, basic, direct, mordant, vat, and developing dyes and lakes and pigments), and on the basis of the most important fibers on which they have been used (e.g. acetate dyes). Obviously there is considerable overlapping between various classes within one system as well as between systems, but members of any of these classes can be used.

The following are illustrative of the chemical classes of dyes which are used, as classified by the Society of Dyers and Colourists: nitroso, nitro, mono-, di-, tris-, and tetrakisazo, stilbene, pyrazolone, ketimine, diand triphenylmethane, xanthene, acridine, quinoline, thiazole, indamine, indophenol, azine, aniline black, oxazine, thiazine, sulphide, hydroxyketone, hydroxylactone, anthraquinone (acid, vat, and mordant), arylidoquinone, and indigoid. The important chromophores (color bearers) in the above dyestufis are the azo(N=N-), thio (C=S), nitroso(N=O) and groups, along with the weaker nitro(NO carbonyl(C=O), and ethenyl(C=C-) groups. The auxochromes (which affect the intensity of the color) in the important dyes are the N(CH3)z NHCH NH OH, and OCH groups.

Acid dyes are one of the most important and useful dyes in this invention. They usually contain or are derived from dyes containing sulfonic acid (SO H) groups, and are generally marketed in the form of the water soluble salts containing SO Na groups. They are applied from dyebaths having a pH ranging from 2 to 8, which may be obtained by adjusting the bath with acids such as sulfuric, formic, or acetic or with salts such as ammonium sulfate. C.I. Acid Red 5 (14905) is a good example of an acid dye.

Many metallizable dyes (eg. chrome dyes, mordant dyes) are acid dyes. This latter type of acid dye has an organic structure such that complex compounds can form with metals such as chromium to produce a water-insoluble product. The metal can be added before the dyest-uff (bottom-chrome method), with the dyestuff (metachrome or chromate process) or after the dyestuif (top, or afterchrome process). C.I. Mordant Yellow 1 14025), C.I. Mordant Red 9 (16105), and Cl. Mordant 'Brown 12 are examples of dyes which can be used in any one of the above three methods. (Cl. stands for the Color Index classification of the AATCC and the Society of Dyers and Colourists of Bradford, England.) The five digit number appearing in parentheses behind the names of the dyestuflfs is the color index number as found in the Technical Manual of the American Association of Textile Chemists and Colorists and published by the American Association of Textile Chemists and Colorists. Chromium (as sodium bichromate) is the most widely used mordant, but other metal salts such as copper sulfate, aluminum sulfate, iron sulfate, and tin chloride can be used in similar fashion.

Acid dyes are also available in the form of pre-metallized acid dyes in which the metal is already complexed with the organic dye molecule, as for example in C.'I. Acid Yellow 98, Cl. Acid Green 35 (13361), and Cl. Acid Blue 158 (14880). Many of such dyes are water soluble. Those in which one atom of metal has combined with one dye molecule are known as 1:1 complexes, and are applied from an acid bath. Neutral dyeing types are also available as 2:1 dye to metal complexes.

Direct or substantive dyes also are of use in this invention. These dyes usually contain the sodium sulfonate group as the solubilizing group and are characterized by long molecular structures in which the aromatic rings are capable of assuming a coplanar configuration. The benzidine based dyes are illustrative of this type.

Most of the direct dyes can also be classified as azo dyes, as can many of the acid and disperse dyes. Azo dyes are prepared by diazotization of a primary aromatic amine by nitrous acid, followed by coupling the resulting diazonium salt with aromatic amino or hydroxy compounds such as Naphthol AS. Azo dyestuffs can contain the solubilizing SO Na groups, or can be insoluble pigments. When an insoluble azo dyestuif is formed right in the fiber it is known as an azoic dye. In this latter instance, the dyer can impregnate the fibers first with the aforementioned coupling compound and then with the diazonium salt, so that coupling takes place within the fibers. When the primary aromatic amines used for diazotization in the preparation of azo dyes are applied to textile fibers and diazotized right on the fiber, and the product then coupled as above, the dye is known as a developed dye or color. Any of these azo or azoic dyeing techniques can be used in this invention.

The disperse or acetate dyes are generally small molecules containing amino groups and are only slightly soluble in water, hence they are dispersed rather than dissolved in neutral or slightly alkaline baths for application to fibers. Dispersing agents such as soap are used to prevent agglomeration of dyestuff particles in the bath. Although the disperse dyes were originally of most importance in the dyeing of acetate fibers, they are now used with almost any of the man-made fibers and can be used 1n this invention. These dyes belong to various chemical groups, anthraquinone, aminoazo, pyrazolon, and indophenol types being illustrative. Typical examples of specific dyes of this type are C.I. Disperse Violet 4 (61105), C.I. Disperse Yellow 14, and Cl. Disperse Orange 3 (11005).

Vat dyes also are of interest here. For the most part they are insoluble compounds and are usually anthraquinone, or thioindigoid derivatives. They are characterized by the presence of 0 0 groups which can be reduced with an agent such as sodium hydrosulfite to COH groups. The reduced form is known as the leuco form, and is soluble in caustic soda solutions, forming C--ONa groups. After application to textiles, the latter are oxidized to their original form by exposure to air or to agents such as sodium perborate, hydrogen peroxide, etc., and the dyeing process is usually then completed by exposing the textile fibers to hot soap or detergent solutions. Soluble vat dyes are also available. These are generally in the form of salts of the sulfuric acid esters of the leuco form of the dye, i.e. they contain C--OSO Na groups.

The sulfur dyes are mixtures of complex sulfur-containing organic compounds, and are further examples of dyes which can be used herein. Like vat dyes, the sulfur dyes must be reduced in an alkaline medium for application. Na S is generally both the reducing agent and the source of alkali to bring about the solution of the reduced form.

The so-called chemically reactive dyes are also of use here. Such dyes ordinarily contain solubilizing groups, an organic molecule portion furnishing the chromophores, and sustituents such as halogen, particularly chlorine, which are capable of reacting directly with cellulosic OH groups. As used herein, such dyes can react not only with any OH groups present in the textile fiber being treated, but also may react with functional groups in the organosilicon compound employed.

The basic dyes are another large class of dyes which can be used in this invention, although they are usually less desirable than other types. These are dyes in which the so-called colored portion of the dye molecule carries a positive charge when the dye is in solution. These dyes are generally marketed in the form of chloride or sulfate salts of the basic organic molecule which makes up the colored portion of the dye. Typical salts are those containing the NH Cl group, as in CI. Basic Orange 2 (11270). Because basic dyes exhaust rapidly from a dyebath, they are usually used in conjunction with a retarding agent. On some fibers, particularly vegetable fibers such as cotton, the basic dyes are generally applied after the fiber has been first mordanted with an acid material such as tannic acid.

As has been noted previously, the term dyestuff is used herein to include pigments as well as dyes. Textile pigments are well known materials, and any such. can be used here. The term resin bonded pigments covers the class of pigments which is most useful herein. The latter are often referred to by an RB number, which is a designation assigned by the American Association of Textile Chemists and Colorists. Typical pigments include those of carbon black, dianisidine blue, phthalocyanine blue or green, Ultramarine blue, iron oxide brown or red, metallized azo brown, benzidine orange or yellow, chrome orange or yellow, titania, zinc oxide, indomaroon, and lithosol yellow. Blends of different pigments are often made to achieve a particular color. Pigments are often marketed in the form of neutral or alkaline aqueous dispersions.

It is to be understood that when reference is made herein to contacting the fibers with a textile dyestufi, the dyestuff can be a single entity or a multiple entity and can be applied by a single step or a multiple step process. In other words, the conventional applications such as those discussed above are contemplated here, and applying a dyestuif can include such diverse processes as those in which two or more colorless materials are applied separately or in which mordants, soaps, detergents or other materials which are not dyestuffs themselves are conventionally applied as a part of the dyeing process. Some dyestuffs can be applied from solutions in organic solvents, but water dispersible dyestuffs are preferred in the industry and in this invention. The term water dispersible is used to include materials which are truly water soluble as well as those which are insoluble or only very slightly soluble in water and hence which are applied as suspensions of finely divided particles in water, usually in the presence of a surface active agent to assure good dispersion of the particles. In general, the water soluble dyestuffs are preferred.

The organosiloxane copolymers employed in this invention consist essentially of polyaminoalkyl substituted siloxane units of the formula and conventional siloxane units of the formula with there being at least 5 percent by weight of the former units present. In these formulae, x and z are integers of from 0 to 2 inclusive and the sum of x+z has a value of from 0 to 2 inclusive, y is an integer of from 0 to 3 inclusive, m is an integer of from 0 to 2 inclusive, and the sum of y+m has a value of from 1 to 3 inclusive. The average values for any of these subscripts can be fractional when the copolymer as a whole is considered. The amounts of the two types of polymeric units present in the copolymer and the values of x and y in each unit should be such that there is an average of at least one organic group attached directly to silicon by carbonsilicon bonding per silicon atom. In other words, the ratio of R+R"'+(Z R) groups to Si atoms is at least 1:1, i.e., the average degree of substitution is at least 1. It will be seen that the average degree of substitution can be as high as 3, but preferably it ranges from 1 to about 2.05 inclusive. The amine nitrogen content of the copolymer should be at least 0.5 percent by weight. It is most preferred that x be 0 or 1, y be 2, and z be 0 or 1, and that there be at least 15 percent by weight of the polyaminoalkyl substituted siloxane units present.

In the defined polymeric units, R can be any aliphatic hydrocarbon radical containing 1 or more than 2 carbon atoms and having a valence of at least two, i.e. it can include, in any aliphatic configuration, any combination and any number of methyl, vinyl, methylene, vinylene,

groups within the scope of the claims.

Each Z can be any monovalent radical attached to R through a carbon-nitrogen linkage, which is composed of hydrogen, carbon and nitrogen atoms, in which preferably all of the nitrogen atoms are present as amine or nitrile groups, and in which there are at least two amine groups per Z radical. The term amine groups comprises primary amine, secondary amine (including imine) and tertiary amine groups. The scope of Z will be better understood from a consideration of the method of producing these siloxanes.

R can be any monovalent hydrocarbon radical free of aliphatic unsaturation. Preferably, however, it contains a maximum of 18 carbon atoms. Illustrative examples of suitable R" radicals include alkyl radicals such as methyl, ethyl, propyl, isopropyl, butyl and octadecyl; aryl radicals such as phenyl, xenyl, and naphthyl; alkaryl radicals such as tolyl and xylyl; aralkyl radicals such as benzyl; and cycloaliphatie radicals such as cyclohexyl. Methyl, ethyl, and phenyl are most preferred.

The Y radicals in the above formulae represent (OH) and/or (OR) radicals where R represents an alkyl radi cal of less than 4 carbon atoms, i.e., methyl, ethyl, propyl, or isopropyl radicals.

In the conventional siloxane units each R can be any monovalent hydrocarbon radical or halogenated aryl radical. Examples of suitable radicals include all of the illustrative R radicals listed above, as well as alkenyl and alkynyl radicals such as vinyl, allyl, cyclohexenyl, and propynyl; and halogenated aryl radicals such as bromophenyl, dichlorophenyl, chloroxenyl, a,a,ot-lllfiu0l0- tolyl, and the like.

In the defined units, each R, R, R, R, Z, or Y radical can of course be the same as or different from each of its fellow radicals in the copolymer.

The preferred method for the preparation of the defined copolymers is that which is illustrated in detail in the copending application of Lawrence H. Brown, filed concurrently herewith and entitled Method for the Preparation of Aminoalkylsiloxane Copolymers. In brief, this method comprises mixing the appropriate amounts of a (polyaminoalkyl)alkoxysilane, i.e.

with a conventional organosiloxane containing a substantial amount of silicon-bonded hydroxy groups, for example, 1 to percent by weight OH. The former reacts with the latter to form new siloxane bonds, as illustrated by the simplified equation:

ESlOR+HOSiE ESlOSlE +ROH The reaction is preferably speeded up by heating the mixture, as for example at 100 to 200 C. Inert solvents can be present if desired. The alcohol which is formed in this reaction can be removed by disillation, thus it is certain that true copolymers are formed. It will be readily apparent that the copolymer can have unreacted (OR) and/or (OH) groups present, depending upon the relative amounts of the two reactants and the amount of (OR) or (OH) present in the reactants initially. If de sired, excess (OR) groups can be hydrolyzed by the addition of Water to the system, and controlling the amount of water so added controls the amount of such groups which remain in the copolymer. Likewise, excess (OH) groups can be caused to condense, as for example by heating the copolymer. Any or all of the alcohol formed by either the initial reaction or any subsequent hydrolysis can be left in the reaction product, if desired. In aqueous solutions or dispersions, the copolymer actually is in a state of equilibrium, and determination of the precise amounts of silicon-bonded (OH) or (OR) present is ordinarily not feasible.

Another method for the preparation of the copolymers employed in this invention is by the cohydrolysis of the (polyaminoalkyl)alkoxysilanes referred to above with the conventional alkoxysilanes of the formula R' Si(OR) The preparation of such cohydrolyzates can be by conventional techniques, and is set forth in detail in my aforesaid copending application Nos. 753,115 and 753,153.

The (polyaminoalkyl) alkoxysilanes employed to prepare the copolymers used herein can be produced by the techniques set forth in greater detail in the above mentioned copending applications and in my aforesaid copending application Ser. No. 723,991. Thus they can be produced by reacting a polyamine with a halogenohydrocarbonalkoxysilane where each halogen atom is on a car- 'bon atom at least gamma to the silicon atom. Alternatively, they can be prepared by reacting the polyamine with an alpha-halogenohydrocarbonalkoxysilane. In these reactions one nitrogen in the polyamine replaces a halogen atom in the halogenohydrocarbon radical, and the halogen acid is given off. The reaction is best carried out at temperatures of from 50 to 200 C. under anhydrous conditions using a molar excess of the polyamine.

The polyamines which can be employed include, for example, the following: ethylenediamine, diethylenetriamine, 1,6 hexanediamine, 3 aminoethyl--l,6-'diaminohexane, N,N dimethylhexamethylenediamine, cadaverine, piperazine, dl-1,2-propanediamine, methylhydrazine, 1 aminoguanidine, 2 pyrazoline, benzenetriamine, ben- Zenepentamine, benzylhydrazine, N-methyl-p-phenylenediamine, N,N dimethyl p phenylenediamine, and 3-0- tolylenediamine.

It can be readily seen that the polyamine employed can be any aliphatic, cycloaliphatic or aromatic hydrocarbon amine containing at least two amine groups, one of which must contain at least one hydrogen atom. The term poly in the specification is intended to include compounds or radicals containing two or more amine groups.

The halogenohydrocarbonsilanes employed in the above described process can themselves be prepared by the well known addition reaction of a halogenated aliphatic hydrocarbon containing at least one unsaturated carbon to carbon linkage, with a halosilane such as that of the formula R" SiHCl where R" and x are as previously defined, after Which the addition product is alkoxylated by reacting it with one or more alcohols of the formula ROH. Examples of suitable halogenated hydrocarbons include allylbromide, allyliodide, methallylchloride, propargylchloride, l chloro- 2 -methylbutene-2, 5- bromo pentadiene 1,3, 16 bromo 2,6dimethylhexadecene-2, and the like. The halogenohydrocarbons can contain more than one halogen atom, as in 3,4-dibromobutene-l and 3-chloro-2-chloromethylpropene-l, so that the radicals resulting therefrom can react with more than one amino nitrogen atom, i.e. n can be greater than 1. Preferably there should be no more than one halogen atom per carbon atom. Furthermore, no halogen atom can be so positioned that after the addition of the halogenohydrocarbon to the silicon there is a halogen atom on a carbon atom which is beta to the silicon.

A second method for preparing the halogenohydrocarbonsilanes described above is that of halogenating an alkylhalosilane with elemental halogen followed by reaction with an alcohol to give the halohydrocarbonylalkoxysilane. This is the method employed when R in the above formula is a methylene radical.

The radical (RZ can be of any length, so long as the ratio of carbon to nitrogen in the radical is less than 6:1. As a practical matter, the R radicals will ordinarily contain no more than 18 carbon atoms, and preferably contain 1 or 3 to 5 inclusive carbon atoms. The preferred Z radicals contain from 1 to 8 carbon atoms, and n is preferably 1, 2, or 3.

The acid salts which can be employed herein can be prepared by contacting the defined copolymers in a liquid phase with the chosen acid. The acid can be organic or inorganic, and is preferably a water soluble acid such as hydrochloric, hydrobromic, nitric, acetic, formic, propanoic, and lactic acids. The salts are generally used in situations where the alkalinity of the amine groups is undesirable, or where a greater degree of water solubility is desired in the organosilicon compound. In preparing the salts, ordinarily the acid will be used in an amount to provide about one equivalent of acid for each amine nitrogen atom present in the copolymer. Of course any amount less than this can be used, if desired, to provide a partial salt having solubility characteristics intermediate between the copolymer per se and the full salt. Such a partial salt is meant to be included within the scope of the term acid salt as it is employed herein. An excess of acid over the equivalent amount can also be used, subject only to the practical limitation imposed by any harm which a large excess of acid might do to textiles or dyestufis in contact with a system which is too highly acid.

The defined copolymers or salts used in the process of this invention are water-miscible materials. The term water miscible is used herein as inclusive of both water soluble and self-emulsifiable materials. In general, the the salts defined herein are truly water soluble in the usual sense of that term. The same is also true of those copolymers which are not salts but which contain a sufficient amount of the polyaminoalkyl substituted polymeric units to impart water solubility. In a dimethylsiloxane copolymer system, for example, those copolymers which contain at least 20 to 25 percent by weight of the polyaminoalkyl substituted units will generally be truly Water soluble. Copolymers containing a. lesser amount of polyaminoalkyl substituted units, e.g. 5 to 20 percent in the aforesaid di methylsiloxane copolymer system, are generally selfemulsifiable. By this it is meant that the latter copolymers donot form true solutions, but do form stable emulsions 9 with water, even in the absence of any added emulsifying agent, i.e., no third ingredient is necessary to form an emulsion.

The organosilicon compounds defined herein can have a beneficial result in the dyeing process regardless of at what stage in the process they are applied to the textile fibers. For example, the fibers can be pretreated prior to coloring by contacting them with the organosilicon compound. Preferably the fibers are then dried before proceeding with the coloring step, but this is not necessary in some cases. If used, the drying step can be carried out at room temperature but preferably is expedited by heating the treated fibers at temperatures of, for example, from 125 to 400 F. (i.e., about 52 to 204 C.). Such heat treatments also tend to improve the fastness of the final colored product.

The pretreatment technique is in general the most preferred one. Good results can also be obtained, however, by mixing the organosilicon compound, water, and textile dyestutf, then applying the entire mixture to the fibers. The application step is then followed by drying the fibers and by any additional steps required for the particular dyestutf employed. When a mixture is used in this fashion, it can be applied either to the bare textile fibers or to fibers which have been pretreated with the organosilicon compound as described above.

A third alternative technique is to first color the fibers by any of the conventional processes, and then treat the colored product with the organosilicon compound.

In any of the application techniques discussed above, conventional processes (such as padding, spraying, or immersion in a treating bath to exhaust the treating material onto a textile) can be used to apply the dyestuff and/or the organosilicon compound. The textile fibers or filaments can be treated as such, or in the form of threads, yarns, fabrics, finished garments, etc. If desired, the treated and colored products obtained by practicing this invention can be further treated with other compounds to render them Water repellent or wrinkle resistant, or to provide a softer hand in the finished fabrics, etc. Aftertreatments with organosilicon compounds such as those described in US. Pats. 2,807,601; 2,728,692; 2,588,365; and 2,588,366 are often most desirable. The present invention can also be useful in coloring textiles which have been pretreated in accordance with the aforesaid U.S. patents.

Aqueous solutions or emulsions of the defined copolymers or copolymer salts can be applied to the textile fibers at any desired concentration. Ordinarily the best results will be obtained by employing material having a concentration of the defined organosilicon compounds ranging from about 0.1 to 5.0 percent by weight, preferably from 0.3 to 2.0 percent. This concentration will generally provide the 0.2 to 0.8 percent by weight pickup of organosilicon compound which is preferred for most fibers. It is often desirable to incorporate a water-miscible solvent (such as the lower aliphatic alcohols dioxane, tetrahydrofuran, etc.) into the aqueous systems employed herein, as an aid in speeding the attainment of homogeneous solutions or emulsions.

Copolymer preparation In the following description and examples, the symbols Me, Et, Vi, and Ph have been used to represent methyl, ethyl, vinyl, and phenyl radicals respectively. Copolymers and salts for use in the examples were prepared by the following general technique, which specifically illustrates the preparation of a 75/25 copolymer:

A mixture was prepared containing 75 g. (MeO Si CH NHCH CH NH and 25 g. of a polymer having the formula (HO Me SiO (Me SiO SiMe (OH) where the average value of a was such that the polymer contained 3.5 percent by weight of (OH) groups. Such a mixture contains about 1.01 mols (OMe) groups and 0.05 mol (OH) groups. The mixture was heated to 150 C. under a refiux condenser, then 8.65 g. H O (0.48 mol, equivalent to the 0.96 molar difference between the OMe and OH groups) was added, followed by 75 g. EtOH (sufficient to provide a solution of about 50 percent of the theoretical organosiloxane product). About one third of the alcohol was removed by distillation and then the product was readjusted to a 50 percent concentration. The resulting ethanol solution is completely soluble in water, and the copolymer product present therein contained about 75 percent units and 25 percent Me SiO units, by weight. The value of z in this copolymeric solution could not be measured because of the alcohol present as solvent, but theoretically would range between 0 and 1. When the alcoholic solution of such a copolymer is itself dissolved in water, a major portion of any residual silicon-bonded methoxy groups are hydrolyzed. When such an aqueous solution is applied to a textile and the treated material is dried, hydrolysis and condensation of the copolymer become substantially complete so that the copolymer consists essentially of only Me SiO and units.

A salt of the copolymer described above was prepared by adding 40.5 g. acetic acid (0.676 mol) to the cool 50 percent alcohol solution, thus providing 1 mol of acid for each gram atom of nitrogen present in the copolymer.

Copolymers and salts similar to those specifically illustrated above were made from the same reactants by the same technique, but using ratios of 10/90, 25/75, 50/50, and /10 in place of the 75/75 ratio described above. Related 50/50 copolymers were prepared by the same technique, except that (M60 MeSi (CH NHCH CH NH (MeO or (MeO) Si(CH NHCH CH N(CH CH CN) were used in place of the (MeO) Si(CH NHCH CH Nl-I reactant.

In the following examples, all parts and percentages are by weight unless otherwise indicated.

EXAMPLE 1 A series of aqueous solutions was prepared by mix ing 98 parts of Water with 2 parts respectively of each one of the 50 percent alcohol solutions of the various copolymers and salts described above under Copolymer Preparation. Thus aqueous solutions were obtained which contained 1 percent respectively of the 10/90, 25/75, 50/50, 75/25, or 90/ 10 copolymers (where the designation 10/90 etc. refers to the theoretical ratio of units to Me SiO units) or 1 percent of the respective 50/50 copolymers specifically described above, where the polyaminoalkyl substituted units were NHgCHgCHgNH (CH SiMeO or units, 01' 1 percent of the respective acetate salts of these various copolymers. All of the salts, and all of the copolymers except the 10/90, formed true aqueous solution. The 10/ 90 copolymer formed a stable emulsion.

A number of test pieces of undyed Orlon, Dacron, nylon, acetate, cotton, silk, wool, viscose, and glass fiber textiles were each padded with one of the solutions by dipping into the solution and running the wet fabric through squeeze rollers. The pickup of organosilicon compound was about 0.5 percent in each case, based on the weight of the fabric. The Orlon samples were dried for 5 minutes at 260 F., and all others were dried for 20 minutes at 255 F. Specimens of each treated fabric were then dyed with various dyes as shown below.

Part A A number of acid and metallized acid dyes were applied to the treated fabrics by the following exhaustion technique. Aqueous solutions of each dye were made up containing 3 parts dye, 2 parts ammonium acetate, and 100 parts water based on the weight of the test fabric. Each specimen of fabric was immersed in one of the solutions for 30 minutes while the solution was held at 170 F., and was then rinsed with cold water and allowed to dry at room temperature. The dyes employed were as follows, with Color Index designations being shown in parentheses: Cibalan Black BLG, Erio Fast Brown 5 GL, Supranol Orange RA (C.I. Acid Orange 45) (22195), Pontacyl Green BL (Acid Green 3) (42085), Nigrosine ESB Extra (C.I. Acid Black 2) (5042 Calcocid Fast Light Orange 2G (C.I. Acid Orange 10) (16230), Erio Anthracene Blue 4 GL (C.L. Acid Blue 23) (61125), Gycolan Dark Green BL (C.L. Acid Green 35) (13361), Kiton Fast Orange GR (C.I. Acid Orange 22), Brilliant Croceine 3 BA (C.I. Acid Red 73) (27290), Kiton Red S (C.I. Acid Red 7) (14895), Cibalan Yellow GL (C.I. Acid Yellow 114), Cibalan Orange RLW (C.I. Acid Orange 86), Cibalan Brown 2 'RL (C.I. Acid Brown 45 Cibalan Bordeaux GRL (C.I. Acid Red 213), Calcofast Brown MF (C.I. Acid Brown 97), and Calcofast Olive Brown G (C.I. Acid Brown 93). Treated fabrics were also dyed with Neolan Yellow BE (19010), using the same technique except that 4 parts H 80 were used in place of the salt in the dye solution.

Each of the above treated fabrics had a good depth of shade and a good color yield from. each of the dyes. Orlon, cotton, glass and Dacron fabrics which had no pretreatment were only poorly dyed or not colored at all when subjected to the same dyeing process, i.e., they were at best only slightly stained by the dyes.

Part B Direct dyes were applied to the treated fabrics by padding with solutions containing 0.55 part dye, 100 parts water, and 0.5 part Tergitol TMN (a trimethylnonyl ether of polyethylene glycol used as a wetting agent). The dyed fabrics were then heated for 5 minutes at 260 F., rinsed with cold water, and dried at room temperature. The dyes employed were Chlorantine Fast Orange GRLL (C.I. Direct Orange 34) (40215/20-,) Chlorantine Fast Red 5 BRL (C.I. Direct Red 80) (35780), Chlorantine Fast Blue 2 RLL (C.I. Direct Blue 80), and Calcomine Sky Blue FF Extra Conc. (C.I. Direct Blue 1) (24410). Each fabric had a good depth of shade and color yield, whereas Orlon, Dacron, glass and wool fabrics were only slightly stained when these dyes were applied without the organosilicon pretreatment.

Part C Solutions containing 0.55 part of a reactive dye, 100 parts water, and 0.5 part Tergitol TMN were padded onto the organos'ilicon treated fabrics, and the wet fabrics were dried for 5 minutes at 260 F. The dried fabrics were then washed in soapy water at 56 C., rinsed with cold water, and dried at room temperature. The dyes employed were the Cibacron dyes Turquoise Blue G, Yellow R, Black BG, and Brilliant Red 3 B; the Remazol dyes Yellow G and Red B; and the Procion dyes Brilliant Blue R, Yellow R, Brilliant Red 5 B and 2 B, Brilliant Yellow 6 G, and Printing Green 5 G. Each fabric had a good depth of shade and color yield, whereas again untreated glass,

12 Orlon and Dacron would only take a slight stain from the same dyes.

Part D Disperse dyes Eastone Red B (C.I. Disperse Red 30) and Eastone Orange 3 R (C.I. Disperse Orange 17) were applied to the treated fabrics by the exhaustion technique of Part A above. Each fabric was found to be truly dyed and not merely stained, although the depth of shade obtained was less satisfactory than that obtained in Parts A to C above.

EXAMPLE 2 A single bath dyeing process was carried out by preparing solutions of 2.2 parts of a reactive dye, 2.44 parts of the respective 50 percent alcohol solutions of the 50/50 copolymers described in Example 1, and parts of water, padding samples of each untreated fabric of Example 1 with one of the solutions, drying each fabric at room temperature followed by 5 minutes heating at 260 F., then washing each fabric in warm soapy water, rinsing with cold water, and again drying the fabric at room temperature. The reactive dyes employed were Procion Blue 3 G and Procion Red B. All of the fabrics were suitably colored :by this technique. Greater bath stability was obtained in this system 'by adding NH OH up to a final concentration of 10 percent.

EXAMPLE 3 When (EEO EtSi CH gNHCHgCHgNHg,

(E) 2PhSi CH gNHCHzCHzNHZ (M60 )gSiC Hz C H2 0 HNH C H2 0 HZNHZ,

HQNI'IC HQCIIZNHZ (MeO sicn stnc nns Me (M00 S1 CH NH (CH NHz s 2 a s a z 2 or (MeO) Si(CH NMe(CH NHMe is substituted for the (MeO) Si(CH NHCH CH NH used in the preparation of the copolymers shown in Example 1, and the resulting copolymers and salts are used for fabric treatment and dyeing processes in accordance with that example, comparable results are obtained.

EXAMPLE 4 The various 1 percent solutions in water of the copolymers of Example 1 were mixed with formic, adipic, hydrochloric, or nitric acids respectively in an amount to provide 1 molecule of the acid for each N atom, thus forming the respective salts. When these salt solutions are employed to treat the fabrics of Example 1 by the technique employed in that example, and the treated fabrics are then dyed as in that example, the dyed fabrics have a comparable depth of shade and color yield.

EXAMPLE 5 The organosilicon-treated fabrics of Example 1 were each padded with various commercial pigment dyestuffs in the form of aqueous suspensions or dispersions containing about 5 parts of the as-marketed dispersion and 95 parts water. After padding, the fabrics were dried at room temperature and then heated for 5 minutes at 250 F. Each sample had a good depth of shade and color yield. Equivalent results were obtained from a single bath system by padding the untreated fabrics with a solution of 1.0 part of one of the organosilicon copolymers of Example 1 and 94.0 parts water in which there was dispersed 5 parts of any one of the as-marketed dispersions of the same commercial pigments, followed by air drying the fabrics and heating them for 5 minutes at 250 F The commercial pigment dispersions employed in both of the above dyeing processes were the alkaline dispersion types Aridye Gray K (RB 10), Aridye Yellow N (RB 93), Aridye Yellow K (A.A.T.C.C. designation 13 RB 92) Aridye Brown R (RB 31), and Primal Burgundy; and the Aridye SXN neutral dispersion compositions Brown R (RB 31), Red B (RB 60), Yellow R (RB 94), Blue 2 G (RB 20), and Green B (RB 40). These commercial pigment dispersions contain from about 25 percent to about 60 percent solids, and the extent to which they are diluted for application to fabrics depends almost entirely upon the shade of color desired on a particular fabric.

EXAMPLE 6 When paper or any fabrics of the acrylic, modacrylic, polyester, Saran, nytril, or polyethylene types are pretreated as in Example 1 and dyed as in Parts A to D of that example, the materials pickup good deep shades of the color employed. The shade obtained from any particular dye could be varied over a wide range by varying the concentration of dye in the dyeing bath.

EXAMPLE 7 A series of copolymers was prepared by mixing the amine (MeO) Si(CH NHCH CH NH with one or more of various conventional alkoxysilanes, heating the mixture to 50 to 100 C., and slowly adding water up to an amount equivalent to the alkoxy groups present. The entire reaction product from each was diluted with water to a concentration of 1 percent organosiloxane content and each solution was neutralized with 1 mol acetic acid per gram atom of nitrogen. The types and weight ratios of silanes employed were as follows:

(A) 25 amine/75 Me Si(OEt) (B) 50 amine/25 Me Si(OEt) /25 MeSi(OEt) (C) 54 amine/46 ViSi(OEt) (D) 50 amine/25 MePhSi(OEt) /25 C1 C H Si(OEt) (E) 70 amine/30 PhSi(OEt) (F) 70 amine/10 Me Si(OEt) /1O MeSi(OEt) /1O Me SiOEt When the 1 percent solutions of the salts of the above cohydrolyzates are used as the organosilicon treatment in the processes of Example 1, approximately the same results are obtained in the dyeing operations of that example.

The preparation of the various (polyaminoalkyD- alkoxysilanes used to make the copolymers described in the preceding examples is set forth in detail in the copending applications previously mentioned. The compound can be prepared by reacting 3 moles of acrylonitrile with 1 mol (MeO) Si(CH NHCH CH NH keeping the exothermic reaction down to about 55 C. until it subsides, heating the reaction product at about 95 C. for 4 hours, and flash distilling that mass to a pot temperature of 168 C. at 15 mm. Hg pressure to remove the 1 mol of unreacted acrylonitrile. The resulting residue consists essentially of the desired product, n 1.4615, and is a brown oily liquid.

That which is claimed is: 1. A process for coloring textile fibers which comprises contacting said fibers with (I) an aqueous dispersion of an organosiloxane copolymer selected from the group consisting of (A) water-miscible copolymers consisting essentially of polymeric units (1) of the formula Rn(ZnR')slY;O3 x

Where. R is an aliphatic hydrocarbon radical selected from the group consisting of aliphatic hydrocarbon radicals containing 1, 3, 4, and 5 carbon atoms and having a valence of n+1 where n is an integer of from 1 to 3 inclusive, Z is a monovalent radical attached to R by a carbon-nitrogen bond and which contains up to 8 carbon atoms and is composed of carbon, nitrogen and hydrogen atoms and contains at least 2 amine groups, the ratio of carbon atoms to nitrogen atoms in the substituent ---R'Z being less than 6:1, each R" is a monovalent hydrocarbon radical free of aliphatic unsaturation, Y is selected from the group consisting of (OH) and (OR) radicals where R is an alkyl radical of less than 4 carbon atoms, x is an integer of from 0 to 2 inclusive, z is an integer of from 0 to 2 inclusive, and the sum of x+z has a value of from 0 to 2 inclusive, and polymeric units (2) of the formula R SiYmO where each R'" is selected from the group consisting of monovalent hydrocarbon radicals and halogenated aryl radicals, Y is as above defined, y is an integer of from 0 to 3 inclusive, m is an integer of from 0 to 2 inclusive, and the sum of y+m has a value of from 1 to 3 inclusive, there being at least 5 percent by weight of the (1) units present in the copolymer and the copolymer having an average degree of substitution of at least 1 organic group attached directly tosilicon by carbon-silicon bonding per silicon atom and said copolymer having an amine nitrogen content of at least 0.5 percent by weight, and (B) water-miscible acid salts of (A), and (II) a textile dyestutf.

2. In a process for coloring textile fibers by contacting said fibers with a textile dyestuff, the improvement which comprises contacting the fibers with an aqueous dispersion of an organosiloxane copolymer selected from the group consisting of (A) water-miscible copolymers consisting essentially of polymeric units (1) of the formula where R' is an aliphatic hydrocarbon radical selected from the group consisting of aliphatic hydrocarbon radicals containing 1, 3, 4, and 5 carbon atoms and having a valence of n+1 where n is an integer of from 1 to 3 inclusive, Z is a monovalent radical attached to R by a carbon-nitrogen bond and which contains up to 8 carbon atoms and is composed of carbon, nitrogen and hydrogen atoms and contains at least 2 amine groups, the ratio of carbon atoms to nitrogen atoms in the substituent ---RZ being less than 6:1, each R" is a monovalent hydrocarbon radical free of aliphatic unsaturation, Y is selected from the group consisting of (OH) and (OR) radicals where R is an alkyl radical of less than 4 carbon atoms, x is an integer of from 0 to 2 inclusive, z is an integer of from 0 to 2 inclusive, and the sum of x+z has a value of from 0 to 2 inclusive, and polymeric units (2) of the formula R ySiYmO 15 there being at least 5 percent by weight of the (1) units present in the copolymer and the copolymer having an average degree of substitution of at least 1 organic group attached directly to silicon by carbon-silicon bonding per silicon atom and said copolymer having an amine nitrogen content of at least 0.5 percent by weight, and

(B) water-miscible acid salts of (A).

3. In a process for coloring hydrophobic textile fibers by contacting said fibers with a water dispersible textile dyestufi', the improvement which comprises pretreating said fibers prior to coloring by contacting the fibers with an aqueous dispersion of an organosiloxane copolymer selected from the group consisting of (A) water-miscible copolymers consisting essentially of polymeric units (1) of the formula where R is an aliphatic hydrocarbon radical selected from the group consisting of aliphatic hydrocarbon radicals containing 1, 3, 4, and 5 carbon atoms and having a valence of ru-l-l where n is an integer of from 1 to 3 inclusive, Z is a monovalent radical attached to R by a carbon-nitrogen bond and which contains up to 8 carbon atoms and is composed of carbon, nitrogen and hydrogen atoms and contains at least 2 amine groups, the ratio of carbon atoms to nitrogen atoms in the substituent RZ being less than 6:1, andeach R" is a monovalent hydrocarbon radical free of aliphatic unsaturation, Y is selected from the group consisting of (OH) and (OR) radicals where R is an alkyl radical of less than 4 carbon atoms, x is an integer of from to 2 inclusive, 2 is an integer of from 0 to 2 inclusive, and the sum of x-i-z has a value of from 0 to 2 inclusive, and polymeric units (2) of the formula where each R' is selected from the group consisting of monovalent hydrocarbon radicals and halogenated aryl radicals, Y is as above defined, y is an integer of from O to 3 inclusive, m1 is an integer of from 0 to 2 inclusive, and the sum of y+m has a value of from 1 to 3 inclusive, there being at least 5 percent by weight of the (1) units present in the copolymer and the copolymer having an average degree of substitution of at least 1 organic group attached directly to silicon by carbon-silicon bonding per silicon atom and said copolymer having an amine nitrogen content of at least 0.5 percent by weight, and

(B) water-miscible acid salts of (A), and then drying said fibers.

4. A process for coloring hydrophobic textile fibers which comprises contacting said fibers with a mixture consisting essentially of (I) an aqueous dispersion of an organosiloxane copolymer selected from the group consisting of (A) water-miscible copolymers consisting essentially of polymeric units (1) of the formula where R is an aliphatic hydrocarbon radical selected from the group consisting of 1 and more than 2 carbon atoms and having a valence of ni+1 where m is an integer of from 1 to 3 inclusive, Z is a monovalent radical attached to R by a carbon-nitrogen bond and which contains up to 8 carbon atoms and is composed of carbon, nitrogen and hydrogen atoms and contains at least 2 amine groups, the ratio of carbon atoms to nitrogen atoms in the substituent -R'Z being less than 6: 1, and each R" is a monovalent hydrocarbon radical free of aliphatic unsaturation, Y is selected from the group consisting of (OH) and (OR) radicals where R is an alkyl radical of less than 4 carbon atoms, x is an integer of from 0 to 2 inclusive, z is an integer of from O to 2 inclusive, and the sum of x+z has a value of from 0 to 2 inclusive, and polymeric units (2) of the formula R' SiYmO where each R is selected from the group consisting of monovalent hydrocarbon radicals and halogenated aryl radicals, Y is as above defined, y is an integer of from O to 3 inclusive, m is an integer of from O to 2 inclusive, and the sum of y-i-m has a value of from 1 to 3 inclusive, there being at least 5 percent by weight of the 1) units present in the copolymer and the copolymer having an average degree of substitution of at least 1 organic group attached directly to silicon by carbon-silicon bonding per silicon atom and said copolymer having an amine nitrogen content of at least 0.5 percent by weight, and (B) water-miscible acid salts of (A), and

(II) a water dispersible textile dyestuff, and then drying said fibers.

5. In a process for coloring textile fibers selected from the group consisting of glass, nylon, polyacrylonitrile, dihydric alcohol-terephthalic acid polyester, polyvinylidene chloride, polyvinylidene dinitrile, cellulose acetate and polyolefin fiber-s with a water dispersible textile dyestuft', the improvement which comprises pretreating said fibers prior to coloring by contacting the fibers with an aqueous solution of a water-soluble acid salt of an organosiloxane copolymer consisting essentially of polymeric units (I) of the formula where Y is selected from the group consisting of (OH) and (OR) radicals where R is an alkyl radical of less than 4 carbon atoms, and z is an integer of from O to 2 inclusive, and polymeric units (II) of the formula (OH )zSi(OH)mO where m is an integer of from 0 to 1 inclusive, there being at least 15 percent 'by weight of the (I) polymeric units present in said copolymer, and then drying said fibers.

6. In a process for coloring textile fibers selected from the group consisting of glass, nylon, polyacrylonitrile, dihydric alcohol-terephthalic acid polyester, polyvinylidene chloride, polyvinylidene dinitrile, cellulose acetate and polyolefin fibers with a water dispersible textile dyestuff, the improvement which comprises pretreating said fibers prior to coloring by contacting the fibers with an aqueous solution of a water-soluble acid salt of an organosiloxane copolymer consisting essentially of polymeric units 1 7 (I) of the formula where Y is selected from the group consisting of (OH) and (OR) radicals Where R is an alkyl radical of less than 4 carbon atoms, and z is an integer of from to 1 inclusive, and polymeric units (II) of the formula where m is an integer of from 0 to 1 inclusive, there being at least 15 percent by weight of the (I) polymeric units present in said copolymer, and then drying said fibers.

7. A process for coloring textile fibers selected from the group consisting of glass, nylon, polyacrylonitrile, dihydric alcohol-terephthalic acid polyester, polyvinylidene chloride, polyvinylidene dinitrile, cellulose acetate and polyolefin fibers which comprises contacting said fibers with an aqueous dispersion of a mixture consisting essentially of (I) an aqueous solution of a water-soluble acid salt of an organosiloxane copolymer consisting essentially of polymeric units l) of the formula NH;CH2CHzNH(CHz)3SiY;O

where Y is selected from the group consisting of (OH) and (OR) radicals where R is an alkyl radical of less than 4 carbon atoms, and z is an integer of from O to 2 inclusive, and and polymeric units (2) of the formula a)2 (O )mO References Cited UNITED STATES PATENTS 2,436,304 2/1948 Johannson 88 2,754,311 7/1956 Elliot. 2,832,754 4/1958 Jex et a1. 2,865,918 12/1958 Hurwitz et al 874 X 2,927,839 3/ 1960 Balley et a1. 88 2,971,864 2/1961 Speier.

FOREIGN PATENTS 553,033 12/1956 Belgium.

OTHER REFERENCES 1962 Technical Manual of the American Association of Textile Chemists & Colorists; vol. XXXVIII, pages D76-D884, Pub. by Amer. Assoc. Textile Chemists & Colorists, 1962.

Textile World, vol. 109, No. 7, pp. 43-44.

DONALD LEVY, Primary Examiner U.S. Cl. X.R.