US3429650A - Including finishing agents in at least one of two mutually immiscible solutions containing coreactants and serially applying said solutions to fibrous materials - Google Patents

Description

United States Patent INCLUDING FINISHING AGENTS IN AT LEAST ONE OF TWO MUTUALLY IMMISCIBLE SO- LUTIONS CONTAINING COREACTANTS AND SERIALLY APPLYING SAID SOLUTIONS TO FIBROUS MATERIALS William L. Wasley, Berkeley, and Robert E. Whitfield and Lowell A. Miller, Walnut Creek, Calif., assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Filed May 29, 1962, Ser. No. 198,653

The portion of the term of the patent subsequent to Feb. 19, 1980, has been disclaimed US. Cl. 8-115.6 19 Claims Int. Cl. D06m 13/54 A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates in general to finishing of textiles. The objects of the invention include novel processes of applying finishing agents to textiles and other fibrous materials. Further objects of the invention will be obvious from the following description wherein parts and percentages are by weight unless otherwise specified.

In the processing of textiles it is conventional practice to apply finishing agents to impart a desired property or characteristic to the textile. For example, the textile may be impregnated with an insecticide such as dieldrin so that the fabric will be resistant to attack by insects. Other finishing agents may be applied to enhance the waterrepellancy or oil-repellancy of the fabric, to increase its resistance to becoming soiled, to make it resistant to attack by fungi, to render it softer, to give it a desired color or luster, to provide it with a specified odor, etc. Ordinarily, these finishing agents are applied by a system which involves dispersing the agent in a volatile liquid carrier, immersing the fabric in the resulting dispersion and then drying the fabric to evaporate the volatile carrier and leave the finishing agent on the fabric. Such techniques have the disadvantage that the treatment is only temporary. When the fabric is subjected to laundering or dry-cleaning, the finishing agent is removed so that if the same quality is desired in the cleaned fabric, the finishing agent must be re-applied. This is a very common practice; for example, with raincoats where the waterrepellant finishing agent must be renewed each time that the garment is dry-cleaned.

In the copending application of Miller, Whitfield, and Wasley, Ser. No. 98,718, filed Mar. 27, 1961, now Patent No. 3,078,138, granted Feb. 19, 1963, there are disclosed processes for shrinkproofing wool wherein a condensation polymertypically a polyamideis formed in situ on the wool fibers and grafted to the wool, that is, chemically combined therewith. In a typical embodiment of the process, a wool fabric is serially impregnated with two solutions-one being a solution of a diamine in water, the other being a solution of a diacid cholride in a waterimmiscible, volatile, inert solvent. By such treatment the fibers are coated with superposed layers of the mutuallyinsoluble solutions, for example, an inner layer of diamine in water and an outer layer of diacid chloride in water-immiscible solvent. Under these conditions the diamine and diacid chloride react almost instantaneously at the interface between the phases, producing in situ on the fibers a high-molecular weight, resinous polyamide which coats the fibers and renders the fabric shrinkproof without detriment to the hand, porosity, and other valuable properties of the fabric. Moreover, the polyamide is chemically bonded to the wool so that the shrinkproof- 3,429,650 Patented Feb. 25, 1969 ing effect is highly durable, i.e., the polyamide deposit is not removed by repeated washing of the treated fabric in conventional soap and water or detergent and waterlaundering formulations, or in conventional dry-cleaning formulations. From a procedural standpoint, the process has the advantage of simplicity and rapidity in that the basic operation is simply a serial impregnation of the fabric in the two solutions. Another point is that the process does not require any heat curing of the treated fabric as is commonly necessary in most resin shrinkproofing procedures.

It has now been found that the interfacial polymerization system described above can be adapted for applying finishing agents of many kinds to textiles. In accordance with the present invention, finishing agents are applied to textiles by a procedure which locks the agent to the textile fiber so that the quality imparted to the textile by the selected agent is durable in that the textile can be repeatedly laundered or dry-cleaned without removal of the finishing agent. Accordingly, a primary object of the present invention is the provision of processes whereby textiles may be provided with durable finishes. This object is attained by a process which involves forming, under interfacial polymerization conditions, an organic condensation polymer in situ on the fibers of the textiles while providing a textile finishing agent at the locus where the interfacial polymerization takes place. As a result of such procedure, the finishing agent is entrapped or enmeshed in the polymer as it is formed and is thus securely locked to the fibers of the textile. In a typical embodiment of the invention, a wool textile is first impregnated with an aqueous solution of hexamethylene diamine. Then the textile is impregnated with a solution containing sebacoyl chloride and dieldrin in a water-immiscible solvent, such as toluene. By such treatment the fibers are coated with superposed layers of the mutuallyinsoluble solutions. Under these conditions the diamine and the diacid chloride (sebacoyl chloride) react almost instantaneously at the interface between the two phases, producing in situ on the fibers a high molecular weight, resinous polyamide which is chemically bonded to the fibers and which enmeshes the dieldrin. The net result is that the treated fabric is not only shrinkproof but it is resistant to attack by moths. Moreover, these qualities are durable in that the treated fabric can be subjected to dry-cleaning or washing in aqueous media and still retain its characteristics of being shrinkproof and resistant to insect attack.

The invention is of wide applicability and can be employed for fixing finishing agents of all kinds to textiles. Typical examples of such agents are: antiseptics, antistatic agents, agents for imparting fireor flame-resistance, insecticides, insect repellents, lubricants, textile conditioners or softeners, odorants, deodorants, pigments or other coloring agents, sizing agents, oil repellents, water repellents, soil repellents, and the like. Agents to perform such functions are well known in the art and form no part of the present invention. Nevertheless, examples of particular materials which may be applied to achieve desired qualities in the treated fabric are provided below merely by way of illustration and not limitation.

Agents for imparting resistance to flame or fire.-Sodium borophosphate, ammonium sulphamate, chlorinated diphenyl, chlorinated paraffin, the bromoform adduct of triallyl phosphate, etc.

Antiseptics, that is, agents which impart to the textile resistance against attack by mildew, fungi, bacteria, or other forms of microorganisms.Beta naphthol, o-phenylphenol, 2,4,5-trichlorophenol, 2-bromo-4-phenylphenol, tetrachlorophenol, pentachlorophenol, 4-chloro-2-phenylphenol, 6-chloro-2-phenylphenol, sodium o-phenylphenate, sodium 2,4,5-trichlorophenate, sodium tetrachlorophenate,

sodium pentachlorophenate, lauryl pyridinium chloride, 2,2 dihydroxy-S,5'-dichloro-diphenylmethane, salicylanilide, quaternary ammonium compounds such as dodecyl dimethyl benzyl ammonium chloride, sodium dimethyl dithiocarbamate, lauryl amine salt of tetrachlorophenol, dodecylamine salt of lactic acid, dodecyl amine salt of salicylic acid, etc.

Soil repellents.-These agents may be of the types effective against water-borne soil or oil-borne soil or they may be effective against both kinds of soil. Typical materials which may be used are: emulsions of waxes and aluminum acetate or zirconium acetate; silicone compounds such as polydimethyl siloxanes, polymethylhydrogen siloxanes, fluorinated compounds such as polyvinyl perfluorobutyrate, polyperfluorobutyl acrylate, chromium complexes of perfluorinated aliphatic carboxylic acids such as those of the formula:

CF (CF COOH Oil repellents-Chromium complexes of perfluorinated aliphatic carboxylic acids such as those of the formula:

CF (CF COOH fluorinated compounds such as polyvinyl penfluorobutyrate, polyperfluorobutyl acrylate, copolymers of vinyl perfluorobutyrate and perfluorobutyl acrylate.

Water repellents-Waxes; aluminum acetate; zirconium acetate; emulsions of waxes and aluminum or zirconium acetate; chlorinated paraflin waxes, for instance, those containing 42 to 70% chlorine; aluminum soaps; cetyl palmitate; stearyl stearate; silicone compounds such as polydimethylsiloxane and polymethyl hydrogen siloxane.

Insecticides.p-Dichlorobenzene; silicofluorides such as sodium silicofiuoride; pyrethrins; dieldrin; pentachlorodihydroxy-triphenylmethane sodium sulphonate; extract of derris root; pentachlorophenol; dinitronaphthol, dinitroorthocresol, benzene hexachloride; D.D.T.; N,N-diethyl- N-acetyl thiocarbamo sulfenamide, N,N-diphenyl-N'- acetyl thiocarbamo sulfenamide.

Insect repellents.--N-ethyltoluamide; 2-ethyl-1,3-hexanediol; dimethyl phthalate; dimethyl carbate (Dimelone); butopyronoxyl; etc.

Sizing agents.Starches, gums as tragacanth, karaya, arabic, etc., methyl cellulose, sodium carboxymethylcellulose, sodium alginate, gelatin, polyvinyl alcohol, polyvinyl acetate, polyacrylic acid, sodium polyacrylate, etc.

Pigments or other coloring materials.Typical among these are conventional dyes such as those of the acid, direct, sulphur, and solvent types. However, the invention is of particular advantage in that pigments-that is, coloring materials which are not classed as dyescan be durably fixed to textile materials. Typical of such pigments are barium chromate, strontium chromate, zinc chromate, venetian red, turkey red, indian red, carbon black, siennas, umbers, ochres, cinnabar (red mercury sulphide), powdered metals such as aluminum, copper, brass, bronze, zinc, gold, titanium dioxide, zinc oxide, lithopone, basic lead carbonate, basic lead sulphate, pigment yellow 1 (CI11680), pigment yellow 34 (CI- 77600), pigment orange 5 (CI-12075), pigment orange 13 (CI-21110), pigment red 4 (CI-12085), pigment red 101 (CI-77015), pigment blue 15 (CI-74160), pigment green (CI-74260), pigment brown (CI-12480), and pigment red 106 (CI-77766). The invention is also adapted for fixing to textiles fluorescent brightening agents (the so-called optical bleaches), for example, those listed in the Colour Index under Nos. 40,630, 40,600, 40,620, 40,605, and 40,640. A special advantage of the invention involves fixing a white pigment, such as titanium dioxide, to wool textiles whereby the product is less readily yellowed by exposure to light than is the untreated fabric. Also, such product is measurably whiter than the untreated fabric as shown by reflectance tests, particularly when the reflectance is measured over a dark background.

Softeners, often referred to as lubricants or conditioners.Fatty acid esters of diethylene glycol such as the lauric or stearic acid esters, polyethylene glycols, sulphonated animal or vegetable fats, high molecular weight aliphatic alcohols such as decyl alcohol, oleyl alcohol, dodecyl alcohol, cetyl alcohol, blends of waxes and sulphonated oils, fatty acids such as stearic and palmitic, derivatives of sorbitol such as sorbitan monolaurate, monopalmitate, monostearate, condensation products of fatty acids and alkylolamines, fatty acid esters of ethylene glycol monoalkyl ethers such as the oleic acid, stearic acid, or palmitic acid esters of monobutyl ether of ethylene glycol, condensation products, of fatty acids and amino sulphonic acids; for example, the sodium salt of N-oleoyl taurine, quaternary compounds such as stearamidomethyl pyridinium chloride, and octadecyloxymethyl pyridinium chloride.

Antistatic agents, that is, agents which will reduce the tendency of textiles to develop static electrical charges.- Polymers of beta-propiolactone; gamma-stearamidopropyl dimethyl heneicosaethenoxy ammonium chloride; gammastearamidopropyl dimethyl nonaethenoxy ammonium chloride; gamma-stearamidopropyl di(dodecaetheneoxy) ammonium chloride; gamma-stearamidopropyl tri-dodecaetheneoxy) ammonium chloride; N-cetyl N-ethyl morpholinium ethosulphate; etc.

In applying the process of the invention, the textile to be treated is successively impregnated with two solutions, each containing one of the pair of complementary condensation polymer-forming intermediates. The finishing agent to be applied to the textile may be added to either of the solutions, or, it may be added to both. Depending on the particular case, it may be preferred to add the finishing agent to one or the other of the solutions. For example, if the finishing agent is water-soluble is would be preferable to add it to the solution which contains water as a solvent. On the other hand, if the finishing agent is Water-insoluble but soluble in organic solvents it would be preferable to add it to that solution which contains an organic solvent. However, it is not essential that the finishing agent be actually dissolved; it is only necessary that it be present. Thus the agent may be dissolved, suspended, or in any other dispersed form. It is also evident that it is within the purview of the invention to add more than one finishing agent; for example, one may add both a soil-repellent and an insecticide, or both a soil-repellent and a coloring material. Further extensions of this concept will be obvious from these examples. The amount of finishing agent to be used will vary depending on such factors as the efficacy of the agent selected, the characteristics to be imparted to the textile, and so forth. In general, theamount of finishing material may be proportioned so that the product contains anywhere from 0.01 to 10% of finishing agent, based on the weight of the textile, per se. The textile material to which the process of the invention is applied may be in the form of bulk fibers, slivers, rovings, yarns, felts, woven textiles, knitted textiles, or even completed garments or garment parts.

By a suitable choice of the complementary polymerforming reagents one can utilize many different types of polymers for fixing the selected finishing agent to the textile substrate. Reagents suitable for this purpose and methods of applying them are described in our copending application, Ser. No. 98,718, filed Mar. 27, 1961, of which this application is a continuation-in-part. However, this material is reiterated herein for the sake of completeness of disclosure. The particular polymer-forming reagents-- herein termed Component A and Component Bwhich are to be used will depend on the type of polymer desired. In general, Component A may be a diamine, a diol, or a mixture of a diamine, and a cliol. Dependent on the reagent selected as Component A, Component B may be, for example, a diacid chloride, a bischloroformate, a diisocyanate, or mixtures of these classes of compounds. Typical choices which may be made and the type of polymer formed are set forth below by way of example:

ents of Component A are soluble in water and may thus be applied to the textile in aqueous solution. In such case Since components A and B may be selected to form any desired type of condensation polymer, these components may be aptly termed as complementary organic condensation polymer-forming intermediates. They may further be appropriately designated as fast-reacting or direct-acting because they form the resinous polymers rapidly and directly under interfacial conditions without requiring any aftertreatments, such as treatment with curing agents, oven cures, etc.

Having selected the desired Components A and B, these are formed into separate solutions for application to the textile to be treated. An essential consideration in the preferred modification of the invention is that the solvents used in the respective solutions of Components A and B be substantially mutually immiscible so that a liquidliquid interface will be set up between the two solutions on the wool fibers. Thus, for example, Component A is dissolved in water and Component B is dissolved in benzene, carbon tetrachloride, toluene, xylene, ethylene dichloride, chloroform, hexane, octane, petroleum ether or other volatile petroleum distillate, or any other inert waterimmiscible solvent. (As set forth hereinabove, the selected finishing agents to be fixed to the textile are dispersed in either or both of these solutions.) The two solutions are then applied to the textile serially; that is, the textile is treated first with one solution, then with the other. The order of applying the solutions is not critical. Generally, the solution of Component A is applied first and the solution of Component B is applied next; however, the reverse order gives good results and it is within the ambit of the invention to apply the solutions in either sequence.

The solutions may be applied to the textile in any desired way as long as they are applied serially. A preferred method involves immersing the textile in one solution, removing excess liquid as by use of squeeze rolls, immersing the textile with the second solution, again removing excess liquid, rinsing the treated fabric in water and then drying it. Conventional apparatus consisting of tanks, padding rolls, squeeze rolls, and the like, are generally used in applying the respective solutions. The amount of each solution applied to the textile may be varied by altering the residence time in the solutions, the pressure exerted by the squeeze rolls and by varying the concentration of the active materials in the respective solutions. To decrease carry-over of the solvent from the first treating solution to the second solution, the textile after its immersion in the first solution may be subjected to drying conditions such as a current of warm air to concentrate the solution carried by the fibers.

As noted above, a critical factor in the preferred form of the invention is that the complementary agentsComponent A and Component B (plus the added finishing agents)are serially applied to the textile dispersed in solvent, which are substantially mutually immiscible, whereby to secure interfacial polymerization conditions. The nature of the solvents is of no consequence as long as they are essentially inert and possess the above-stated property of substantial immiscibility. Usually, volatile solvents are preferred as they may be removed from the treated textile by evaporation. However, non-volatile solvents can be used, in which case they may be removed from the product by extraction with suitable volatile solvents therefor or Washed outwith soap and water or detergent and water formulations. In many cases the ingredithe solvent for Component B may be any inert, essentially water-immiscible organic solvent. Typical illustrative examples thereof are benzene, toluene, xylene, carbon tetrachloride, ethylene dichloride, chloroform, hexane, octane, petroleum ether or other volatile petroleum fraction. It is, however, not essential that Component A be employed in aqueous solution. Thus, one may utilize a system of two essentially immiscible organic solvents, Component A being dispersed in one solvent and Component B in the other. As an example, Component A may be dispersed in 2-bromoethyl acetate and Component B dispersed in benzene. Another example involves using formamide, dimethylformamide, or dimethylformamide as the solvent for Component A and using n-hexyl ether as the sol vent for Component B. A further example involves a system of adiponitrile as the solvent for Component A and ethyl ether as the solvent for Component B. Examples of other pairs of solvents which are substantially immiscible with one another and which may be used for preparing the solutions of the respective reactants are 2-bromoethyl acetate and n-hexyl ether, ethylene glycol diacetate and n-hexyl ether, adiponitrile and n-butyl ether, adiponitrile and carbon tetrachloride, benzonitrile and formamide, n-butyl ether and formamide, di-N-propyl aniline and formamide, isoamyl sulphide and formamide, benzene and formamide, butyl acetate and formamide, benzene and nitromethane, n-butyl ether and nitromethane, carbon tetrachloride and formamide, dimethyl aniline and formamide, ethyl benzoate and formamide.

The concentration of polymer-forming reagents (Component A and Component B) in the respective solutions is not critical and may be varied widely. Generally, it is preferred that each of the pair of solutions contains about from 1 to 20% of the respective active component. In applying the process of the invention, enough of the respective solutions are applied to the textile to give a polymer deposit on the fibers of about 1 to 1 0% Such amounts of polymer applied on wool afford a substantial degree of shrinkproofing with no significant reduction in the hand of the wool. Greater amounts of polymer may be deposited on the textile, particularly in those cases where it is not desired to maintain the natural hand of the textile. The relative amounts of Component A and Component B applied to the textile may be varied as desired for individual circumstances. Generally, it is preferred to apply the components in equimolar proportions; that is, the amounts are so selected that there are the same number of functional groups provided by Component A as pro vided by the functional groups of Component B.

It is often desirable to add reaction promoters or catalysts to either of the solutions of Component A or B in order to enhance reaction between the active agents. For example, in cases where the system involves reaction between a diamine (or a diol) and a diacid chloride or a bischloroformate it is desirable to add to either of the solutions a sufiicient amount of alkaline material to take up the HCl formed in the reaction. For such purpose one may use a tertiary amine such as pyridine, dimethyl aniline, or quinoline or an alkali-metal hydroxide, or, more preferably, an alkaline material with buffering capacity such as sodium carbonate, sodium bicarbonate, trisodium phosphate, borax, etc. Another plan which may be used in instances where Component A includes a diamine and Component B includes a diacid chloride or hischloroformate, involves supplying the diamine in excess so that it will act both as a reagent and as an HCl-acceptor. The reaction of Components A and B may also be catalyzed by addition of such agents as tributyl tin chloride, stannous tartrate, ferric chloride, titanium tetrachloride, boron trifluoride-diethyl ether complex, or tin salts of fat acids such as tin laurate, myristate, etc. Such catalysts are particularly useful to promote reaction between (1) diols and (2) diisocyanates, diacid chlorides, and bischloroformates.

Where one of the solutions of the reactants contains water as the solvent, it is often desirable to incorporate a minor proportion of a surface-active agent to aid in dispersing the reactant and to assist in penetration of the solution into the textile. For this purpose one may use such agents as sodium alkyl (Cg-C18) sulphates, the sodium alkane (C -C sulphonates, the sodium alkyl (C C benzene sulphonates, esters of sulphosuccinic acid such as sodium dioctylsulphosuccinate, and soaps, typically sodium salts of fat acids. Emulsifying agents of the non-ionic type are suitable, for example, the reaction products of ethylene oxide with fatty acids, with polyhydric alcohols, with partial esters of fatty acids and polyhydric alcohols or with alkyl phenols, etc. Typical of such agents are a polyoxyethylene stearate containing about 20 oxyethylene groups per mole, a polyoxyethylene ether of sorbitan monolaurate containing about 16 oxyethylene groups per mole, a distearate of polyoxyethylene ether of sorbitol containing about 40 oxyethylene groups per mole, iso-octyl phenyl ether of polyethylene glycol, etc. Generally, only a small proportion of surface-active agent is used, on the order of 0.05 to 0.5%, based on the weight of the solution. In addition to, or in place of the surface-active agent, a supplementary solvent may be added to the primary solvent (water) in quantity suflicient to disperse the active reactant. For such purpose one may employ acetone, or other inert volatile solvent, particularly one that is at least partially miscible with water. It is evident that the solutions of Components A and B need not necessarily be true solutions; they may be colloidal solutions, emulsions, or suspensions, all these being considered as solutions for the purposes of the present invention.

Ordinarily, the treatment of the textile with the solutions of the complementary agents is carried out at room temperature as at such temperature the polymerization takes place very rapidly, that is, in a matter of a minute or less. If, however, a higher rate of polymerization is desired-as in continuous operation on long lengths of cloththe second solution may be kept hot, for example, at a temperature up to around 150 C. Also, where the agents used include a diol as such (in contrast to the alkali salt thereof) it is preferable to heat the second solution as the polymerization rates with the diols are generally unsatisfactory at room temperature.

It will be obvious to those skilled in the art that for best results, the finishing agent and the polymer-forming intermediate which are employed together in the textiletreating solutions be selected for compatibility. For example, in the solution which contains Component A (a diamine or a diol) one would avoid using a finishing agent which is reactive with amine or hydroxy groups. Thus typically, the selected finishing agent should be free from such functional groups as acid, acid chloride, or isocyanate radicals. Moreover, with the solution containing the complementary polymer-forming intermediate (Component Bdiacid chloride, bischloroformate, or diisocyanate) one would not use a finishing agent which contained a reactive functional group such as amino or hydroxyl. Taking into account these considerations, if it is desired to apply a finishing agent containing a radical reactive with amines or hydroxy compounds, one would add it to the solution containing the diacid chloride, bischloroformate, or diisocyanate. Conversely, if one desired to apply a finishing agent containing a radical reactive with acid chlorides or isocyanates, one would add it to the solution of the diamine or diol.

COMPONENTS A AND B As noted briefly above, the selection of Components A and B depends on the type of polymer desired to be formed on the fibers. In general, Component A may be a diamine, a diol, or a mixture of a diamine and a diol; Component B may the a diacid chloride, a bischloroformate, a diisocyanate, or a mixture of two or more of these classes of compounds. Typical examples of compounds which can be employed as Component A in a practice of the invention are described below.

As the diamine one may employ any of the aromatic, aliphatic, or heterocyclic compounds containing two primary or secondary amine groups, preferably separated by at least two carbon atoms. The diamines may be substituted if desired with various non-interfering (non-functional) substitnents such as ether radicals, thioether radicals, tertiary amino groups, sulphone groups, fluorine atoms, etc. Typical compounds in this category are listed below merely by Way of illustration and not by way of limitation: ethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, octamethylene diamine, decamethylene diamine, N,N'-dimethyl l, 3 propanediamine, 1,2 diamino 2 methylpropane, 2,7 diamino 2,6-dimethyloctane, N,N' dimethyl 1,6 hexanediamine, 1,4-diamino cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 2,2'-diaminodiethyl ether, 2,2'-diaminodiethyl sulphide, ibis (4-aminocyclohexyl) methane, N,N-dimethyl- 2,2,3,3,4,4 hexafluoropentane-l,S-diamine, ortho-, meta-, or para-phenylene diamine, benzidine, xylylene diamine, m-toluylene diamine, ortho-tolidine, piperazine, and the like. If desired, mixtures of different diamines may be used. It is generally preferred to use aliphatic alpha, omega diamines, particualrly of the type wherein n has a value of 2 to 12, preferably 6 to 10.

As the diol one may employ any of the aliphatic, aromatic, or heterocyclic compounds containing two hydroxy groups, preferably separated by at least two carbon atoms. The diols may be substituted if desired with various noninterfering (non-functional) substituents such as ether groups, sulphone groups, tertiary amine groups, thioether groups, fluorine atoms, etc. Typical compounds which may be used are listed below merely by way of illustration and not limitation: Ethylene glycol, diethylene glycol, 2,2- dimethyl propane-1,3-diol, propane-1,3-diol, butane-1,4- diol, hexane-1,6-diol, octane-1,8-diol, decane-LlO-diol, dodecane-hlZ-diol, butane-1,2-diol, hexane-1,2-diol, 1-0- methyl glycerol, Z-O-methyl glycerol, cyclohexane-1,4-diol, hydroquinone, resorcinol, catechol, =bis(parahydroxyphenyl) methane, 1,2-Ibis(parahydroxyphenyl) ethane, 2,2- bis(parahydroxyphenyl) propane, 2,2-bis(parahydroxyphenyl) butane, 4,4dihydroxybenzophenone, naphthalene 1,5 diol, biphenyl-4,4'-diol, 2,2-bis(3-methyl-4-hydroxyphenyl) propane, 2,2-bis(3 isopropyl 4 hydroxyphenyl) propane, 2,2-bis(4-hydroxy-dibromophenyl) pro pane, etc.

If desired, mixtures of different diols may be used. It is also within the purview of the invention, though less preferred, to use the compounds containing more than two hydroxy groups as for example, glycerol, diglycerol, hexanetriol, pentaerythritol, etc. Moreover, it is within the spirit of the invention to utilize the sulphur analogues of the diols. Thus, for example, instead of using the compounds containing two hydroxy groups one can use the analogues containing either (a) two SH groups or (b) one SH group and one OH group.

Among the preferred compounds are the aliphatic diols, for example, those of the type:

wherein n has a value from 2 to 12. Another preferred category of aliphatic compounds are the polyethylene glycols, i.e.:

wherein n has a value from zero to 10. A preferred category of aromatic diols are the bisphenols, that is, compounds of the type R R R cr H 1 1 OH wherein RCR represents an aliphatic hydrocarbon group containing 1 to 12 carbon atoms and R represents hydrogen or a lower alkyl radical. In this category especially preferred compounds are 2,2 -lb-is(parahyd'roxyphenyl) propane, often designated as bisphenol-A- 2,2-his (3-methyl-4-hydroxyphenyl) propane; 2,2-bis(3-isopropyl- 4-hydroxyphenyl) propane; and brominated derivatives of bisphenol A, such as 2,2-bis(4-hydroxy-dibromophenyl) propane.

The diols are employed as such or in the form. of their alkalimetal salts, that is, as alcoholates or phenolates, depending on whether the diols are aliphatic or aromatic. The alkali-metal derivatives are preferred as they will react with the active agents of Component B at room temperature. With the diols, as such, temperatures above room temperature are generally required to promote reaction with their complements in Component B. In such case proper temperature for the reaction can be achieved by holding the second solution into which the textile is immersed, at about ,50 to 150 C. It is obvious that the solvent selected for the second solution will need to be one which has a boiling point above the temperature selected, or, in the alternative, a pressurized system can be used to maintain the solvent in the liquid phase.

In the modification of the invention wherein water is used as the solvent for Component A (a diol in this case) and Component B is dispersed in a water-immiscible, inert solvent, it is preferred to use aromatic diols in their salt (phenolate) form. This affords several distinct advantages. Thus the alkali-metal phenolates are quite soluble in water, they are relatively stable in aqueous solution (in contrast to the alcoholates), and they will react at room temperature with diacid chlorides, bischloroformates, or diisocyanates so that no heating is required.

Typical examples of compounds which can be employed as Component B in a practice of the invention are described below.

As the diacid chloride one may employ any of the aliphatic, aromatic, or heterocyclic compounds containing two carbonylchloride (COCl) groups, preferably separated by at least two carbon atoms. The diacid chlorides may be substituted if desired with non-interfering (non-functional) substitutents such as ether groups, thioether groups, sulphone groups, etc. Typical examples of compounds in this category are listed below merely by way of illustration and not limitation: Oxalyl chloride, maleyl chloride, fumaryl chloride, malonyl chloride, succinyl chloride, glutaryl chloride, adipyl chloride, pimelyl chloride, suberyl chloride, azelayl chloride, sebacyl chloride, cyclohexane-1,4 biscarbonylchloride, phthalyl chloride, isophthalyl chloride, terephthalyl chloride, 4,4'-biphenyl-dicarbonyl chloride, fl-hydromuconyl chloride, i.e., ClCOCH CH:CHCH -COCl, diglycollic acid chloride, i.e., O(CH COCl) higher homologues of this compound as ()(CH CH COCl) dithiodiglycollic acid chloride, diphenylolpropanediacetic acid chloride, i.e., (CH C(C H OCH C0Cl) and the like. If desired, mixtures of different diacid chlorides may be used. It is also evident that the sulphur analogues of these compounds may be used and are included within the spirit of the invention. Thus, instead of using compounds containing two 'COC1 groups one may use compounds containing one CSC1 and one COC1 group or compounds containing two -CSCl groups. Moreover, although the diacid chlorides are preferred as they are reactive and relatively inexpensive, the corresponding bromides and iodides may be used.

As the diacid chloride, it is generally preferred to use the aliphatic compounds containing two carbonylchloride groups in alpha, omega positions, particularly those of the type:

ClCO(CH COCl wherein n has a value from 2 to 12. Another preferred category includes the compounds of the formula ClCOAOOCl (where A is the benzene or cyclohexane radical), especially para-substituted compounds such as terephthalyl and hexahydroterephthalyl chlorides.

As the bischloroformate one may use any of the aliphatic, aromatic, or heterocyclic compounds containing two chloroformate groups preferably separated by at least two carbon atoms. The bischloroformates may be substituted if desired with noninterfering (nonfunctional) substitutents such as sulphone groups, ether groups, thioether groups, etc. Typical examples of compounds in this category are listed below merely by way of illustration and not limitation: Ethylene glycol bischloroformate, diethylene glycol bischloroformate, 2,2-dimethyl propane 1,3-diol bischloroformate, propane-1,3-diol bischloroformate, butane-1,4-diol bischloroformate, hexane-1,6-diol bischloroformate, octane- 1,8-diol bischloroformate, decane-1,10-diol bischloroformate, butane-1,2-diol bischloroformate, hexane-1,2- diol bischloroformate, lmethoxyglycerol-1,3-bisch1oroformate, glycerol-1,2-bischloroformate, glycerol-1,3-bischloroformate, digylcerol bischloroformate, hexanetriol bischloroformate, pentaerythritol bischloroformate, cyclohexane-l,4-diol bischloroformate, hydroquinone bischloroformate, resorcinol bischloroformate, catechol bischloroformate, bischloroformate of 2,2-bis(parahydroxyphenyl) propane, bischloroformate of 2,2-bis(parahydroxyphenyl) butane, bischloroformate of 4,4-dihydroxybenzophenone, bischloroformate of 1,2-bis(parahydroxyphenyl) ethane, naphthalene-1,5-diol bischloroformate, biphenyl-4,4'-diol bischloroformate, etc. 1f desired, mixtures of different bischloroformates may be used.

Among the preferred compounds are the aliphatic bischloroformates, for example, those of the type:

of aromatic bischloroformates are the bisphenol chloroformates, that is, compounds of the type:

u 1 u R wherein RCR represents an aliphatic hydrocarbon group containing 1 to 12 carbon atoms and R is hydrogen or a low alkyl radical.

It is also evident that the sulphur analogues of the bischloroformates may be used and such are included within the spirit of the invention. Thus, instead of using the compounds containing two groups one may use any of the compounds containing the sulphur analogues of these groups, for example, the compounds containing two groups of the formula X-ii-Cl wherein one X is sulphur and the other is oxygen or wherein both Xs are sulphur. Moreover, although the bichloroformates are preferred because they are reactive and relatively inexpensive, it is not essential that they contain chlorine and one may use the corresponding bisbromoformates or bisiodoformates.

As the diisocyanate one may employ any of the aliphatic, aromatic, or heterocyclic compounds containing two isocyanate (NCO) groups preferably separated by at least two carbon atoms. The diisocyanates may be substituted if desired with non-interfering (non-function) substituents such as ether groups, thioether groups, sulphone groups, etc. Typical examples of compounds in this category are listed below merely by way of illustration and not limitation: lEthylene diisocyanate, propylene diisocyanate, butylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, cyclohexylene diisocyanate, bis(Z-isocyanatoethyl) ether, bis(2-isocyanatoethyl) ether of ethylene glycol, o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene-Z,6-diisocyanate, 3,3'-bitolylene-4,4-diisocyanate, i.e.,

CH3 CH3 diphenyl ether-4,4'-diisocyanate, i.e.,

3,5,3',5'-bixylylene-4,4-diisocyanate, i.e.,

R R l (R is CHa) diphenylmethane-4,4'-diisocyanate, i.e.,

biphenylene diisocyanate, 3,3-dimethoxy-biphenylene- 4,4-diisocyanate, naphthalene diisocyanates, polymethyl polyphenyl isocyanates, etc. It is also evident that the sulphur analogues of these compounds may be used and such are included within the spirit of the invention. Thus for example, instead of using the compounds containing two NCO groups one may use their analogues containing either two NCS groups or one NCO group and one NCS group. Another point to be made is that it is within the spirit of the invention to utilize the derivatives which yield the same products with compounds containing active hydrogen as do the isocyanates. Particular reference is made to the biscarbamyl chlorides which may be used in place of the diisocyanates. Thus one may use any of the above-designated compounds which contain carbamyl chloride groups (N( i-c1) or their sulphur analogues in place of the isocyanate groups.

Among the preferred compounds are the aliphatic diisocyanates, for example, those of the type wherein n has a value from 2 to 12. Other preferred compounds are the toluene diisocyanates, xylylene diisocyanates, and diphenylmethane-4,4'-diisocyanate which may also be termed methylene-bis(p-phenylisocyanate).

There has been set forth above a comprehensive disclosure of the preferred types of complementary agents, that is, diamines, diols, diacid chlorides, bischloroformates, diisocyanates, and their equivalents. Although it is preferred to use these agents for optimum results, they are by no means the only compounds which may be used. The invention in its broadest aspect includes the application of many other types of complementary agents which have the ability to form condensation polymers when applied by the disclosed procedures. Various examples are thus set forth of other types of compounds which may be used.

Polysulphonamides-forrned by conjoint use of a diamine and a disulphonyl chloride. A typical example in this category involves applying to the wool an aqueous solution of a diamine, followed by applying to the wool a disulphonyl chloride dissolved in benzene, toluene, or other inert, essentially water-immiscible solvent. Any of the diamines above described may be used in conjunction with such disulphonyl chlorides as benzene-1,3-disulphonyl chloride, biphenyl-4,4-disulphonyl chloride, toluene disulphonyl chlorides or aliphatic compounds such as those of the formula wherein n has a value from 2 to 12. Related polymers can be formed by applying these disulphonyl chlorides (as Component B) in conjunction with such compounds as urea, guanidine, thiourea, biuret, dithiobiuret, or the like as Component A.

Polysulphonatesformed by the conjoint use of a diol and a disulphonyl chloride. In a typical example in this area, an aqueous solution of a diolpreferably in the form of its alkali-metal salt-is first applied to the wool, followed by application of a disulphonyl chloride in inert, essentially water-immiscible solvent. For this purpose one may use any of the diols and disulphonyl chlorides ex emplified above. A variant of this procedure is to use the corresponding dithiol in place of the diol, thus to form a polythiolsulphonate.

An alternative to the diacid chlorides is the use of mixed anhydrides of the corresponding dicarboxylic acids with monobasic acids such as trifluoroacetic acid, dibutylphosphoric acid, or the like. Such mixed anhydrides may be employed, for example, as Component B in conjunction with a diamine, diol, or dithiol as Component A to form polyamides, polyesters, or polythiolesters, respectively.

Another plan involves the use of urea, thiourea, biuret, dithiobiuret, guanidine, or the like (as Component A) in conjunction with diacid chlorides as Component B to form polyureas, polythioureas, etc.

The invention is further demonstrated by the following illustrative examples.

The tests for shrinkage referred to in the examples were conducted in the following Way: The W001 samples were milled at 1700 rpm. for 2 minutes at 4042 C. in an Accelerotor with 0.5% sodium oleate in aqueous solution, using a liquor-to-wool ratio of to 1. After this washing operation the samples were measured to determine their area and the shrinkage was calculated from the original area. With this severe Washing method, samples of control (untreated) wool cloth gave an area shrinkage of 48%. The Accelerotor is described in the American Dyestulf Reporter, vol. 45, p. 685, Sept. 10, 1956.

The tests for water repellency referred to in the examples were conducted as follows: The cloth sample was laid fiat and drops of water placed on it and the cloth then covered with an upturned beaker. The system was observed at intervals to note the time required for the drops to penetrate into the cloth. With an untreated cloth sample, water drops penetrated in to minutes.

Tests for oil repellency were performed as above described except using drops of mineral oil instead of water. With the untreated cloth the mineral oil drops penetrated instantly.

Example l.-Application of water-repellent (A) SOLUTIONS Solution I: 4% hexamethylene diamine in water. Solution II: 2% sebacoyl chloride and 2% behenoyl chloride in carbon tetrachloride.

(B) APPLICATION OF SOLUTIONS A sample of wool cloth was immersed in solution I for 30 seconds, run through squeeze rolls to remove excess liquid, immersed for 30 seconds in solution II, run through squeeze rolls to remove excess liquid, given a 15-minute wash in warm water and detergent, rinsed in water, and dried in air.

(C) RESULTS The treated wool displayed a weight increase of 7.2% and on washing in the Accelerotor exhibited an area shrinkage of 13.6%.

In the water-repellency test it was found that water drops did not penetrate the treated fabric for 8 hours or longer.

Example 2.Application of water-repellent Solution I: 4% hexamethylene diamine in water.

Solution H: 3% sebacoyl chloride and 3% polyethylene (molecular weight about 5,000 to 10,000) in carbon tetrachloride.

Wool cloth was treated with solutions I and II as described in Example 1, part B.

The treated cloth displayed a weight increase of 6.7% and on washing in the Accelerotor exhibited an area shrinkage of 4%.

In the water-repellency test it was found that water drops did not penetrate into the treated fabric for 8 hours or longer.

Example 3.Application of water-repellent Solution 1: 3% polyethylene emulsion and 4% hexamethylene diamine in water. (The 3% polyethylene emulsion contained polyethylene of molecular weight about 5,000 to 10,000, 5% of alkyl aryl polyethylene glycol, 1.5% potassium hydroxide solution, and 73.5 water.)

Solution I: 3% sebacoyl chloride in carbon tetrachloride.

Wool cloth was treated with solutions I and II as described in Example 1, part B.

The treated cloth displayed a weight increase of 3.9% and on washing in the Accelerotor exhibited an area shrinkage of 12.6%.

In the water-repellency test, water drops did not penetrate into the treated cloth for 8 hours or longer.

Example 4.-Application of a soil-repellent Three runs were carried out, using the following solutions:

RUN A Solution I: 2% hexamethylene diamine in water plus 4% 'Na CO and 4 ml. (per 100 ml. of solution) of a soil-repellent.

Solution 11: 3% sebacoyl chloride in carbon tetrachloride.

RUN B Solution I: 2% hexamethylene diamine in water plus 4% Na CO and 8 ml. (per 100 ml. of solution) of a soilrepellent.

Solution II: 3% sebacoyl chloride in carbon tetrachloride.

RUN C Solution 1: 3% sebacoyl chloride in carbon tetrachloride.

Solution II: 2% hexamethylene diamine plus 4% Na CO and 8 ml. (per ml. of solution) of a soilrepellent.

The soil repellent used in these runs was a product designated as PC-139 available from Minnesota Mining and Manufacturing Company and believed to be an emulsion containing as the active ingredient a polymerized perfluoro acrylate ester.

Wool cloth was treated with the solutions as described in Example 1, part B. Weight increases and shrinkages (after Accelerotor washing) of the products were as follows:

Weight Increase, Percent Area Shrinkage, Percent ceno The treated fabrics displayed excellent oiland waterrepellency. In the oil-repellency test, oil drops did not penetrate into the fabric for 7 days; in the water-repellency test, water drops did not penetrate into the fabric for over 12 hours. It was also found that the samples which had been washed in the Accelerotor (this represents a very severe washing) retained their oiland water-repellency essentially unimpaired.

Example 5.Application of water-repellent Solution I: 4% hexamethylene diamine in water. Solution II: 3% sebacoyl chloride and 4% of a polymerized methyl hydrogen siloxane of the formula:

H is-as Wool cloth was treated with solutions I and II as described in Example 1, part B. The treated cloth displayed a weight increase of 2.7% and on washing in the Accelerotor exhibited an area shrinkage of 12.6

In the water-repellency test it was found that it required 12 hours for water drops to penetrate into the treated fabric.

Example 6.-Application of water-repellent Solution 1: 4% hexamethylene diamine in water. Solution II: 3% sebacoyl chloride plus 4% of polydimethyl siloxane.

Wool cloth was treated with solutions I and H as described in Example 1, part B. The treated cloth displayed a weight increase of 2.9% and on washing in the Accelerotor exhibited an area shrinkage of 13.5%.

In the water-repellency test it was found that it required 12 hours for the water drops to penetrate into the treated fabric.

Example 7.Application of water-repellent Solution I: 4% hexamethylene diamine in water. Solution II: 3% sebacoyl chloride and 4% carnauba wax in carbon tetrachloride.

15 16 Solution II: 3% sebacoyl chloride and 0.05% Heliogen A sample of the product which had been subjected blue (a phthalocyanine pigment-Cl. pigment blu 15, only to the process wash (following application of solu- 74160) in a Volatile Petroleum hydrocarbon tions I and II) and a sample of the product which had distillate, 133 to been washed in the Accelerotor were subjected to tests (B) APPLICATION OF SOLUTIONS 5 for resistance to attack by moths. As a control, a sample of the untreated fabric was also subjected to the tests.

A sample of wool cloth was Immersed m Sohmon I In the tests, fabric samples of identical size were placed for 15 seconds, run through squeeze rolls to remove excess liquid, immersed for 15 seconds in solution II, and m a vessel together Wlth f P bcetle larvae, 51X run through squeeze rolls to remove excess liquid. The Week 14 days, examlnatfqfl Was made 0 treated cloth was then given a 15-minute process wash in 10 termlne moftallty 0f the beetles, Vlslble f g the warm water and detergent, rinsed in water, and dried in fabric, and the excrement 0f the es Welghed. The air. results are tabulated below:

Visible Weight of Sample Mortality damage excrement to fabric Treated fabric All dead None 1 mg. Treated fabric, washed in Accelerotor 4 dead, 6 in abnormal condition do 1 mg. Untreated fabric All alive and normal Yes 10 mg.

RESULTS Example 11.-Application of Insecticide and Soil- The treated cloth displayed a weight increase of 2% and Repellent on washin; in the Accelerotor exhibited an area shrink- Solution I: 3% hexamethylem diamine 6% z 3 and ageo 18 0. is I The treated fabric displayed a uniform pastel blue color fgjf 3 3 Polymenzed perfluoro butyl acry which remamed fast dmng the Pmess Wash (Mbwmg Solution n: 3% sebacoyl chloride and 1% of a dieldrin application of solutions I and II) and during the succeeding wash in the Accelerotor. It is to be noted that concentrate (20%) m toluene the Heliogen blue used in this experiment is not Wool cloth was treated with solutions I and II as destannve for W001 scribed in Example 1, part B. The treated cloth displayed Example 9.Application of soil-repellent a weight increase of 2% and on washing in the Accelerotor exhibited an area shrinkage of 13.5%.

The treated fabric displayed excellent oil and water repellency. In the oil-repellency test, oil drops did not penetrate into the fabric for 60 hours; in the water-re- Solution I: 3% hexamethylene diamine, 6% Na CO and 1% of a soil-repellent in water. Solution II: 3% sebacoyl chloride in carbon tetrachloride.

The soil-repellent used in this test was a commercial pellency test, water drops did not penetrate into the fabric product PC-208 available from the Minnesota Mining for 6 hours. It was also found that when the samples and Manufacturing Company and believed to be a polymhad been washed in the Accelerotor (which represents a erized perfluoro butyl acrylate. very severe washing), their oil and water repellency re- Wool cloth was treated with solutions I and II as demained essentially unimpaired. scribed in Example 8, part B. The treated cloth displayed Samples of the product which had been subjected only a weight increase of 216% and on washing in the Acceleroto the process wash (following application of solutions tor exhibited an area shrinkage of 12.6%. I and II) and a sample of the product which had been In the repellency tests it was found that oil drops and washed in the Accelerotor were subjected to tests for water drops required and over 12 hours, respectively, resistance to attack by moths, as described in Example to penetrate into the fabric. 10. The results are tabulated below:

Visible Weight of Sample Mortality damage excrement to fabric Treated fabric All dead N0ne 1 mg. Treated fabric washed in Accelerotor 6 dead, 4 abnormal ..do 1 mg. Untreated fabric All alive and normaL Yes 10 mg.

Example 10.Application of insecticide Example l2.,--Application of insecticide Solution 1: 3% hexamethylene diamine and 6% Na CO Solution 1: 3% hexamethylene diamine, 6% Na CO and in water. 1% of a water-soluble insecticide (pentachlorodihy- Solution II: 3% sebacoyl chloride and 1% of a 20% 60 droxy-triphenylmethane sodium sulphonate) in water.

solution of dieldrin, in toluene. Solution II: 3% sebacoyl chloride in toluene.

Dieldrin is the common name of the compound: 1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4a,5,6,7,8,8 Wool cloth was treated with solutions I and II as deoctahydro-l,4,5,S-dimethano-naphthalene. scribed in Example 1, part B. The treated cloth displayed a weight increase of 2% and on washing exhibited an Wool cloth was treated with solutions I and II as dearea shrinkage of 23.5%. scribed in Example 8, part B. The treated cloth displayed The products were tested for resistance to attack by a weight increase of 2.0% and on washing in the Acmoths as described in Example 10. The results are tabcelerotor exhibited an area shrinkage of 4.9%. ulated below:

Visible Weight 01 Sample Mortality damage excrement to fabric Treated fabric 5 dead, 5 abnormal None 1 mg.

Treated fabric washed in Accelerotor 2 dead, some larvae normal Slight 3 mg.

Example 13.-Application of soil-repellent RUN A Solution I: 2% hexamethylene diamine and 4% Na CO in water.

Solution H: 3% sebacoyl chloride plus 1% of EC-13 9 (described in Example 4) in a volatile petroleum hydrocarbon distillate.

RUN B Solution I: 2% hexamethylene diamine and 4% Na CO in water.

Solution II: 3% sebacoyl chloride plus 5% of FC13 9 (described in Example 4) in a volatile petroleum hydrocarbon distillate.

Samples of wool cloth were treated with the solutions as described in Example 8, part B.

It was found that the products had excellent oiland water-repellency as oil drops and water drops did not penetrate the treated fabrics for 24 hours.

Example 14.Application of water-repellent Solution 1: 2.5% hexamethylene diamine and 5% sodium carbonate in water.

Solution II: 3% sebacoyl chloride and 2% para- (trifluoromethyl) benzoyl chloride in xylene.

Samples of wool cloth 'were treated with the solutions as described in Example 1, part B.

It was found that the products had excellent waterrepellency as water drops remained on the fabric surface more than 12 hours without wetting the fabric.

The present invention finds its greatest field of utility in the treatment of wool textiles, particularly because it yields a dual benefit, that is, the wool is provided with a fixed deposit of finishing agent and the wool is also shrinkproof. However, in its broad aspect the invention encompasses the treatment of any other type of fibrous material,

typical examples being animal hides; leather; animal hair; cotton; hemp; jute; ramie; flax; wood; paper; synthetic cellulosic fibers such as viscose, cellulose, acetate, and cellulose acetate-butyrate; casein fibers; polyvinyl alcoholprotein fibers, alginic fibers; glass fibers; asbestos; and organic non-cellulosic fibers such as poly(ethylene glycol terephthalate), polyacrylonitrile, polyethylene, polyvinyl chloride, polyvinylidene chloride, etc. With all such fibrous materials the invention is of usefulness to provide them with fixed deposits of finishing agents whether or not shrinkage protection is also afforded.

Having thus described the invention, what is claimed is:

1. A process for treating a fibrous material which comprises serially applying to said material a pair of complementary direct-acting, organic, polyurea-forming intermediates in separate phases of limited mutual solubility,

at least one of said phases also containing a textile finishing agent.

2. A process for shrinkproofing wool without significant impairment of its hand and for concomitantly applying thereto a textile finishing agent, which comprises serially impregnating wool with two solutions,

one solution containing a diamine dispersed in water,

the other solution containing a diisocyanate dispersed in an inert, volatile, essentially water-immiscible solvent,

at least one of said solutions also containing a textile finishing agent,

the said diamine and diisocyanate reacting to form in situ on the wool fibers a resinous polyurea having enmeshed therein the said finishing agent.

3. The process of claim 2 wherein the finishing agent is an insecticide.

4. The process of claim 2 wherein the finishing agent is a soil-repellent.

5. The process of claim 2 wherein the finishing agent is a water-repellent.

6. The process of claim 2 wherein the finishing agent is a coloring material.

7. The process of claim 2 wherein the finishing agent comprises an insecticide and a soil-repellent.

8. A modified wool fiber which exhibits improved shrinkage properties as compared with the unmodified wool fiber and which is provided with a durable finish, comprising wool fiber having a polyurea formed in situ thereon and chemically bonded to the wool,

said polyurea having a textile finishing agent enmeshed therein and thereby fixed to said wool fiber.

9. The product of claim 8 wherein the finishing agent is an insecticide.

10. The product of claim 8 \wherein the finish'mg agent is a soil-repellent.

11. The product of claim 8 wherein the finishing agent is a water-repellent.

12. The product of claim 8 wherein the finishing agent is a coloring material.

13. The product of claim 8 wherein the finishing agent comprises an insecticide and a soil-repellent.

14. A process for shrinkproofing wool without significant impairment of its hand and for concomitantly applying thereto a textile finishing agent, which comprises serially impregnating wool with two solutions,

one solution containing a diamine dispersed in water,

the other solution containing a diacid chloride dispersed in an inert, volatile, essentially water-immiscible solvent,

at least one of said solutions also containing a textile finishing agent,

the said diamine and diacid chloride reacting to form in situ on the W001 fibers a resinous polyamide having enmeshed therein the said finishing agent.

15. The process of claim 14. wherein the finishing agent is an insecticide.

16. The process of claim 14 wherein the finishing agent is a soil-repellent.

17. The process of claim 14 wherein the finishing agent is a water-repellent.

18. The process of claim 14 wherein the finishing agent is a coloring material.

19. The process of claim 14 wherein the finishing agent comprises an insecticide and a soil-repellent.

References Cited UNITED STATES PATENTS 3,078,138 2/1963 Miller et a1. 8-l28 FOREIGN PATENTS 579,340 7/ 1946 Great Britain.

NORMAN G. TORCHIN, Primary Examiner. I. CANNON, Assistant Examiner.

US. Cl. X.R. 894.1, 115.5, 116.2, 120, 127.6, 128, 129

Claims (1)

1. A PROCESS FOR TREATING A FIBROUS MATERIAL WHICH COMPRISES SERIALLY APPLYING TO SAID MATERIAL A PAIR OF COMPLEMENTARY DIRECT-ACTING, ORGANIC, POLYUREA-FORMING INTERMEDIATES IN SEPARATE PHASES OF LIMITED MUTUAL SOLUBILITY, AT LEAST ONE OF SAID PHASES ALSO CONTAINING A TEXTILE FINISHING AGENT.