US3741721A - After-fixing dyes with monoaminoalkylsilicones with aminoalkyl chainshaving 3 carbon atoms - Google Patents

Abstract

IN A PROCESS FOR IMPROVING THE FASTNESS OF DYEINGS AND PRINTS ON PREVIOUSLY DYED AND PRINTED PRINTED SUBSTRATA SUCH SUBSTRATA HAVING BEEN DYED AND PRINTED WITH WATERSOLUBLE DIRECT DYESTUFFS, THE IMPROVEMENT THAT COMPRISES AFTER-TREATING THE SUBSTRATE TO DEPOSIT THEREON A COATING OF A DYE-FIXATIVE SELECTED FROM THE GROUP CONSISTNG OF AMINOALKYL SILICONES AND METAL COORDINATED COMPLEXES OF THE SAME SELECTED FROM THE GROUP CONSISTING OF MONOMERIC AMINOALKYLSILANES, AMINOALKYPOLYSILOXANES, COPOLYMERS OF AMINOALKYPOLYSILOXANES WITH AT LEAST ONE OTHER POLYSILOXANE, BLADE OF AMINOALKYLPOLYSILOXANES WITH AT LEAST ONE OTHER POLYSILOXANE AND METAL COORDINAED COMPLEXES OF SUCH AMINOALKUL SILICONES, SUCH AMINOALKYL SILICONE COLORING ASSISTANT CONTAINING AT LEAST ONE AMINO SUBSTITUENT WHEREIN THE NITROGEN ATOM OF THE AMINO GROUP IS CONNECTED TO A SILICON ATOM OF THE SILICONE DIRECRLY THROUGH A DIVALENT HYDROCARBON RADICAL AND THE AMINO NITROGEN IS SEPARATED BY AT LEAST THREE CARBON ATOMS FROM THE SILICON ATOM.

Description

United States Patent lint. Cl. 1106p 5/02 U.S. Cl. 8-74 18 Claims ABSTRACT OF THE DISCLOSURE In a process for improving the fastness of dyeings and prints on previously dyed and printed printed substrata such substrata having been dyed and printed with watersoluble direct dyestuffs, the improvement that comprises after-treating the substrate to deposit thereon a coating of a dye-fixative selected from the group consisting of aminoalkyl silicones and metal coordinated complexes of the same selected from the group consisting of monomeric 'aminoalkylsilanes, aminoalkylpolysiloxanes, copolymers of aminoalkylpolysiloxanes with at least one other polysiloxane, blends of aminoalkylpolysiloxanes with at least one other polysiloxane and metal coordinated complexes of such aminoalkyl silicones, such aminoalkyl silicone coloring assistant containing at least one amino substituent wherein the nitrogen atom of the amino group is connected to a silicon atom of the silicone directly through a divalent hydrocarbon radical and the amino nitrogen is separated by at least three carbon atoms from the silicon atom.

This is a continuation of application Ser. No. 804,882, filed Apr. 8, 1959 now Pat. No. 3,572,833.

The present invention relates, in general, to the chemistry of coloring, and involves the provision of improved processes for fixing colors on previously dyed or printed substrata of various types including, for example, fibrous textile products, leather goods, and the like. More particularly, the invention is concerned with both process and product improvements resulting, in part, from my discovery that aminoalkyl silicon compounds and coordinated metal complexes of these compounds constitute a unique class of dye-fixatives which can be used in the aftertreatment of numerous substrate materials of both natural and synthetic origin to promote enhanced overall fastness, and, notably, washfastness or insolubilization, of substantive dyestuffs contained thereon. The processes of the invention find specific application in the production of washfast substantive colors on cellulosic substrate materials of all types.

In general, the two most important properties of a dyestuff are its substantivity and overall fastness to removal and modification. The substantivity of a dyestufi enables it to be exhausted from a dye bath or printing medium and transferred in uniform manner to a substrate undergoing coloring, whereas, once the dyestulf has been deposited on the substrate, it is expected to remain thereon and not change to any appreciable extent in intensity or shade under influence of factors such as wash solutions, perspiration, rain, ironing, light, atmospheric contaminants, etc., or, in sort, it must possess good fastness. Under ordinary circumstances, i.e., in the absence of any form of aftertreatment, the substantive dyestufi molecule is held to the substrate by the same forces or mechanism which enabled it to be deposited or exhausted from the dye bath, and it is frequently found that these forces are inadequate to counteract the re-solution tendency of the dyestutf when the colored substate is placed in aqueous solution or aqueous soap and alkaline solutions. That is ice to say, the equilibrium of the system, water-dyestuff-substrate, is initially upset or destroyed by the attracting forces acting between the substrate and dyestulf molecule during the dyeing or printing cycle, and it is obvious that new conditions of equilibrium can set in when the colored substrate is again placed in aqueous solution, particularly in the presence of catalytic influences such as heat, soaps, alkaline agents, etc. In order to insure that a soluble dyestulf (or the soluble derivative of an insoluble dyestuff) will not be released to solution under these conditions, or, in essence, to enhance the normal natural aflinity of the dyestuff for the substrate and thereby promote improved equilibrium for the substrate-dyestulf system, it is often necessary or desirable, particularly with dyestuffs of the substantive classes, or when working with a coloring agent having insuflicient natural afiinity for a particular substrate material, to subject the dyed or printed substrate to an aftertreatment with a suitable dyefixing agent.

Heretofore, a great many different types of dye-fixatives have been developed and employed to varying extents by the textile and allied coloring industries. By way of illustration, formaldehyde, its urea and melamine monomers, cationic softening agents and heavy metal salts have been shown to be effective in minimizing the bleeding of most textile substrates dyed with direct colors, whereas the washfastness of certain acetate dyeings can be enhanced through use of similar agents. In addition, it has been established that the washfastness of direct dyeings and prints on rayon substrate materials are generally improved through finishing treatments with metallic salts, such as zinc, magnesium or aluminum acetate, by use of cationic softening agents, and by use of cationic resinous copper complexes. Other cationic resinous complexes, such as the polyanthrenes, are used to produce washfast colors on viscose substrata dyed with direct dyes, and, under certain conditions, these agents are reportedly capable of promoting some improvement in the lightfastness of the direct colors.

While it is recognized that a great variety of dye-fixing agents have been developed heretofore, the most common forms of aftertreatment presently employed by industry to promote increased fastness of pre-dyed substrates include, finishing techniques involving use of the formaldehyde-type dye-fixatives; aftertreatments with metallic salts such as copper and chrome salts, or resinous copper complexes such as copper coordinated base resins consisting of condensates of diethylene triamine, triethylene tetramine, or tetraethylene pentamine with dicyandiamine; and, for amino-containing dye-stuffs, the application of conventional diazotization and coupling mechanisms.

Since the fastness to light of a dyed substrate involves a photochemical reaction which is largely dependent on the constitution of the dyestuff molecule, per se, as distinguished from the dyestuff-substrate system involved in the mechanism of washfastness, improvement in the former property is not ordinarily sought by colorists through application of separate aftertreatment techniques. On the other hand, it commonly occurs that certain forms of conventional dye-fixatives intended for application to previously dyed substrate materials to induce improved washfastness of substantive colors, will actually decrease the normal lightfastness characteristics of the dyestulf molecule. In a similar manner, other commonly used dyefixing agents result in appreciable shade changes or changes in the intensity of coloration of previously dyed substrata, such that the colorists must regulate the dyeing or printing cycle to provide for these changes.

The diazotization and coupling type of fastness treatment is based on the ability of the dyestuff molecule to react with aromatic compounds containing activating groups, and, as such, is restricted in its applications to dyestuffs which contain at least one free primary ammo group. The aftertreatment techniques involving use of copper salts have been found to be effective chiefly for increasing fastness of the dyestuff to light, whereas, the chromium salt-type of aftertreatment increases fastness to washings, but, in both instances, these types of dye-fixing agent produce considerable change in the original shade of dyed substrata. In the case of the formaldehyde fixatives, the chief objection to use of these agents stems from the characteristic formaldehyde odors which they impart to the dyed materials, and, in the same manner, the commonly used amino resin dye-fixatives produce objectionable fishy amine odors, and are not readily compatible for use with other textile processing chemicals.

In contrast to the foregoing, I have found that the aminoalkyl silicones and their coordinated metal complexes are extremely effective dyefixing agents, functioning, even at relatively low concentrations, to insolubilize substantive dyestuffs contained on virtually any substrate material, and serving to prevent bleeding, leaching, and washing-out of the dyestuffs under the most severe conditions or criteria of washfastness. The dye-fixatives of the invention are entirely compatible with most other textile processing chemicals, free of objectionable odors, capable of effecting fixation with substantially less shade changes than are customarily encountered through use of conventional dye-fixing agents, and further capable of imparting improved storage stability and greater durability to dyed substrata treated in accordance with the general processing techniques of my invention.

Owing to their general physical properties, the aminoalkyl silicone dye-furatives can be applied as a Wet processing operation as, for example, by exhaustion, following the usual dyeing or printing cycle, or they can be applied from aqueous media as a finish on the dyed and dried substrata. The actual choice of procedures in this connection will depend upon a number of factors peculiar to existing plant installations and conventions, and to the particular characteristics of the dyestuff and substrate involved, including, by way of illustration, the physical nature and form of the substrate, the recommended processing techniques normally required for most efficient utilization of the dyestuff, such as post-drying cycles, etc., and the presence or absence of auxiliaries or other finishing agents within the overall dyeing and finishing operations. While most dyeing or printing and finishing operations can be suitably modified to permit application of either type of aftertreatment, it is found to be most convenient to apply the dye-fixatives by Wet processing techniques immediately following the normal dyeing or printing cycle.

In actual practice of the invention, I prefer to apply the aminoalkyl silicone dye-fixatives to colored substrate materials by a simple immersion operation within a suitable aqueous solution of the aminoalkyl silicone, but it is entirely possible, and practical, to accomplish the req uisite loading by spraying or padding techniques or any other means normally used by industry. If necessary or desirable, the aminoalkyl silicone can be solubilized beyond its normal solubility in pure aqueous solutions through use of acid, neutral or alkaline reagents, or emulsions of the dye-fixatives can be employed with entirely satisfactory results. Enhanced solubilization of the aminoalkyl silicone dye-fixatives may also be effected by salt formation, or by direct chemical modification of the base compounds to introduce solubilizing groups, such as by hydroxy ethylation, and the like. Virtually any solvent system which is substantially non-reactive with the aminoalkyl silicones can be employed to promote more uniform distribution or dispersion of the dye-fixative onto the dyed or printed substrate materials. In addition, most of the commercially available wetting agents normally in use within the dyeing and finishing industries can be employed to further promote enhanced dispersion of the silicones.

Among the specific solvents which have been employed with success in the practice of the invention are included the aliphatic oxygen-containing compounds such as the akanols and the ether alcohols, such as ethanol, propanol, isopropanol, methoxyethanol, ethoxyethanol, and the like. In addition, monobasic acids such as formic, acetic and propionic acids are excellent solubilizing agents for the aminoalkyl silicone dye-fixatives. Included as monobasic acids, such as, lactic acid, gluconic acid, glycolic acid, other hydroxy carboxylic acids are suitable for use as solubilizing agents and provide improved fixing properties. Other carboxylic acids, such as, diglycolic acid, can be used. Mineral acids may also be employed as may the standard aromatic hydrocarbon solvents such as benzene, toluene, xylene, and the like, but these solubilizing agents are not as preferred for general use as are the simple aqueous systems or the aqueous-alcoholic and monobasic acid-modified solvent systems. Lastly, the dye-fixatives may also be deposited from aqueous alkaline solutions. In actual practice, I have found that an aqueous system comprised of from about 40 to 60 parts water and from about 40 to 60 parts of an organic alcohol such as ethanol or isopropanol, and containing approximately five percent (5%) by volume of a monobasic acid such as acetic acid, provides an excellent medium for solubilizing and dispersing the aminoalkyl silicone dye-fixatives onto virtually any dyed or printed substrate material.

The concentration of the aminoalkyl silicone dyefixatives contained within the aftertreatment solutions is found to be relatively non-critical from the standpoint of establishing good fastness properties for the substantive colors on various types of substrata. Thus, for example, as established by the experimental data presented hereinafter, a decrease in solution concentration from an initial value of 5% by Weight of aminoalkyl silicone solids to 1% by weight, representing a decrease of from 3.0% to 0.6% by weight of silicone solids actually deposited from solution onto a previously direct-dyed textile material, produced little or no change in the washfastness properties of the respective end-products. While the concentration of the dye-fixatives can be varied anyhwere within the range of from 0.1 to 5.0% by weight, or higher, based on deposited silicone solids, it is found that for most substantive dyestuffs good dye-fixing properties can be produced at deposited solids concentrations within the range of from 0.1 to 2.0% by weight, whereas concentrations of the order of from 0.1 to 1.0% by weight are actually highly effective for many of the substantive dyestuffs. Ordinarily, the solution concentration of the aminoalkyl silicone solids is regulated in accordance with the percentage wet pick-up characteristics for the particular dyed or printed substrate material undergoing dye-fixing, which is dependent, in turn, on the relative hydrophilic or hydrophobic nature of the various substrate materials. That is to say, by suitably adjusting the solution concentration in accordance with the wet pick-up characteristics for a particular substrate undergoing treatment, it is relatively simple to adjust the aftertreatment solution to an optimum concentration of silicone solids for the dyestuffsubstrate system involved. These factors are well known to experienced dyers and finishers who must adjust the relative concentrations of most known auxiliaries and finishing agents to meet the exigencies of many varied coloring and finishing operations, and, accordingly, it is not believed to be necessary to comment further on such variables for purposes of this disclosure.

In the dye-fixing processes of the invention, it is desirable to effect forced drying of the aminoalkyl silicone deposits by heating the substrate material at an elevated temperature after it has been removed from the aftertreatment solution, or is otherwise processed to deposit the desired dye-fixative thereon, although simple air-dried substrata have also been dye-fixed to provide good washfastness properties. It is believed that such drying of the dyed or printed and aftertreated substrate materials at elevated temperatures efiectively cures the deposited silicone to the substrate, or, more concisely, the deposit is fixed or bonded to the substrate by the heating operation. In this connection, it should be stated that the exact mechanism or mechanisms of the dye-fixing phenomena of my invention are not fully understood, although it is believed that the aminoalkyl silicones form insoluble complexes with the dyestulf molecules and/ or bonding of the dyestuff to the substrate material. It is assumed, however, that the mechanism involves something more than simple surface coating, and that at least limited penetration, absorption, or depth of reaction, so to speak, occurs between the substrate-dyestuff system and the aminoalkyl silicone dye-fixatives. It should be understood, therefore, that the references to deposits" or coatings or applications as used herein and in the appended claims, having reference to the aminoalkyl silicone aftertreatments, are not to be construed as limitations to a simple surface or physical phenomenon.

Drying and curing of the aminoalkyl silicone deposits can be effected at room temperature over protracted periods or by heating the treated substrate materials at higher temperatures for relatively shorter periods of time. Actually, time and temperature are inversely related in the curing mechanism, such that it is entirely possible to eifect fiash cures within a matter of seconds, provided the particular substrate material will withstand the higher temperatures required for such cures. In actual practice, however, I prefer to operate at curing temperatures within the range of from ZOO-350 F., over periods ranging anywhere from a few minutes to one-half hour, dependent on the particular wet pick-up characteristics of the colored substrate undergoing dye-fixing. When the dyefixing operation is effected by wet processing following the dyeing or printing cycle, the necessary drying and curing operations are advantageously effected as an incident to the normal heating cycles required for the dyeing or printing processes, but the heat treatment can be practiced as a separate step following completion of the normal dyeing or printing process.

Quite naturally, by reason of the fastness problems peculiar to such dyeings and printings, the processes of the invention find particular commercial application in the aftertreatment of cellulosic substrata dyed with substantive dyestuffs. The dyeings or prints which may be subjected to the aftertreatment of the invention may be contained on any fibrous material, however, including single filaments, yarns or fabrics and textiles from either staple or continuous fibers. Suitable common textile materials and natural fibrous materials include substrata such as cotton, linen, ramie, hemp, jute, wood pulp, paper, leather, furs, feathers, cellulose ethers, cellulose esters, e.g., cellulose acetate and cellulose, regenerated cellulose rayons produced by any process, e.g., viscose, cuprammonium, etc., natural silks, tussore silk, wool, and the like. In general, the dye-fixatives of the invention may be employed to increase the fastness of any soluble dyestuff wherever used in accordance with current coloring practices.

Apart from the foregoing conventional fixing applications, however, the processes of the invention may also be applied to effect enhanced fixation of dyestuffs on a great many other types of substrata which are colored through use of coloring agents having relatively inferior natural aifinity for the substrate involved. For example, in my copending, US. application Ser. No. 804,870, filed on Apr. 8, 1959, I have described and claimed processes which are based on the unique color-affinity, for pigments of both natural and synthetic origin as well as anionic dyestuffs, that can be impartedthrough pre-treatment with, and/or concurrent use within the coloring media of the aminoalkyl silicon compounds-- to solid and fibrous substrata including, among others:

(1) materials of normally good substantivity or afiinity for conventional coloring agents, such as natural fibrous substrata and monofilaments derived from animal and vegetable fibers, and semisynthetic fibers from natural raw materials; whereby enhanced use of at least some of the existing coloring agents for these materials can be realized, as well as wider use of certain other coloring agents which have heretofore found only limited acceptance in connection with the coloring of these substrata; and

(2) normally difiicultly colorable substrate materials, including (A) natural fibrous materials such as leather and asbestos fibers; (B) natural solid substrates including inorganic oxides in pulverulent or laminate forms such as silica, titania, quartz, mica, diataomaceous earth, siliceous sands and gravels etc., and metallic substrata containing similar spontaneously-formed insoluble oxide surface layers; (C) semisynthetic fibrous materials including glass fibers and aluminum silicate fibers; (D)

. synthetic fibrous substrata, monofilaments and continuous yarns from fibers such as the polyamides, polyacrylonitriles, polyacrylonitriles modified with vinyl acetate, copolymers of acrylonitrile and vinyl chloride, copolymers of vinyl chloride and vinyl acetate, polymers of tetrafluoroethylene, the polyester fibers, and polyethylene fibers; and (E) mixed or blended fibrous substrata produced by spinning combinations of selected natural, semisynthetic, and synthetic fibers from among the above-enumerated fibrous materials; whereby enhanced coloration of such substrata can be effected by relatively simple techniques and through use of a great variety of coloring agents which are presently viewed as being substantially nonsubstantive or non-affinitative towards these materials.

Whereas the processes and compositions of my copending application are operative for purposes of promoting initial coloration of such substrate materials by pretreatment with, or concurrent use during the coloring cycle, of the aminoalkyl silicones in their capacity as coloring assistants, the after-treatment processes of my present invention may be applied to promote enhanced preservation or fastness of such dyeings and printings through use of the aminoalkyl silicones in their capacity as after-treating dye-fixatives. That is to say, it should be apparent that one could effect a primary coloring operation with a substantive dyestuif according to the principles of my copending application, and thereafter promote enhanced fixation of the dyestuif to the substrate material by aftertreatment of the substrate in accordance with the processing techniques of my present invention. In a similar manner, the processes of the present invention may be employed to promote dye-fixing of coloring agents deposited on the foregoing types of substrata by any means, wherein the resulting dyed or printed substrate might exhibit generally inferior fastness properties.

As a result of a relatively extensive screening of the known aminoalkyl silicones, it has been demonstrated that virtually all stable members of this series, as well as their coordinated metal complexes, can be employed as dye-fixatives according to the processing techniques of my invention, although, unexplainably, certain of these compounds and compositions and their corresponding metallic derivatives do exhibit somewhat superior fixing properties towards most of the substantive dyestuffs, as compared with certain other members of the series. It is essential, only, that the dye-fixatives contain at least one grouping of the formulation:

wherein the divalent R-linkage between the silicon atom and amino nitrogen atom preferably constitutes a linear or cyclic hydrocarbon chain of three (3) or more carbon atoms chain-length, on which the amino nitrogen is substituted no closer than the third carbon atom removed from silicon as, for example, a polymethylene chain of three or more carbon atoms, or a para-substituted cpyridyl radical, and the like. The divalent R-linkage may be unsubstituted or carry additional hyrocarbon substituents along its length. The free valences of the amino nitrogen may both be substituted with hydrogen atoms in primary amine fashion, or as imine (secondary) or nitrile (tertiary) structures carrying organic groups. Illustrative of the organic groups which can satisfy the free valences of the amino nitrogen are the simple alkyl radicals or substituted alkyl groups, particularly those groups which contain carbon, hydrogen and oxygen atoms or carbon hydrogen and nitrogen atoms or carbon hydrogen, nitrogen and oxygen atoms as for example, aminoalkyl, polyaminoalkyl, hydroxyalkyl, alkoxyalkyl, polyalkoxyalkyl, cyanoalkyl, carboakoxyalkyl or carboxyalkyl radicals, and/or aryl substituents such as phenyl or pyrrolidyl radicals, or fused aromatic ring structures such as naphthlene, and the like. Alternatively, the nitrogen atom may be symmetrically substituted in bis-imine or tris-nitrile fashion by means of other polymethylenesilylidyne groupings [-(CH SlE]. The free valences of the one or more silicon atoms may be satisfied with mixed alkoxy and alkyl or aryl substituents where monomeric silanes are involved, or with Si-- linkages and aryl and alkyl radicals in the case of aminoalkylpolysiloxanes or copolymers of aminoalkylpolysiloxanes with other polysiloxanes. In essence, therefore, illustrative functional grouping required in the dye-fixatives of the invention can be represented in general by the following formula:

wherein R is a substituted or unsubstituted hydrocarbon group of at least 3 carbon atoms chain-length; R and R" represent members selected from the group consisting of hydrogen, alkyl, aminoalkyl, cyanoalkyl, hydroxyalkyl, carboalkoxyalkyl, carboxyalkyl, and aryl radicals, and the monovalent grouping:

X is a member selected from the group consisting of alkoxy and siloxylidyne radicals [ESiO-]; and Y and Z are members selected from the group consisting of alkoxy, alkyl and aryl radicals.

As indicated above, the necessary functional aminoalkyl silicon grouping of the dry-fixatives of my invention may be contained within a monomeric aminoalkylalkoxysilane, an aminoalkylpolysiloxane, or a copolymer or simple blend or mixture of an aminoalkylpolysiloxane with one or more other siloxanes. It is not essential that these materials be employed in pure form but crude hydrolyzates or aqueous and aqueous-alcoholic solutions of the silicones can be employed directly to introduce the aminoalkyl silicon groups onto the dyed or printed substrate materials.

Aminoalkylalkoxysilanes which can be employed in practicing my invention can be represented in general by the following formula:

wherein R, R and R" have the same meanings as previously assigned above; X is an alkoxy radical; Y is a member selected from the group consisting of alkyl and aryl radicals; b is zero or a whole number of from 1 to 2; and the sum of c-i-b is not greater than 3 and preferably not greater than 2.

The following specific silanes are illustrative of some of the aminoalkylsilyl-functional derivatives included (III) among the class of compounds defined within Formula 11 above:

beta-methyl-gamma-aminopropyltriethoxysilane gamma-aminopropyltriethoxysilane gamma-aminopropyltripropoxysilane gamma-aminopropylmethyldiethoxysilane gamma-aminopropylethyldiethoxysilane gamma-aminopropylphenyldiethoxysilane delta-aminobutyltriethoxysilane delta-aminobutylmethyldiethoxysilane delta-aminobutylphenyldiethoxysilane gamma-aminoisobutylmethyldiethoxysilane gamma-aminobutyltriethoxysilane gamma-aminobutylmethyldiethoxysilane N-beta-carbethoxyethyl-gamma-aminopropyltriethoxysilane N-gamma-aminopropyl-delta-aminobutylmethyldiethoxysilane N-gamma-aminopropyl-gamma-aminopropyltriethoxysilane N-beta-aminoethyl-gamma-aminopropyltrimethoxysilane N-beta-cyanoethyl-delta-aminobutyltriethoxysilane N-gamma-triethoxysilylpropyl-pyrrolidine N-gamma-tricthoxysilylpropyl-Z,S-dimethyl-pyrrolidine N-phenyl-N-methyl-gamma-aminopropyltriethoxysilane N-phenyl-N-methyl-delta-aminobutyltriethoxysilane N-methyl-beta-methyl-gamma-aminopropyltriethoxysilane bis(gamma-triethoxysilylpropyl)imine bis (beta-methyltriethoxysilylpropyl) imine N,N-dimethyl-gamma-aminopropyltriethoxysilane N-naphthyl-N-methyl-gamma-aminopropyltriethoxysilane N-(furfuryl)-gamma-aminopropyltriethoxysilane, etc.

Aminoalkylalkoxysilanes of the foregoing type and methods for producing compounds of this structure, in general, are described and claimed in US. 2,832,754 issued on Apr. 29, 1958. In addition, those silanes which contain two amino nitrogen atoms can be prepared by the reaction of a diamine with the appropriate chloroalkylalkoxysilane.

The alkoxysilylalkylamines, -imines, -nitriles are generally characterized by their ability to form stable solutions with aqueous admixtures of organic compounds, which is a particularly desirable property from the standpoint of existing practices employed in the textile finishing industries. When placed in aqueous solution, the alkoxy groups hydrolyze at a slow rate such that the silane monomers are eventually converted to water-soluble aminoalkylpolysiloxanes. Aqueous admixtures of such polysiloxanes with water-soluble organic compounds conform to most requirements of stability encountered in the textile coloring and finishing industries.

The aminoalkylpolysiloxanes which can be employed to carry the desired functional group represented by Formula I above for purposes of my invention, may be linear, cyclic or cross-linked in nature. The aminoalkylpolysiloxanes of the cross-linked variety are readily produced by the hydrolysis and condensation of the trialkoxy-substituted silylalkylamines, -imines or -nitriles, and can contain small amounts of silicon-bonded hydroxyl groups or silicon-bonded alkoxy groups depending on the conditions under which polymerization is conducted. For example, aminoalkylpolysiloxanes of this type which are essentially free of residual silicon-bonded alkoxy or hydroxyl groups can be produced by the complete hydrolysis and total condensation of an aminoalkyltrialkoxysilane, whereas polymers containing predominant proportions of residual alkoxy groups can be produced by the partial hydrolysis and total condensation of the same starting silane. In a similar manner, polymers containing predominant proportions of residual silicon-bonded hydroxyl groups can be produced by essentially complete hydrolysis and only partial condensation of the trifunctional silane starting materials. Polysiloxanes of the foregoing types may be represented in general by the following unit structural formula:

wherein R, R and R" have the same meaning as previously assigned above; Z represents hydroxyl and alkoxy groups; and d has an average value of from to 2, and preferably from 0 to 1. Typical polymers from among the compounds of this class include, gamma-aminopropylpolysiloxane, delta-aminobutylpolysiloxane, etc., and related hydroxyland alkoxy-containing hydrolyzates and condensates of these polymers.

Aminoalkylpolysiloxanes of the cyclic and linear varieties may be produced readily by the hydrolysis and condensation of dialkoxyalkylor dialkoxyarylsilylalkylamines, -imines, and -nitriles. These polymers may be represented in general by the following structural formula:

1 IR-E liO lit/I n wherein R, R and R" have the same meanings as previously assigned above; Y is an alkyl or aryl radical; and n is an integer having a value of at least 3, with average values of from 3-7 for the cyclic polysiloxanes, and higher for the linear polysiloxanes. Typical cyclic polymers from among this class include the cyclic tetramers of gammaaminopropylmethylpolysiloxane and delta-aminobutylmethylpolysiloxane, and the like. The linear polymers may be structures of the type of gamma-aminopropylmethylpolysiloxane, gamma aminopropylethylpolysiloxane, delta-aminobutylmethylpolysiloxane, gamma-aminobutylmethylpolysiloxane, and the like. The linear aminoalkylpolysiloxanes further include alkyl, alkoxy and hydroxyl end-blocked materials which contain from 1 to 3 such groups bonded to the terminal silicon atoms of the molecules comprising the polymeric chains. For example, linear polymers such as monoethoxy end-blocked gammaaminopropylethylpolysiloxane, methyldiethoxysilyl endblocked delta aminobutylmethylpolysiloxane, monoethoxydimethylsilyl end-blocked gamma-aminopropylphenylpolysiloxane, and the like, may be employed to impart the desired functional groups to a dyed or printed substrate. ,These end-blocked polymers may be readily produced by the equilibration of cyclic aminoalkylpolysiloxanes with silicon compounds containing predominant silicon-bonded alkoxy groups, or by the cohydrolysis and condensation of trialkylalkoxysilanes with aminoalkylalkyldiethoxysilanes or aminoalkylaryldiethoxysilanes. The hydroxyl end-blocked polymers can be prepared, also, by heating linear or cyclic aminoalkylpolysiloxanes with water.

The copolymeric polysiloxanes which can be employed as dye-fixatives in accordance with my invention may contain siloxane units consisting of any of the typical siloxyalkylamine, -imine or -nitrile groups depicted above, in combination with one or more other hydrocarbon-substituted siloxane units of any desired configuration, as represented in general by the formula:

(VI) we wherein W and W are hydrocarbon radicals; and e is an integer having a value of from O to 2. These copolymers may be produced by the cohydrolysis and condensation of typical aminoalkyl silanes with other hydrocarbonsubstituted silanes, or by the direct equilibration of separate polymeric starting materials. The linear copolymers can also contain chain-terminating or end-blocking groups such as alkyl, hydroxyl and alkoxy radicals. The Various polymeric and copolymeric materials of the types discussed hereinbefore, as well as processes for producing these materials, have also been described in substantial detail and claimed in the aforementioned copending applications.

As indicated hereinbefore, the aminoalkyl silicone dyefixatives may also be employed in the form of their metal coordinated complexes with metallic components of the type of copper, chromium, cobalt, etc. Of primary interest are the copper complexes of the base resins and monomeric silanes, which may be prepared by simple aqueous reaction of the silicones with water-soluble copper derivatives such as cupric chloride, acetate or sulfate, or waterdispersible or insoluble copper derivatives such as the hydroxide, stearate and the like. It has been postulated, heretofore, that copper is capable of forming a bridge between the dyestuff molecule and the dye-fixing agent, with a resulting tendency to stabilize the dyestuff towards fading with light. In general, the aminoalkyl silicone dyefixatives of the invention can be supplied in the form of the base resins for direct use as aftertreatment agents, or they can be supplied in pre-complexed form, or combined with the complexing copper derivative at the time of use to form copper coordinated complexes, in situ, Within the aftertreatment bath.

While all of the aminoalkyl silicones seemingly are operative for purposes of promoting washfastness of dyestufis on the various substrata described, I have found that certain compounds and compositions appear to approach a more universal dye-fixing status from the standpoint of the numerous different types of dyestufis and substrata customarily employed by the dyeing and finishing industries. The specific compounds and compositions listed below have been found to be particularly efficient as dyefixatives of the universal type:

(A) Homopolymer of delta-aminobutylmethylpolysiloxane and copper coordinated complexes thereof;

(B) N-beta-cyanoethyl-delta-aminobutylmethylpolysiloxane; and

(C) Crude hydrolyzates of delta-aminobutylmethylpolysiloxane.

Still other compounds and compositions of unique performance characteristics have been identified within the detailed experimental data presented hereinafter.

It is believed that my invention may be best understood by reference to the following specific examples which illustrate the foregoing principles and procedures as applied to the dye-fixing, on Warious types of substrate material, of different classes of dyestuffs by means of a plurality of typical different aminoalkyl silicones and coordinated metal complexes of the aminoalkyl silicones. For the sake of convenience and brevity, the various noncomplexed aminoalkyl silicones which were employed as dye-fixatives within the experimental work reported in the examples, as consolidated in tabulated form in Table I below, and number-coded for ease of reference in the actual text of the examples.

TABLE I Dye fixatives numetal code designation Compound or composition and and

TABLE IContinued tives nu- Compound or composition meral code designalion 9 Homopolymer of delta-aminobutylmethylpolysiloxane.

10 Copolymoric silicone oil comprised of 75% trimethylsiloxy end-blocked dimothylsiloxano and 25% of delta-aminobutylmothylsiloxy groups.

11 Copolymcric silicone oil comprised of gamma-ammopropyltriethoxysilane and vinyltriethoxysilane (25% resin solids).

12 Copolymeric silicone oil comprised of gamma-aminopropyltrlethoxysilane and amyltriethoxysilane (30% resins solids).

13 Cobrg; Sholate of gamma-armnopropyltriethoxysilane (17% 14 Copolymeric silicone oil comprised of 83.3% trimethylsiloxy end-blocked dimethylsiloxane and 16.7% gamma-aminopropylsiloxy groups.

15 Gammo-aminopropylpolysiloxane; the homopolymer from gamma-aminopropyltriethoxysilano (50% solids in ethanol).

16 N-naphthyl-ga1nma-aminopropyltriethoxysilano.

17 Copolymer comprised of 50% trimethylsiloxy end-blocked dimethylsiloxane and 50% dclta-aminobutylmethylsiloxy groups.

18 Copolymer comprised of 70% trimethylsiloxy end-blocked dimethylsiloxane and 30% N,N-bis(beta-hydroxyethyl)- delta-aminobutylmothylsiloxy groups.

19 Copolymer comprised of 27% trimethylsiloxy end-blocked dimethylsiloxane, 40% diphenylsiloxy groups, and 33% delta-aminobutylmethylsiloxy groups.

20 Copolymcr comprised of 68.5% trimethylsiloxy end-blocked dimethylsiloxano, diphenylsiloxy groups, and 6.5% dclta-amiuobutylmcthylsiloxy groups.

21 N-gamma-tricthoxysilypropylpyrrolideno hydrochloride.

. N-bota-cyanoethyl-dclta-aminobutyltriethoxysilane.

23 NaNddimothyl-garnma-aminopropyltriethoxysilane hydrolo- 24 Beta-methyl-gamme aminopropyltrlethoxysilane.

25 Bis-(beta-methyltrietho xysilylpropyDimine.

26 N-methyl-beta-mcthyl-gamma-ami nopropyltriethoxysilane.

27.-. N-beta-carbcthoxyethy1gamma-aminopropyltriethoxysilano.

28.-- N-beta-cyanoethyl-dclta-aminobutyhnethylpolysiloxane (mainly cyolics) 20. N-(beta-Iuriuryl)-gamma-aminopropyltriethoxysilane.

30- Delta-aminobutylmcthyldiethoxysilano.

31.. Dolta-ominobutylmothylpolysiloxano (crude product otherwise comparable to 9 above; made by non-solvent hydrolysis of 30).

32 Same as 31 except made by solvent hydrolysis.

33 Delta-aminobutyhncthylpolysiloxane incompletely condensed and thus probably containing silicon-bonded ethoxy or hydroxyl groups (60% solids in ethanol).

34 Aminomethyltriethoxysilanc.

35. N-l eta-aminoethyl-gannna-aminopropyltriethoxysrlane.

36 Copolymer comprised of 60% trimethylsiloxy end-blocked dimethylsiloxane and 40% N-betaaminoethyl-gammaaminoisobutylmethylsiloxy groups.

37 N, III-bis(beta-hydroxypropyl)-garnma-aminopropylpolys1 oxane.

38 N, N-bis(beta-hydroxystearyl)-gamma-aminoisobutylmethyldiethoxysilane.

39 N-oetyl-gamma-aminoisoloutylmothyldiethoxysilane.

EXAMPLE I Cotton Substrate: Direct Dyestuif Swatches of white, kier-boiled and bleached cotton sheeting were dyed with a dye having a Color Index number of 29225, a direct dyestufii, in a dye bath consisting of 1% of the dyestuff and a volumezfa bric ratio of 40:1, at 180 F. The swatches were dyed for 20 minutes after which time 15% sodium chloride on fabric weight was added to increase exhaustion. The dyeing was then continued for 15-20 minutes more, and the dyed swatches were thereafter removed from the dye bath and rinsed with water.

The dyed cotton swatches were individually placed in 1% solids solutions of aminoalkyl silicone dye-fixatives Nos. 1, 4, 8, 9 and 10 (Table I), containing 1% acetic acid and a 50/50 mixture of water and isopropanol, at room temperature. After stirring in these solutions for 15 minutes, the swatches were removed, rinsed in cold water and dried for five minutes at 250 F. After drying, a white piece of cotton was stapled onto each of the dyed and silicone-treated swatches. These specimens were then individually immersed in water (160 F.), stirred for one hour, removed, rinsed, and finally dried. The color removal on the cloth, the color of the wash liquor, and the degree of transfer of color to the white swatch were noted for each of the treated swatches and closely compared to a dyed swatch which was not aftertreated with a dye-fixing agent. In all cases, the aminoalkyl silicone dye-fixatives had appreciably improved the fastness of the dyestuif as determined by all three test properties. The respective dye-fixatives were rated in order of increasing improvement in washfastness as follows:

Untreated Control-Poorest Dye-Fixative No. 1 Dye-Fixative No. 4 Dye-Fixative No. 9 Dye-Fixativc No. 10 Dye-Fixative No. 8Best EXAMPLE II Viscose 'Rayon Substrate: Direct Dyestuffs Five (5) viscose rayon fabrics which had previously been dyed in a mill with a red, a turquoise, a navy blue, a brown and a copper brown direct dyes, were each finished with aminoalkyl silicone dye-fixatives Nos. 1, 3, 4, 8, 9, 10, 11 and 12 to improve the washfastness of the dyes. In these finishings, a 5% solution of each dye-fixative was made in a 50 water-isopropanol mixture containing 5% acetic acid. The swatches of dyed viscose were padded with each dye-fixing solution at 65% wet pick-up, and then dried for 5 minutes at 320 F.

After the drying operation, the washfastness of the dyes was determined in accordance with the same test procedures described in Example I. A swatch of each dyed fabric that had not been with a dye-fixative was also tested for comaprison. Again, on all five dyed fabrics, all of the dye-fixatives tested improved the washfastness of the dyestulf in the following approximate orders of effectiveness, from poorest to best. The numerical designations of the various dye-fixatives correspond to their listing in Table I.

Rayon Substrate: Direct Dyestuifs (A) Dye-fixatives Nos. 1, 8, 9 and 10, and a leading commercial dye-fixing agent consisting of a copper coordinated metal complex of an amine resin, were each applied to a navy blue and a brown direct-dyed rayon fabric at various concentrations. In this series of tests, the commercial dye-fixative was dissolved in water. The aminoalkyl silicone dye-fixatives were dissolved in a 50/ 50 mixture of isopropanol and water containing 1% by weight of acetic acid. Swatches of the dyed fabrics were padded through the solutions at wet pickup and dried for 10 minutes at 300 F. The concentrations of dye-fixatives employed were as follows:

Solution concentration: Deposited on cloth, percent The treated swatches of fabrics were stapled to a white piece of cotton and were individually immersed in beakers of water at 160 F. They were then held, with periodic stirring, at 160 F. for one hour, removed, rinsed and finally pressed dried. The color of each water extract was again noted, as was the transfer of color to the white cotton bleeder.

At these reduced concentrations, aminoalkyl silicone dye-fixative No. 9, at all concentration levels and on both dyed fabrics, produced substantially better dye-fixing effects than the commercial dye-fixative. The commercial dye-fixative produced the next best results, and was closely followed by dye-fixatives Nos. 10, 8 and 1, in that order of etficiency.

(B) A further type of dye-fixing application was performed involving use of dye-fixative No. 9 in a typical resin finishing bath containing conventional wrinkle-proofing and stabilizing resins. Two different types of resin finishing mixes were employed, and a direct-dyed navy blue rayon fabric was used for the tests. The following compositions were evaluated:

10% urea-formaldehyde resin (50%) 1% 2-amino-2-rnethyl-l-propanol hydrochloride (30% solution) (catalyst) 1% dye-fixative No. 9

10% urea-formaldehyde resin (50%) 1% 2-amino-2-methyl-l-propanol hydrochloride (30% solution) (catalyst) 1% commercial dye-fixative (copper complex of amine resin) 10% urea-formaldehyde resin (50%) 1% 2-amino-2-methyl-l-propanol hydrochloride (30% solution) (catalyst) No dye-fixing agent 30% urea-formaldehyde paste resin (60%) 1.5% 2-amino-2-methyl1-propanol hydrochloride (30% solution) (catalyst) 1% dye-fixative No. 9

30% urea-formaldehyde paste resin (60%) 1.5 2-amino-2-methyl-l-propanol hydrochloride (30% solution) (catalyst) 1% commercial dye-fixative (copper complex of amine resin) 30% urea-formaldehyde paste resin (60%) 1.5% 2-amino-2-methyl-l-propanol hydrochloride (30% solution) (catalyst) No dye-fixing agent Untreated dyed fabric In preparing the foregoing solutions, dye-fixative No. 9 was employed in solution form containing 10 parts of the aminoalkyl silicone, 1 part acetic acid and 89 parts of a 50/50 water-isopropanol mixture. The rayon fabric swatches were padded at 60% wet pick-up and cured for 5 minutes at 320 C. The dye-fixing properties were then evaluated by the procedures described in the preceding examples.

It was found that the finishing resins alone produced only a very slight dye-fixing efifect. Aminoalkyl silicone dye-fixative No. 9 and the commercial dye-fixative produced approximately equal dye-fixing, but No. 9 was better than the commercial agent in resin mixes l and 2 above, whereas with resin mixes 4 and 5, the commercial dye-fixative was slightly superior.

These tests demonstrate that the aminoalkyl silicone dye-fixatives are compatible with standard thermosetting 14 finishes such that they may be applied both in the dyeing operation and in the finishing stages.

EXAMPLE IV Rayon Substrate: Direct Dyestuff with Copper Coordinated Complexes Several copper coordinated complexes of aminoalkyl silicone dye-fixative No. 9 were prepared on the basis of the following formulations:

Complex Complex Complex Components 9-A 9-B 9 C Moles of dye fixative No. 9 l. 0 1. 0 0. 5 Moles of Ouch-21110 1.0 0. 5 1. n

respective pH values:

pH with Complex pH alone acetic acid With no acid, all three complexes gave cloudy solutions, whereas with the acid, all solutions were clear and blue.

All six of the complex solutions were padded onto the dyed fabrics at 60% wet pick-up so as to deposit 0.6% solids of the complex. The swatches of cloth were then dried for 10 minutes at 300 F. The dye fixing properties were evaluated by the procedures described in the preceding examples. In all cases superb dye-fixation was obtained. The three acid solutions appeared to show equal performance for all three of the copper-silicone complexes. In the non-acidified samples, complex 9A showed slightly inferior fixing action, but this complex also gave the most cloudy solution ad coarse dispersion.

EXAMPLE V Rayon Substrate: Direct Dyestuff with Cobalt Chelate Dye-fixative No. 13, consisting of a cobalt chelate of gamrna-aminopropyltriethoxysilane (17% in H O), was applied to a brown and navy blue direct-dyed rayon substrate at 1% pad solids concentration and 60% wet pickup, followed by drying for 10 minutes at 300 F. and testing by the usual procedures. On the brown fabric, this dye-fixative gave excellent dye-fixation, whereas on the navy-dyed fabric, the dye-fixing properties were somewhat less eflicient.

EXAMPLE VI Viscose Rayon Challis: Direct Dyestuffs In an effort to further evaluate the dye-fixing properties of dye-fixative No. 9 as compared with those of a leading commercial amine resin dye-fixative, a direct dyestuff having a Color Index number of 29225 was selected for laboratory dyeings on viscose rayon challis. In the actual dyeings, the dye bath contained 2% dye on the weight of the cloth samples. The fabriczbath ratio was 30.1. The dyestuff was pasted with small amounts of a sodium alkyl sulfate wetting agent and water to full volume. The samples of fabrics were wet and then placed in the dye bath. The bath temperature was then raised to 180 F. gradually. After 15 minutes of dyeing, 7.5% of Glaubers Salt on fabric weight was added to the dye bath. Dyeing was continued for 15 more minutes, 7.5 additional Glaubers Salt was added, followed by 15 minutes more dyeing at 180 F. The samples were then removed from the dye bath, rinsed in cold water and dried.

The following treatments were applied to each of the above dyed fabrics for dyefixing tests:

(A) Control-none;

(B) 0.5% of dye-fixative No. 9, plus 1% acetic acid in water;

(C) 0.5% of commercial dye-fixative in water.

The samples were padded at 60% wet pick-up to deposit 0.3% dye-fixing agent based on the weight of the cloth. They were then dried and cured for 10 minutes at 300 F.

Dye bleeding and staining tests were made as previously described and rated on the basis of the following schedule:

Rating of 4=heavy dye bleeding and staining Rating of 3=medium dye bleeding and staining Rating of 2=light dye bleeding and staining Rating of 1=minor dye bleeding and staining Rating of =no bleeding and no staining The results of these dye-fixing studies are presented in tabulated form in Table II below, based on the foregoing rating scale. These results establish that with the particular dyestuff used, dye-fixative No. 9 is superior to the commercial dye-fixative in preventing bleeding of the dye in water at 160 F., and in preventing staining of white fabrics.

TABLE II [Comparison of aminoalkyl silicone dye fixative No. 9 and commercial agent in dye fixing of direct dyed rayon substrata] Dye bleeding and staining ratings Viscose Gabardine: Direct dyestuifs with chromium coordinated complexes A series of chrome metal coordinated complexes were prepared using arninoalkyl silicone dye-fixatives Nos. 9 and 10. These modified dye-fixatives were prepared as water solutions or pastes containing 20% solids complexes based on the following formulations:

Complex designation: Composition 9-A 1 mole CrCl to 1 mole dye-fixative No. 9

9-B' 1 mole CrCl to 2 moles dye-fixative No. 9

9-C' 1 mole CrCl to 3 moles dye-fixative No. 9

10-A 1 mole CrCl to 1-NH EQ. in dye-fixative 10-B 1 mole CrCl to 2-NH EQ. in dye-fixative l0-C 1 mole CrCl to 3-NH EQ. in dye-fixative With dye-fixative No. 9, the chromic chloride was dissolved separately in water, and then the aminoalkyl silicone was added with stirring. Heat was evolved. The solutions were cooled with stirring and bottled. The complexed dye-fixatives Nos. 9-A', 9-B', and 9-0 were dark opaque green liquids. On dilution with water, all samples gave cloudy dispersions. On adding acetic acid, all formed clear dark green solutions.

In the case of the dye-fixative No. 10 complexes, the chromic chloride was also dissolved separately in water, and the aminoalkyl silicone was dissolved in isopropanol and then added to the salt solution. In all cases, heat was evolved on mixing. Complexed dye-fixative No. 10-A was a dark green solution, whereas Nos. 10-B and 10-0 16 were dark green dispersions. All formed cloudy dispersions on dilution with water which cleared by the addition of acetic acid.

The foregoing metal complexes were comparatively tested on a scarlet direct-dyed viscose gabardine cloth which is normally finished with a commercial amine resin type of dye-fixative. The latter agent was also tested along with an untreated control. Comparisons were made at 0.5% solids concentration in padding solution. As an additional control, a sample was also treated with dyefixative No. 9 alone.

The treatments were conducted as described in the preceding examples from aqueous solutions containing 1% acetic acid, followed by drying and curing at 300 F. for 10 minutes. The bleeding tests were run at F.

The results of these tests are presented in tabulated form in Table III below, based on the dye-fixing scale of Example VI. These data show that the 0.5% chrome complexes of dye-fixative No. 9 in the padding bath gave about the same results as 0.5 of No. 9 alone and 0.5% of the commercial dye-fixative. At the 0.5 concentration, the chrome complexes of dye-fixative No. 10 were not as effective. Significantly, however, whereas the commercial fixative changed the initial shade of this dyestuif from scarlet red to a deep blue maroon color, all of the other samples retained the original dye shade.

TABLE III Comparative dye-fixing with chrome complexes of dyefixatives Nos. 9 and 10, dye-fixative No. 9 alone and commercial amine resin dye-fixative Scale of bleeding and staining Lw-hOOOOO-P EXAMPLE VIII Rayon Substrata: Direct dyestuffs under severe washing conditions and lightfastness tests (A) The degree of washfastness of direct-dyed fabrics after-treated with dye-fixing agents is evaluated by a large number of procedures depending upon the particular performance characteristics required for the finished products. For example, some fabrics need only possess resistance to cold water bleeding, whereas others must have resistance to hot wateror hot soap washes. In general, the best overall fastness is obtained on rayons when the dyefixing agents are combined with thermosetting resins. Furthermore, the concentrations of dye-fixatives used by a textile plant generally rise as the degree of fastness is increased. Since the aminoalkyl silicone dye-fixative No. 9 and its metal coordinated complexes are extremely eflicient at relatively low concentrations for both cold and hot water bleeding, testswere conducted to evaluate these products from the standpoint of required concentrations under more drastic washing conditions.

In a first series of tests, three direct-dyed rayon fabrics were treated with the following formulations from aqueous solutions:

1% dye-fixative No. 9+1% acetic acid 1% diye-fixative No. 9-C (copper complex)+1% acetic act 1% dye-fixative No. 9-B' (chrome complex)+1% acetic acid 1% dye-fixative No. 17+1% acetic acid 1% commercial amine resin dye-fixative Untreated control 17 The treatments were conducted as described in the preceding examples. After curing, the samples were tested by a modified AATCC No. 2 wash test using 0.5% of a commercial soap flake product at 120 C. for 30 minutes followed by two rinses at 105 F. and flat bed pressing.

A second series of dye-fixatives was prepared using 3% solids of the various dye-fixing formulations listed above. These samples were tested in soap solution by a different test procedure at 140 F.

A third series of samples of the 3% paddings was given the No. 3 AATCC wash test using 0.5% soap and 0.5 sodium carbonate for 45 minutes at 160 F. The results of these tests are all presented in tabulated form in Table IV below on the basis of the rating scale of Example VI.

In the evaluation of these results it was very difiicult to give ratings comparable with the commercial dye-fixative because of the very difierent shades produced. Moreover, bleeding evaluations could not be employed as such since in these soap solutions, the white cotton test piece was initially colored, but the color was then removed by the soap wash. Evaluation ratings were arrived at by examining the amount of color removed and by the stain left on the White cotton bleeders. As an overall result of these testings, it can be concluded that dye-fixatives Nos. 9 and 17 yield performance characteristics similar to or better than the commercial dye-fixative.

TABLE IV [Comparative dye-fixing efficiencies of selected aminoalkyl silicone dyefixatives and commercial product under severe washing conditions] Loss of color on washing (B) In an effort to evaluate the effects of the aminoalkyl silicone dye-fixatives on lightfastness properties, the samples of the brown fabric treated with the 1% products in the preceding section were subjected to Fadeometer exposures and examined for fading every 20 hours. The results of these tests are presented in tabulated form in Table V below. With reference to these data, it will be seen that dye-fixatives Nos. 9 and 17 without metals reduced the lightfastness of this particular dyestuff. On the other hand, both the copper and chromium complexes greatly improved resistance to fading. The copper complex of dye-fixative No.9 (9-A) was equivalent to the commercial dye-fixative.

TABLE V [Fadeometer studies on direct dyestufl aftertreated with various dyefixing agents] Fading rating* 40 hours 60 hours 80 hours Dye-fixative employed 20 hours *N N B =No appreciable break-good; SB =Slight break-good; AB Appreciable break-fair.

18 EXAMPLE IX Rayon Substrate: Direct dyestuff with various aminoalkyl silicone dye-fixatives (A) A group of different aminoalkyl silicone dye-fixatives were compared on a single brown rayon direct-dyed fabric using 1% solids in the padding bath at 60% Wet pick-up followed by the usual drying and curing and hot water bleeding tests. The results of these studies are presented in tabulated form in Table VI below based on the rating scale of Example VI. On the basis of 0.6% deposited solids, it was found that dye-fixatives Nos. 18, 19 and 23 (Table I) were the most efficient. Significantly, these covered primary, secondary and tertiary amino groups within the aminoalkyl silicones. The aromatic phenyl and naphthyl amine based silanes (dye-fixatives Nos. 7 and 16, respectively) were relatively ineffective at this concentration.

TABLE VI Dye-fixing efficiency of miscellaneous aminoalkyl silicone dye-fixatives and controls Dye-Fixative: Dye bleeding and staining (B) Additional dye-fixing tests were conducted with dye-fixatives Nos. 9, l0 and 17 at 0.5% pad bath solids concentrations using aqueous solutions containing 1% acetic acid. The padding procedures and tests were conducted as described in the preceding examples. Four different direct dyestuffs were used.

The results of these tests are summarized in tabulated form in Table VII below on the basis of the rating scale of Example VI. The data show that dye-fixative No. 10 is the least effective agent at this concentration, whereas both dye-fixatives Nos. 9 and 17 are superior to the commercial amine resin dye fixative. On the scarlet fabric, for example, while none of the aminoalkyl silicone dye-fixatives produced any change in shade, the commercial dyefixative produced a blue maroon color.

TABLE VII [Dye-fixing efficiency of aminoalkyl silicone dyefixatives Nos. 9, 10 and 17 on direct-dyed rayon fabric at 0.3% deposited solids concentration] (C) Further dye-fixing tests were conducted with dyefixatives Nos. 5, 9, 14 and 15 in which 1% of each product was applied from 1% acetic acid solutions in 5050 water-isopropanol solvent. The results of these studies are 19 presented in tabulated form in Table VIII below on the basis of the rating scale of Example VI.

These results demonstrate the difference in efiiciency between a common monomer and polymer (dye-fixatives Nos. 5 and 15, respectively); the latter showing greatly increased dye-fixing performance. Again, dye-fixative No. 9 gave the best overall performance, however.

TABLE VIII D e-fixin eflicieney i aminoalkyl silicone dye-fixatives Nos. 9 1i and lfi on direct-dyed rayon fabrlc at 0.6% deposited sohds' concentration] Dye bleed- Dye-fixative ing and employed Dyestufi staining None Brown 4 No. 5 .d 3 No. 14. 2 No. 15. 1 No. 0 .do 0

None Turquoise 4 N o. 6 .d 3 1 EXAMPLE X Rayon Fabrics: Direct dyestutf fixed with crude hydrolyzates of aminoalkyl silicones A series of crude hydrolyzates of aminoalkyl silicones were tested for dye-fixing efliciency in the form of the free resins and as copper coordinated complexes. In these tests, the following two groups of treating solutions were prepared in water (all as percentage solids):

GROUP I (1 0.5 dye-fixative No. 9+ 1 acetic acid (2) 0.5% dye-fixative No. 31+1% acetic acid (3) 0.5 dye-fixative No. 32+ 1 acetic acid (4) 0.5 dye-fixative No. 33,+1% acetic acid (5) 0.5 dye-fixative No. 30+ 1 acetive acid (6) 0.5% dye-fixative No. 2+1% acetic acid (7) 0.5% commercial amine resin dye-fixative GROUP II The foregoing aftertreatment solutions were applied to direct-dyed rayon fabric by padding at 60% wet pick-up, and the fabrics were dried for minutes of 300 F. All of the solutions were permitted to age 30 minutes before application to the cloth swatches.

Those fabrics which had been treated with the low concentrations of the plain aminoalkyl silicone dye-'fixatives (Group I above, 1-7) were tested for bleeding and washfastness by immersion for one hour in water at 160 F. containing 0.1% of a sodium alkyl sulfate wetting agent, with periodic stirring. As in the preceding examples, a

20 piece of white cotton fabric was stapled to each dyed sample to determine dye transfer.

Those fabrics which had been treated with the corresponding copper coordinated complexes (Group II above, 5 8-14) were tested for washfastness using a modification of AATCC No. 2 test wherein the dyed samples and a white cotton control are placed in water at 140 F. containing 0.5% of a commercial soap flake product and agitated for 30 minutes.

After each of the above tests, all of the samples were allowed to air dry and then the color loss and transfer to the white fabric were rated on the basis of the rating scale defined in Example VI.

The results of the Group I series of tests (samples l-7) are shown in tabulated form in Table 'IX below. Here at the low concentration and neutral bleeding hot water test, the three crude hydrolyzate-type dye-fixatives were found to be identical in performance to the pure aminoalkyl silicone dye-fixative No. 9, and as good or better than the commercial amine resin dye-fixative. The two monomeric dye-fixatives were somewhat inferior to the polymers and showed varying performance on the four different directdyed fabrics.

The results of the soap wash tests with the Group II series (samples 8-14) have been presented in tabulated form in Table X below. These results show that for higher concentrations of dye-fixatives plus copper chloride, there was very little difference between dye-fixative No. 9 and the three crude hydrolyzates which performed as well or better than the commercial amine resin dyefixative. Here again, the two monomers were inferior to the polymers. As with previous studies, all of the copper containing dye-fixatives produced appreciable shade changes as compared with the pure aminoalkyl silicone products.

TABLE IX Dye fixing efficiency of crude hydrolyzate-type aminoalk l silicone d fixatives and others on direct-dyed rayon fabric (Groiip 1)] ye Dye-fixative Degree of bleeding and staining 4O employed (Samples 1-7) Turquoise Red Copper Brown TABLE X [Dye fixing etliclency of crude hydrolyzate-type, copper-containing Rayon Fabrics: Direct Dyestuifs and Miscellaneous Aminoalkyl Silicone Dye-Fixatives Dye-fixatives Nos. 24, 25, 26, 28, 29, 30 and 34 (Table I) were tested for dye-fixing efiiciency on four direct-dyed rayon fabrics at 1% solution concentration (percent on solids) with 1% acetic acid. In each case, the solutions were padded on the dyed fabrics, and then dried for 10 minutes at 300 F. The 160 F.-one hour hot water bleeding test was employed to evaluate dyefixing efficiency. The results of these studies are set forth in tabulated form in Table XI below on the basis of the rating scale of Example VI. While the samples were difiicult to rate visually because of shade changes during By exhaustion the bleeding tests, all of the dye-fixatives tested did perform with various degrees of dye-fixing efficiency. The most efficient compound was No. 28, whereas, as was to be expected, the aminomethyl compound (No. 34) was most inefiicient.

TABLE XI [Dye fixing efficiency of various aminoalkyl silicone dye fixatives on direct dyed rayon fabric] Degree of bleeding and staining Dye-fixative employed Turquoise Red Copper Brown EXAMPLE XII Cotton and Rayon Fabrics: Difiiculty Fixable Direct Dyestuffs A series of five direct dyestulfs which are known to be difficult to fix were applied to cotton and rayon fabrics and then aftertreated under various conditions with dyefixative No. 9. The dyestuffs involved and the concentration of each are listed below:

2% direct dye having a Color Index number of 24895 3% direct dye having a Color Index number of 28160 2% direct dye having a Color Index number of 29225 3% direct dye having a Color Index number of 22590 2% direct dye having a Color Index number of 741 80 In order to obtain varied data on the performance of the dye-fixative with these dyes, it was applied over a wide range of conditions using a number of different finishing formulations and methods of application. Thus, the dye-fixative was employed in combination with thermosetting finishes :both alone and as the corresponding metal coordinated complexes. It was also applied in reduced concentrations with non-resin mixes to obtain such effects as cold water fastness, hot water fastness, fastness to perspiration, and fastness to wet and dry pressing. The series of treatments listed below were made in each case with all five dyed fabrics:

RAYONS Treatment A Treatment B 1.5% dye-fixative No. 9 1.0% CuCl -2H O 1.0% acetic acid Pad at 80% wet pick-up. Dried and cured 10 min./ 300 F.

Treatment C 1.0% dye-fixative No. 9 1.0% acetic acid Pad at 80% wet pick-up. Dried and cured 10 min/300 F.

Treatment D on fabric weight Treatment B By exhaustion 1.5% dye-fixative No. 9 1.0% CuCl -2-H O u} on fabric weight 1.0% acetic acid Fabric: Bath ratio of 1:10 R.T. to 140 F. in 30 min. Extracted Dried 5 min/250 F.

Treatment F Untreated-Control COTTON Treatment G 20.0% urea-formaldehyde resin (60% 1:1.33 U:F) 1.5% dye-fixative No. 9 1.0% CuCl -2H O 1.0% acetic acid Pad at wet pick-up. Dried and cured 1 0 min/300 F.

Treatment H 10.0% dimethylol ethylene urea 1.5 dye-fixative No. 9 1.0% CrCl -6H O 1.0% acetic acid Pad at 80% wet pick-up. Dried and cured 10 min./ 300 F.

Treatment I 10.0% methylated methylol melamine resin 3.2% MgCl -6H O catalyst (60% solution) 1.5% dye-fixative N0. 9 1.0% acetic acid Pad at 80% wet pick-up.

Dried and cured 10 min/300 F.

Treatment I By exhaustion ZZZ $252232;ijjjjjjjjjj} on fabric Weight Fabric: Bath ratio of 1:10 R.T. to F. in 30 min. Extracted Dried 5 min/250 F.

Treatment K By exhaustion d 1;: g iff ?i on a r welght Fabric: Bath ratio of 1:10 R.T. to 140 F. in 30 mins. Extracted Dried 5 mins./250 F.

Treatment L Untreated-Control All of the 60 samples resulting from the foregoing treatments were tested in the F. hot water bleeding test and the modified AATCC No. 2 test wherein the dyed samples and a white cotton control are placed in water at 140 F. containing 0.5% of a commercial soap flakes product and agitated for 30 minutes. The results of these tests have been presented in tabulated form in Tables XII, XIII, XIV, and XV, below based on the rating scale of Example VI.

For the cotton samples in the hot water bleeding test (Table XII) all treatments were equally effective for all of the dyestuffs. Similar results were found with the rayon fabrics (Table XIV), except for the direct dye having a Color Index Number of 28160 with three of the treatments and the directdye having a Color Index number of 22590 with two of the treatments.

TABLE XII [Ratings after the 160 F. hot water bleeding tests (cotto11)] Degree of bleeding and staining No. No. No. No. No.

Treatment applied None G H I J K TABLE XIII [Ratings after the modified No. 2 soap wash tests (eotton)] Degree of bleeding and staining No. No. No. No. No. Treatment applied None G H J K Dye on cloth (abbreviated):

TABLE XIV [Ratings after the 160 F. hot water bleeding tests (rayon)] Degree of bleeding and staining [Ratings after the modified No. 2 soap wash tests (rayon)] Degree of bleeding and staining No. No. No. No. No.

Treatment applied None A B C D E Dye on cloth (abbreviated):

EXAMPLE XHI Cotton and Rayon Fabrics: Direct Dyestuffs The following four direct dyestuffs were used to dye cotton and rayon fabrics for aftertreatment with aminoalkyl dye-fixative No. 4:

Direct dye having a Color Index of 30145 Direct dye having a Color Index of 29225 Direct dye having a Color Index of 29065 Direct dye having a Color Index of 29125 The nine rayon samples were cut into swatches and treated with the following treatment solutions:

Treatment A 30% urea-formaldehyde resin (60% 121.33 UzF) 1.5% dye-fixative No. 9

1.0% acetic acid 1.0% CuCl -2H O Treatment B 30% urea-formaldehyde paste resin (60% 111.33 UzF) 1.0% acetic acid 1.0% 2-amino-2-methyl-l-propanol hydrochloride (30% solution) (catalyst) Treatment C 30% urea-formaldehyde paste resin (60% 1:1.33 UzF) 2.0% commercial amine resin dye fixative 1.0% 2amino-2-methyl-l-propanol hydrochloride (30% solution) (catalyst) Treatment D None-Control The foregoing treatments were elfected by padding at 94% wet pick-up followed by drying and curing in one operation for 10 minutes at 300 F. The samples were not afterwashed.

The four cotton samples were cut into swatches and treated with the following treatment solutions:

Treatment E 1.5% dye-fixative No. 9 1.0% CuCI -ZI-I O 1.0% acetic acid Treatment F 2.0% dye-fixative No. 9 2.0% acetic acid Treatment G 2.0% commercial amine resin dye-fixative Treatment H None-Control The foregoing treatments were effected by padding at 70% wet pick-up followed by drying for 10 minutes at 300 F. The samples were not afterwashed.

The samples were subject to dye bleeding and washfastness tests as described in the preceding examples. The results of these tests are presented in tabulated form in Tables XVI and XVII below on the basis of the color scale of Example VI.

With reference to the tables, it will be seen that on both the cotton and rayon fabrics, dye-fixative No. 9 produced dye-fixation comparable to that of the commercial dye-fixative. In addition, dye-fixative No. 9 plus CuCl was slightly more effective than higher concentrations without the cupric chloride.

TABLE XVI [Dye bleeding and staining of direct-dyed rayon in modified No. 2 soap wash test] Dye bleeding and staining (A) A series of lightfastness studies was conducted on four direct-dyed rayon fabrics previously used for dyefixing tests. These fabrics were treated with the following difierent agents:

(11) 0.5% dye-fixative No. 9+1% acetic acid (12) 1% commercial amine resin dye-fixative 13) Untreated controls These treatments were effected by padding followed by drying only for five minutes at 250 F. and no afterrinsing. The results of the Fadeometer tests are tabulated in Table XVIII below. By reference to the table, it will be seen that both the commercial dye-fixative and the silicone treatments reduced the lightfastness of all four dyestuffs about equal amounts. Further exposure, however, did not result in further fading.

TABLE XVIII [Lightfastness tests on direct-dyed rayon fabrics treated with aminoalkyl silicone complex and commercial agent] Fadeometer exp0surehours to fade Treatment applied Red Turquoise Copper Brown None-control 40 40 80 80 Dye fixative No. 9/CuCIz 20 20 40 60 Commercial 20 20 40 60+ (B) A further series of lightfastness tests was made on the same brown direct-dyed fabric used above, and treated with the following different agents:

fixing agents] Fadeometer exposure hours to fade,

Treatment applied copper brown Noneeontrol 80 Dye fixative N o. 9 40 Dye fixative No. 9/CuOl2- 60 Dye fixative No. 9/Cr0l; 6O

Dye fixative N o. 17 40+ Commercial 60 EXAMPLE XVI When dye-fixatives of the type of Nos. 35, 36, 37, 38 and 39 are applied to direct-dyed fabrics in the manner described in Example II good washfastness and resistance to bleeding properties are noted.

Having thus described the subject matter of my invention, what it is desired to secure by Letters Patent is:

What is claimed is:

1. In a process for improving the fastness of dyeings and prints on previously dyed and printed substrata such substrata having been dyed and printed with water-soluble direct dyestuffs, the improvement that comprises aftertreating the substrata to deposit thereon a coaing of a dye-fixative selected from the group consisting of aminoalkyl silicones and metal coordinated complexes of the same selected from the group consisting of monomeric aminoalkylsilanes, aminoalkylpolysiloxanes copolymers of aminoalkylpolysiloxanes with at least one other polysiloxane, blends of aminoalkylpolysiloxanes with at least one other polysiloxane and metal coordinated complexes of such aminoalkyl silicones, such aminoalkyl silicone coloring assistant containing one amino substituent wherein the nitrogen atom of the amino group is connected to a silicon atom of the silicone directly through a divalent hydrocarbon radical and the amino nitrogen is separated by at least three carbon atoms from the silicon atom.

2. Process for improving the fastness of dyeings and prints on previously dyed and printed substrata such substrata having been dyed and printed with water-soluble direct dyestufis that comprises aftertreating the substrate to effect deposition thereon of an aminoalkyl silicone dyefixative selected from the group consisting of monomeric aminoalkylsilanes, aminoalkylpolysiloxanes, copolymers of aminoalkylpolysiloxanes with at least one other polysiloxane, blends of aminoalkylpolysiloxanes with at least one other polysiloxane, and metal coordinated complexes of such aminoalkyl silicones, containing at least one functional grouping of the formula:

wherein R is a divalent hydrocarbon linkage of at least three carbon atoms chain-length, in which the amino nitrogen is substituted at least three carbon atoms remove from silicon, R and R represent members selected from the group consisting of hydrogen atoms, alkyl, cyanoalkyl, hydroxyalkyl, carboxyalkyl, carboalkoxyalkyl and aryl radicals, and the monovalent grouping:

X is a member selected from the group consisting of alkoxy and Si-O linked siloxylidyne radicals [-O-SiE];

and Y and Z are members selected from the group consisting of alkoxy, alkyl and aryl radicals; and thereafter subjecting the substrate to a heat treatment at an elevated temperature to effect drying and curing of the dye-fixative thereon.

3. The process as claimed in claim 2 wherein the aminoalkyl silicone dye-fixative is a monomeric silane selected from the group represented by the formula:

wherein R, R and R have the same meanings as defined within claim 2; X is an alkoxy radical; Y is a member selected from the group consisting of alkyl and aryl radicals; b has a value of from 0 to 2; c is a whole number (if value from 1 to 2; and the sum of c-l-b is not greater t an 3.

4. The process as claimed in claim 2 wherein the amino alkyl silicone dye-fixative is a crude hydrolyzate of a monomeric silane selected from the group represented by the formula:

wherein R, R and R" have the same meanings as defined within claim 2; X is an alkoxy radical; Y is a member selected from the group consisting of alkyl and aryl radicals; c is a whole number from 1 to 2; b has a value of from 0 to 2; and the sum of c+b is not greater than 3. 5. The process as claimed in claim 2, wherein the aminoalkyl silicone dye-fixative is an aminoalkylpolysiloxane selected from the group represented by the unit formula:

wherein R, R and R" have the same meanings as defined within claim 2; Z is a member selected from the group consisting of hydroxyl and alkoxy radicals; and d has an average value of from to 2.

6. The process as claimed in claim 2, wherein the aminoalkyl silicone dye-fixative is an aminoalkylpolysiloxane selected from the group represented by the formula:

R Yr, I-R-SiO [1 1.

wherein R, R and R have the same meanings as defined within claim 2; Y is a member selected from the group consisting of alkyl and aryl radicals; and b is an integer having a value from 0 to 2; and at least one other siloxane unit represented by the formula:

wherein W and W are hydrocarbon radicals; and e is an integer having a value of from 0 to 2.

8. The process as claimed in claim 2, wherein the aminoalkyl silicone dye-fixative is a mixture of polysiloxanes containing siloxane units represented by the wherein R, R and R" have the same meanings as defined within claim 2; Y is a member selected from the group consisting of alkyl and aryl radicals; and b is an integer having a value from 0 to 2; and at least one other siloxane unit represented by the formula:

wherein W and W are hydrocarbon radicals; and e is an integer having a value of from 0 to 2.

9. The process as claimed in claim 2, wherein the aminoalkyl silicone dye-fixative is delta-aminobutylmethylsiloxane.

10. The process as claimed in claim 2, wherein the aminoalkyl silicone dye-fixative is a copolymeric siloxane containing trimethylsiloxy end-blocked dimethylsiloxane and delta-aminobutylmethylsiloxy groups.

11. The process as claimed in claim 2, wherein the aminoalkyl silicone dye-fixative is N-beta-cyanoethyldelta-aminobutylmethylpolysiloxane.

12. The process as claimed in claim 2, wherein the aminoalkyl silicone dye-fixative is a crude hydrolyzate of delta-aminobutylmethylpolysiloxane.

13-. The process as claimed in claim 2, wherein the dye-fixative is a copper coordinated complex of an aminoalkyl silicone of the class described.

14. The process as claimed in claim 2, wherein the dye-fixative is a chromium coordinated complex of an aminoalkyl silicone of the class described.

15. The process as claimed in claim 2, wherein said dye-fixative is deposited on the substrate from aqueous solution.

16. The process as claimed in claim 2, wherein said dye-fixative is deposited on the substrate from an alcoholic solution.

17. The process as claimed in claim 2, wherein said dye-fixative is deposited on the substrate from an aqueous solution containing a monobasic organic acid.

18. The process as claimed in claim 2, wherein said dye-fixative is deposited on the substrate from a solution consisting of approximately equal parts of water and isopropanol and containing a small amount of acetic acid.

References Cited UNITED STATES PATENTS DONA-LD LEVY, Primary Examiner US. Cl. X.R. 8-165 UljIITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 741, 721 Dated Ju e 26, 1973 11Qmenick D Ga li- It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

The term of this pate t subsque t. to December 8, 1987, has

bee disclaimed.

Signed and Scaled this Twenty-eighth Day Of September 1976 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner nj'larems and Trademarks