US3504998A - Dyeing textile coated with an aminoethylaminopropyl trialkoxy silane - Google Patents

Description

United States Patent US. Cl. 8-31 7 Claims ABSTRACT OF THE DISCLOSURE Textile such as cotton, linen, wool, silk, acrylic fibers, polyester fibers, acetate fibers, nylon and polyolefin fibers, plastic coated metal fibers and metal coated plastic fibers are coated with a compound having the following formula wherein R is a short chain alkyl group:

and then colored with dyes, pigments and lakes of all types. Specifically, CI. 14905, 0.1. 16105, C.l. 13361, CI. 14880, CI. 61105, and CI. 11005 of the acid, metallizable azo and disperse types are used.

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

This application is a continuation-in-part of copending applications Ser. No. 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-inpart of copending application Ser. No. 723,991, filed Mar. 26, 1958 (now US. Patent No. 2,971,864), 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 cleaning, the atmosphere, or other color destroying agents. The crocking of dyed fabrics (i.e., the undesirable property by which coloring matterrubs off 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 synthetic textile fibers, especially those which are relatively hydrophobic and which are thus resistant to swelling in the aqueous dyebaths normally employed. Dyestuffs 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, ditficult 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 difficulties discussed above. The invention can be particularly described as a process for coloring non-siliceous textile fibers which comprises contacting said fibers with (1) an aqueous solution of an organo- ,silicon compound selected from the group consisting of 3,504,998 Patented Apr. 7, 1970 (A) water soluble reaction products of water and a polyaminoalkylsilane of the formula where x is an integer from 0 to 1 inclusive, each R is an alkyl radical of less than 4 carbon atoms, R is an aliphatic hydrocarbon radical containing a number of carbon atoms selected from the group consisting of l 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 attachedto R by a carbon-nitrogen bond and is composed of carbon, nitrogen, and hydrogen atoms and contains at least two amine groups, the ratio of carbon atoms to nitrogen atoms in the substituent RZ being less than 6:1, and R" is a monovalent hydrocarbon radical free of aliphatic unsaturation, and (B) water soluble acid salts of (A), and (2) a textile dyestuff.

The described process is applied to all non-siliceous textile fibers (i.e., both natural and synthetic fibers, other than siliceous fibers such as glass fibers). 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 benefitted 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 the hydrophobic synthetic organic textile fibers. The term hydrophobic is not necessarily used herein the limited sense that some special chemical treatment has been given to the fibers to render them unusually water repellent, 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 acrylic (at least 85% acrylonitrile units), modacrylic (at least 35% but less than 85% acrylontrile 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 of 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 p. 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 metalcoated plastic. Any metal used in the commercial metallic yarns is suitable here, but aluminum is preferred.

Any textile dyestulf can be used in the present invention. The term dyestuff 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 develo ing 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, indarnine, 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 dyestuffs are the azo(N N), thio(C -S), nitroso(N=O) and azoxy 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(CH )2 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 (SOgH) 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 (e.g. 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 waterinsoluble product. The metal can be added before the dyestutf (bottom-chrome method), with the dyestuff (methachrome or chromate process) or after the dyestulf (top, or afterchrome process). C.I. Mordant Yellow 1 (14025), 01. 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. (C.I. stands for the Color Index classification of the Society of Dyers and Colourists of Bradford, England.) The five digit number appearing in parentheses behind the names of the dyestuffs 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 premetallized" acid dyes in which the metal is already complexed with the organic dye molecule, as for example in C1. 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 dyestuff is formed right in the fiber it is known as an azo 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 in 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 CI. 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 groups which can be reduced with an agent such as sodium hydrosulfite to C-OH groups. The reduced form is known as the leuco form, and is soluble in caustic soda solutions, forming CONa 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 So ution 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 substituents 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 carr-ies 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 C1. 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 notedpreviously, the term dyestufi 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 oryellow, titania, zinc oxide, indomaroon, and lithosol yellow. Blends of difierent 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 dyestuif, the dye stuif 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 dyestutf 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 dyestufis themselves are conventionally applied as a part of the dyeing process. Some dyestuifs 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 water soluble reaction products of water and the defined polyaminoalkylsilanes, and the acid salts of such reaction products, are fully described in the aforementioned patent applications Nos. 753,115 and 753,153, the disclosures of which are hereby incorporated by reference. The reaction products in question can be prepared by intimately mixing water with one or more of the polyaminoalkylsilanes in any proportions, although preferably the amount of water is at least equivalent to 50 molar percent of the (OR) groups present in the silane. (One molecule of water is equivalent to two (OR) groups.) For convenience in mixing or for shipping or storage purposes, from 50 to 200 percent of the equivalent amount of water may be used initially to form a master batch. The resulting reaction product will then ordinarily be further diluted With water, before application to the textile fibers, until the solution has an organosilicon concentration of from about 0.1 to 5.0 percent, and preferably from 0.3 to 2.0 percent, by weight. This concentration will generally provide the 0.2 to 0.8 percent pickup of organosilicon compound which is referred for most fibers. Alternatively the silane can be mixed with sufficient water, in one step, to form a solution of the desired concentration for the fiber treatment. In either case, it is often desirable to incorporate a water miscible solvent (such as the lower aliphatic alcohols, dioxane, or tetrahydrofuran) into the mixture as an aid in speeding the attainment of a homogeneous system. An alcohol corresponding to the (OR) group in the silane will of course be formed from the hydrolysis which takes place during the mixing operation.

Although it is known that hydrolysis takes place when the defined silanes are mixed with water, and that some polymers and/or c-opolymers of siloxane units are formed at the time, it is felt that it is not practical to define the hydrolyzate by reference to its formula. Some, but probably not all, of the (OR) groups are converted to siliconbonded (OH) groups. Some but not all of the latter then condense to form siloxane linkages. Thus the aqueous solution employed undoubtedly contains the full range of possible types of polymeric siloxanes in equilibrium with one another and with the various monomeric silanols and alkoxysilanols possible from such a system. In other words, the reaction product can contain polymers or c0- polymers of units such as R"(Z R)SiO, (Z R)SiO (Z,,R')Si(OH)O, and (Z R)Si(OR)O alone or in any combination, as well as unreacted monomers and partially reacted monomers such as R(Z R')Si(OH) (OR),

Such a product can be said to be one in which the polymeric units and monomeric components both fall within the formula where x is an integer of from 0 to 1 inclusive, 2 is an integer of from 0 to 3 inclusive, x+z is from 0 to 3 inclusive, and Y represents (OH) and/or (0R) groups. However, it is not presently possible to analyze the aqueous solution to determine how much of the (OH) and (OR) groups present in the solution are silicon bonded, or to determine how many of the silanols have condensed to form siloxane linkages. Hence the only practical definition of this material is as a reaction product of the reactants which form it, and it is immaterial what amounts or ratios of the undetermined constituents are present so long as the product is water soluble.

The acid salts which can be employed herein can be prepared by contacting either the aqueous solution of the reaction product referred to above or the silane itself 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, ropanoic, and lactic acids. The salts are generally used only 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 the polyaminoalkyl silanes which are employed to form the above discussed reaction products with water, each R can be any alkyl radical of less than 4 carbon atoms, i.e. methyl, ethyl, propyl and isopropyl radicals. The R radicals can be the same or different. 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 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 silanes.

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 cycloaliphatic radicals such as cyclohexyl. Methyl, ethyl, and phenyl are most preferred.

The polyaminoalkylsilanes can be produced by reacting a polyamine with a halogenohydrocarbonalkoxysilane where each halogen atom is on a carbon atom at least gamma to the silicon atom. Alternatively, they can be p pared by reacting the polyamine with an alpha-halogenohydrocarbon alkoxysilane. 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-1,6-diaminohexane, N,N dimethylhexamethylenediamine, cadaverine, piperazine, dl-l,2-propanediamine, methylhydrazine, 1- aminoguanidine, 2-pyraz0line, benzenetriamine, benzenepentamine, benzylhydrazine, N methyl-p-phenylenediamine, N,N-dimethyl-p-phenylenediamine, and 3-o-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, 1-chloro-2-rnethylbutene-2, S-bromo-pentadiene- 1,3, 16-bromo-2,6-dimethylhexadecene-2, and the like. The halogenohydrocarbons can contain more than one halogen atom, as in 3,4-dibromobutene-1 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 halohydrocarbonalkoxysilane. This is the method employed when R in the above formula is a methylene radical.

The radical (R'Z 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 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 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 dyestuff, 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 dyestulf 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 dyestutf 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 U.S. Patents 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.

The following examples are illustrative only. The symbols Me, Et and Ph have been used to represent methyl, ethyl and phenyl radicals respectively. The monomeric silanes employed in these examples Were obtained as illustrated by the following preparations. HSiCl and allyl chloride were reacted in the presence of chloroplatinic acid to produce ClCH CH CH SiCl The latter was reacted with methanol to produce the corresponding chloropropyltrimethoxysilane, which was in turn reacted with ethylenediamine at reflux temperature to produce B.P. 140.5 C. at 15 mm. Hg pressure. By using the same technique, but starting with MeHSiCl there was produced (MeO) MeSi(CH NI-ICH CH NH B.P. 150 to 152 C. at 25 mm. Hg, n 1.4500, d 0.9675. Using the same technique, but starting with methallyl chloride and MeHSiCl there was produced the compound MeO MeSiCH CHMeCH NHCH CI-I NH which was flash distilled at about C. at 15 mm. Hg, 11 1.4497, d., 0.958, neutral equivalent 112 (theory Unless otherwise indicated, all parts and percentages in the following examples are by weight.

EXAMPLE 1 Aqueous solutions were prepared by mixing 1 part of (MeO) Si (CH NHCH CH NH (MeO) S1 (CH NHCH CH N (CH CH CN) 2 (MeO) MeSi(CH NHCH CH NH or (MeO) MeSiCH CHMeCH NHCH CH NH respectively with 99 parts water. A number of test pieces of undyed Orlon, Dacron, nylon, acetate, cotton, silk, wool, and viscose were each padded with one of the solutions by dipping into the solution and running the wet fabric through squeeze rollers. The pick up of organosilicon compound was about 0.5% 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 225 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) (50420), Calcocid Fast Light Orange 2G (C.I. Acid Orange (16230), Erio Anthracene Blue 4 GL (C.I. Acid Blue 23) (61125), Gycolan Dark Green BL (01. 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 (0.1. Acid Red 7) (14895), Cibalan Yellow GL (C.I. Acid Yellow 114), Cibalan Orange RLW (Cl. Acid Orange 86), Cibalan Brown 2 RL (C.I. Acid Brown 45 Cibalan Bordeaux GRL (C.I. Acid Red 213, Calcofast Brown MF (Cl. 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, 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 (Cl. Direct Orange 34) (40215/20), Chlorantine Fast Red 5 BRL (C.I. Direct Red (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, 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, parts water, and 0.5 part Tergitol TMN were padded onto the organosilicon 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 IR, Black BG, and Brilliant Red 3 B; the Remazol dye s 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 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, 1.22 parts of one of the organosilicon compounds of Example 1, and 100 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.

EXAMPLE 3 (EtO)2EtSi(CH2)aNHCH;GHzNH2, (EtO)2PhSi(CHz) NHCHzCHQNHz (MeO) SiCH2CH2OHNHCHzCH2NH2, (Me0) siCH NHCflHlNMe CHZNHOHQCHENHZ (MeOhSi(CH2) NH(CH2)sNH2, (MeO) Si(OH2)sNHCaH (NH1)z (MeO) Si(CH2)aNMc(CH2)aNHMe is substituted for the organosilicon compounds employed in Example 1 in the fabric treatment and dyeing processes of that example, comparable results are obtained.

EXAMPLE 4 The aqueous solutions of organosilicon compounds in Example 1 were mixed with acetic, 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 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 0.5 part of one of the organosilicon compounds of Example 1 and 94.5 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 Grey K (RB Aridye Yellow N, (RB 93), Aridye Yellow K (A.A.T.C.C. designation 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 pick up 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.

That which is claimed is:

1. In a process for coloring textile fibers selected from the group consisting of nylon, polyacrylonitrile, dihydric alcoholterephthalic acid polyester, polyvinylidene chloride, polyvinylidene dinitrile, cellulose acetate, polyvinylchloride 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 an organosilicon compound which is the reaction product of water and a polyaminoalkylsilane of the formula where each R represents an alkyl radical of less than 4 carbon atoms, and then drying said fibers.

2. In a process for coloring textile fibers selected from the group consisting of nylon, polyacrylonitrile, dihydric alcoholterephthalic acid polyester, polyvinylidene chloride, polyvinylidene dinitrile, cellulose acetate, polyvinylchloride 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 an organosilicon compound which is the reaction product of water and a polyaminoalkylsilane of the formula where each R represents an alkyl radical of less than 4 carbon atoms, and then drying said fibers.

3. A process for coloring textile fibers selected from the group consisting of nylon, polyacrylonitrile, dihydric alcoholterephthalic acid polyester, polyvinylidene chloride, polyvinylidene dinitrile, cellulose acetate, polyvinylchloride and polyolefin fibers, which comprises contacting said fibers with a mixture consisting essentially of (1) an aqueous solution of an organosilicon compound which is the water soluble reaction product of water and a polyaminoalkylsilane of the formula where each R represents an alkyl radical of less than 4 carbon atoms, and

(2) a water dispersible textile dyestuff, and drying said 4. A process for coloring textile fibers selected from the group consisting of nylon, polyacrylonitrile, dihydric alcoholterephthalic acid polyester, polyvinylidene chloride, polyvinylidene dinitrile, cellulose acetate, polyvinylchloride and polyolefin fibers, which comprises contacting said fibers with a mixture consisting essentially of (1) an aqueous solution of an organosilicon compound which is the water soluble reaction product of water and a polyaminoalkylsilane of the formula (RO) (CH )Si(CH NHCHgCH NH where each R represents an alkyl radical of less than 4 carbon atoms, and

(2) a water dispersible textile dyestulf, and drying said 5. A polyaminoalkylsilane having the formula (MeO Si (CH NHCH CH N (CH CH CN) 2 where Me represents a methyl radical.

6. In a process for coloring textile fibers selected from the group consisting of natural cellulosic, natural proteinaceous, synthetic linear polyamide, polyacrylonitrile, a dihydric alcohol-terephthalic acid polyester, polyvinyl chloride and a polyolefin 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 an organosilicon compound which is the reaction product of water and a polyaminoalkylsilane of the formula (RO) Si(CH NHCH CH NH where R represents an alkyl radical with less than 4 carbon atoms, and then drying said fibers.

7. A process for coloring textile fibers selected from the group consisting of natural cellulosic, natural proteinaceous, synthetic linear polyamide, polyacrylonitrile dihydric alcohol-terephthalic acid polyester, polyvinyl chloride and polyolefin fibers, which comprises contacting said fibers with a mixture consisting essentially of (1) an aqueous solution of an organosilicon compound which is the Water soluble reaction product of water and a polyaminoalkylsilane of the formula (R0) Si(CH NHCH CH NH where each R represents an alkyl radical of less than 4 carbon atoms, and

(2) a water dispersible textile dyestuif, and drying said fibers.

References Cited UNITED STATES PATENTS OTHER REFERENCES Book of A.S.T.M. Standards, 1961, pp. 10 and 67-69.

1962 Technical Manual of the American Association of Textile Chemists and Colorists, pub. 1963, pp. B21 and B-32 to B-36.

Textile World, vol. 109, No. 7, 1959, pp. 43-44.

DONALD LEVY, Primary Examiner US. Cl. X.-R.