US2539366A - Treatment of wool-containing textile materials - Google Patents

Description

umreo STATES PATENT OFFICE TREA T OF WOOL-CONTAINING TEXTILE MATERIALS Linton A. Flock, Jr., Plnckemin, N. 1., and John E. Lynn, Old Greenwich, and Eleanor L. MePhee, Stamford, Conn l-Isignors to American Cyanamid Company, New York, N. Y a corporation 01 Maine No Drawing. Appllcaflon August 1!, 194:, Serial No. 53,904

8 Claims. (GI. 8-1153) This invention relates to the treatment or texsodium hypochlorite), alone or in the presence of tile materials, and more particularly to the treatacidifying ents; alkalies (e. g., sodium or potasment of wool and wool-containing fabric and sium hydroxide) or organic bases, such agents other textile materials to impart improved propbeing used under conditions such that only the erties thereto, specifically increased resistance to 5 surface structure of the wool fibers is altered: shrinking. Still more particularly the invention enzymes such as papain; and reducing agents is concerned with a process of reducing the such as sodium hydrogen sulfide and mercaptoshrinking tendencies of a. wool-containing textile acetic (thioglycolic) acid. Another proposed material which comprises precondition ng the said hrinkage-control proces has involved treating textile material by first treating it with an alkathe wool-containing textile with an aqueous soluline solution, specifically an alkaline aqueous sotion of a heat-curable re which is thereafter lution or an alkaline organic solvent (e. g.. an cured in situ, and then with a chlorine solution. alkaline alcoholic) solution, of a peroxy com- Still another suggested proces has involved first pound (e. g., hydrogen peroxide, an organic or treatng the woolen fabric with an alcoholic inorganic peroxide, a perhorate, a persulfate, etc.) caustic solution in such a manner that there is and thereafter removing the excess alkaline mano intrinsic damage to the fibers and no harmful terial, e. g., by washing the preconditioned texeffect on the hand of the fabric. In the second tile. The pretreated textile, with or without bestep of the process the woolen fabric is impreging dried, is then impregnated with an impregnated with an aqueous solution or dispersion of nant comprising a curable (polymerizable) catia heat-curable amino-aldehyde (e. g., ureaonic aminoplast, more particularly a colloidal soformaldehyde, melamine-formaldehyde, etc.) resiution (specifically an aqueous colloidal solution) in-forming material or precondensate, after 01' a curable, cationic product of reaction of inwhich the impregnated fabric is heated to ingredients comprising an aminotrlazine. e. g., solubiiiae the lmpregnant. (For a more complete melamine, and an aldehyde, e. g., formaldehyde. description of this last-mentioned process, see The colloidal solutions or dispersions of cationic Pfeiler, Jr. et al. Patent No. 2,395,791 wherein aminopiasts used in practicing our invention are also are discussed the prior art processes deacidic, and the glass electrode pH value thereof scribed briefly above and why they 'are objecmay range, for example, between about 0.25 and tionable or fail completely to meet the requireabout 5 or 6, or even as high as 6.8, when the ments of a wool shrinkage-control agent or proccationic aminoplast (for instance, a partially ess.) polymerized, positively charged product of reac- It was also suggested prior to our invention tion of ingredients comprising an aminotriazine, (see British Patent No. 553,923) that wool-cone. g., melamine, and an aldehyde, e. g., Iormaldetainlng textile materials be treated with an hyde) constitutes, on a net dr basis, about 6% aqueous alkaline solution (pH of 8 to 12) of a by weight of the said solution. The cationic substance capable of evolving oxygen (e. g., hyaminopiasts contained in the colloidal solutions drogen peroxide, sodium peroxide, a persulfate, are hydrophilic, and their degree of polymerizaetc.) in order to reduce the tendency of the textlon is less than that which characterizes gels tile to felt and shrink. This treatment may be and precipitates which are undispersible by agiapplied to the textile either before or after it has tation with water but sufllcient to bring the been treated with a sulfur-containing reducing particles thereof within the colloidal range. agent, e. g., sulfur dioxide, a sulfite, a bisulfite, a

Many different methods and agents have been hydrosulflte, etc. (see British Patent No. 579,584)

used or suggested for use in the treatment of Another proposed shrinkage-control treatment fabrics and other textiles composed of or con- 4 (see British Patent No. 564,958) has involved subtaining wool in order to obviate or minimize their jecting the wool-containing textile material to a tendency to shrink on washing. The proposed mild chlorlnatlng o1- brominating treatment contreating agents have included halogens such as trolled at a pH of 4 and then to treatment with chlorine or bromine, solutions of sulfuryl chloanaqueous alkaline solution of hydrogen peroxide. ride, hypochlorous acid, hpyochlorites (e. g., 59 Stillanother proposed method (see British Patent No. 569,730) of imparting shrinkage-resistance characteristics to wool-containing textiles has involved treating the textile with an aqueous solution of a permanganate, e. g., potassium permanganate, and subsequently with either an aqueous solution or suspension of a nitrogenchloro compound, e. g., nitrogen trichloride, monochloroamine, etc., or a dilute aqueous solution of an alkaline hypochlorite or hypobromite.

A process which is now widely used to render woolen and wool-containing textile materials resistant to shrinkage involves treating the textile with an aqueous solution or dispersion of an alkylated, specifically methylated, methyiol melamine, Iollowed by heating the impregnated material to cure the alkylated methylol melamine to a substantially water-insoluble condition. This method is described, for example, in Johnstone, Jr. et al. Reissue Patent No. 22,566.

It was also suggested prior to our invention that the fastness of dyed textile material, specifically cotton, mercerized cotton, ramie, jute, hemp, sisal, silk, artificial silk and wool could be improved by immersing the dyed material, immedi ately after the dyeing thereof, in an aqueous bath consisting of a solution of an aminotriazinealdehyde resin, more particularly a melaminetormaldehyde resin, in a water-soluble stage, which solution has been subjected to the action of a strong mineral acid, specifically hydrochloric acid, for a period of time suflicient to convert the resin into substantive state. The bath contains the amount of resin which it is desired to apply to the textile material, and since the resin is substantive it is exhausted from the solution and deposited on and between the fibers of the textile material. The final step of the process is the dryim of the wet impregnated textile.

The present invention is based on our discovery that a wool-containing textile material including wool itself in fabric or other form can be rendered highly resistant to felting and shrinking by means of a cationic aminoplast which is curable or polymerizable at normal or at an elevated temperature and which is applied in the form of 45 a colloidal solution. more particularly an aqueous colloidal solution, provided that the woolcontaining textile is preconditioned as described briefly in the first paragraph of this specification prior to treatment with the cationic aminonlast, 50

which may be, for example, a cationic (positively charged) methylated or other alkvlated methylol melamine. The instant invention is separate and patentablv distinct from that disclosed and claimed in the copending application oi as Linton A. Fluck, Jr., John E. Lynn and Edward A. Schuman, Serial No. 43,963, filed concurrently herewith, and in which last-named application the'disclosed and claimed invention involves an improvement in a method of reducing the shrinking tendencies of a wool-containing textile material with an aminoplast, more particularly a non-cationic aminoplast, adapted to effect this result, which improvement comprises treating the said textile material with an alkaline solution of a peroxy compound, e. g., hydrogen peroxide, prior to treatment with the said non-cationic aminoplast.

It was wholly unobvious and unexpected that pretreating a wool-containing textile with an alkaline solution of a peroxy compound would make it possible to use a cationic aminoplast as an agent for rendering such textiles highly shrink-resistant. and that. as a result of such pretreatment, a substantially lesser amount of It the various persalts such an aminoplast can be employed as compared with a similar aminoplast which has not been rendered cationic and still obtain a desired degree 01' shrinkage resistance together with other advantages described below. The results are all the more surprising in view of our findings that the combination of treatments produces results quite diflerent from either treatment alone, as shown by examples which follow, and results which are not merely the sum of the individual treatments.

Other advantages flowing from the peroxy pretreatment, and which a so were quite surprising and in no way could have been predicted, include the general uniformity in the results obtained with a given cationic aminoplast in treating a wider variety of textiles composed of or containing a proteinaceous material, specifically wool; and the ability to impart shrink-resistant properties to woolen textiles which heretofore could not be rendered resistant to shrinking to an appreciable Or a commercially satisfactory degree by previously known methods. Still another advantage accruing from our invention is that the applied cationic aminoplast can be dried and cured or polymerized, as by a condensationpolymerization reaction, to its ultimate form (in which form the cured or polymerized aminopiast is no longer dispersible in water to form a colloidal solution or dispersion) at a much lower temperature, for example at temperatures ranging from room temperature (65 F.- F.) to 225 F., as compared with the temperature required for similar aminoplasts which have not been rendered cationic, and still impart the same high order 0! shrink-resistant characteristics to the treated textile. Since the use of lower curing or polymerization temperatures provides a material reduction in the cost of treating the textile, it is immediately apparent that this advantage alone is of great practical significance and commercial importance.

The reasons why the treatment of a wool-containing textile with an alkaline solution of a peroxy compound prior to treatment with a cationic methylated methylol melamine or other cationic aminoplast is abe to produce the valuable and unobvious results above described are not understood. One possible explanation, which is supported by our visual observations, is that the treatment in some way alters the physical and/ or chemical characteristics 0! the wool so that better wetting and/or penetration occurs upon subsequent treatment with a cationic aminoplast. This improvement in wettability and/or penetrability is carried through any subsequent dyeing operation, as evidenced by the fact that no substantial differences in results are obtained when a dyeing step intervenes between the initial preconditioning treatment of the undyed wool-containing textile and the final treatment of the textile with a cationic aminop'ast.

In carrying our invention into effect we first prepare an alkaline solution. preferably an aqueous alkaline solution, of a peroxy compound, more particularly such a compound which, in an aqueous medium, yields hydrogen peroxide or. ultimately, oxygen. Illustrative examples of peroxy compounds that may be employed are hydrogen peroxide and other inorganic peroxides (e. g., sodium, potassium and other alkali-metal peroxides), the organic peroxides (e. g., benzoyl peroxide, acetyl peroxide, lauroyl peroxide, succinyl peroxide, tert-butyl hydroperoxide, etc.), including, for instance, the

8 alkali-metal (e. g., sodium, potassium, etc.), ammonium and other perphosphates, persuli'ates, perborates, percarbonates, etc., these persalts in aqueous solutions forming hydrogen peroxide. Organic peracids (e. g., peracetic acid, perbenzoic acid. etc.) and the alkali-metal and ammonium salts of such acids also may be employed. Other percompounds which may be used include organic and organometallic salts of hydrogen peroxide, for instance tetramethyl, tetraethyl and other tetralkyl ammonium peroxides, triethyl tin peroxide, etc.

The concentration of peroxy compound in the alkaline solution may be varied widely depending, for example, upon the particular wool-containing textile employed, the particular peroxy compound used, the time and temperature of the treatment, etc. In general, however, the peroxy compound is used in an amount equivalent (oxidation equivalency) to at least about 0.05% by weight of hydrogen peroxide, based on the weight of the alkaline solution. Thus, when the peroxy compound is hydrogen peroxide, the alkaline pretreating solution ordinarily contains at least about 0.05%, more particularly at least about 0.1%, and preferably at least about 0.2%, by weight of hydrogen perixide; or, if the peroxy compound charged to the bath is other than hydrogen peroxide, then an amount thereof which is chemically equivalent as an oxidizing agent to at least about 0.05%, more particularly at least about 0.1% and preferably at least about 0.2%, by weight of hydrogen peroxide is employed. In most cases optimum results have been obtained when the concentration of the peroxy compound in the alkaline solution is equivalent to a hydrogen peroxide concentration of at least 0.3%, more particularly at least 0.5 or 0.6% by weight thereof. Higher concentrations of peroxy compound, as for example concentrations equivalent to hydrogen peroxide concentrations of the order of 2.5 or 3% or even 4 or 5% or more may be used if desired, but no particular advantages appear to accrue therefrom. Due to its relatively low cost and ease of handling the preferred peroxy compound is hydrogen peroxide, and generally it constitutes from about 0.3 to about 3%, more particularly from 0.5 to 2.5%, by weight of the alkaline solution, which is preferably an aqueous alkaline solution. Although the preferred alkaline solution of the peroxy compound is an alkaline solution of the said compound in water, other alkaline solutions in which the peroxy compound is soluble may be employed such, for example, as alkaline solutions of the peroxy compound in an alcohol (e. g., a monohydric alcohol such, for instance, as ethanol, propanol, butancl, etc.) or in a mixture of water and an alcohol.

If the peroxy compound employed is of a kind which does not yield an alkaline or a suiliciently alkaline treating bath, then the bath is made alkaline or is brought to a desired degree of alkalinity, as for example a pH of from about 8 to about 12, and more particularly to a pH of between 9 and 11, by the addition of an alkaline material or a material which reacts alkaline in aqueous solution. Any material capable of rendering the treating solution alkaline or of bringing the solution to a desired degree of alkalinity may be used, c. g., the sodium, potassium and other alkali-metal hydroxides, acetates, carbonates and bicarbonates, ammonium hydroxide, amines (e. g., triethanolamine) borax, guanidine carbonate, disodium phosphate, sodium silicates,

0 soap, etc. Mixtures of substances which react basic in the aqueous or other solution of the peroxy compound may be used, if desired, for instance mixtures of such substances as those just mentioned by way of illustration.

The wool-containing textile to be preconditioned is treated with the alkaline solution of the peroxy compound in water or other solvent, preferably a volatile solvent, by any suitable method, for example by immersing the textile in the solution. The treatment may be eflected by continuous, semhcontinuous or batch methods, or by combinations of such methods. For instance, a, wool-containing textile in skein, bolt or other form may be immersed in the treating solution for a period sumcient to efl'ect the desired preconditioning treatment; or, the textile in, for example, the form of a woven fabric may be continuously passed through a bath of the solution at a rate such that it is immersed in the bath for a. period suflicient to efl'ect the desired results. If necessary, as for example when the wool-containing textile undergoing treatment contains free acid, additional basic material may be added to the pretreating bath during the treatment in order to maintain the bath at a desired pH value above 7.

The time of the treatment of the wool-containing textile with the preconditioning solution may be varied considerably. Ordinarily, however, the contact time is at least 15 minutes, although in some cases even shorter periods (for instance periods of the order of 5 or 10 minutes) may be eifective. Better results generally are obtained when the textile is in intimate contact with the preconditioning solution for a period longer than 15 minutes, for example 30 minutes or longer. The time of contact may be 3 or 4 hours, or even as much as 1, 2 or more days in some cases, depending, for example, upon the particular wool-containing textile which is being pretreated, the pH and temperature of the treating solution, the kind and concentration of peroxy compound therein, and other influencing factors. In most cases, however, no particular advantages appear to accrue when the contact time is longer than about 30 minutes, such a contact time usually being as eilective as a contact time of minutes or even of 3 hours when the other conditions including the peroxy compound (e. g., hydrogen peroxide), concentration thereof, alkaline material (e. g., sodium silicate), pH of the solution (e. g., about 10), temperature of the solution, etc., are maintained substantially constant.

The temperature of the preconditioning solution also may be varied considerably but ordinarily it is within the range of about 110 F. to about 160 F., the optimum temperature usually being about 125 F. In some cases, however, the solution temperature may be lower than 110 F., e. g., between or F. and F., or it may be higher than F., e. g., F. or F.

After treating the wool-containing textile with the alkaline solution (preferably an aqueous alkaline solution) of the peroxy compound, the textile is water-washed and/or otherwise treated to remove the excess alkaline material. For example, the treated textile, after squeezing out the excess liquid, may be merely water-washed to remove the excess alkali; or, it may be waterwashed and then rinsed in a dilute acid solution (e.g., a 0.2 to 6 or 8% solution of a mineral acid such, for instance as phosphoric acid or sulfuric acid. or a 0.2 to 10% solution 01' an organic acid such, for example, as formic acid or acetic acid). after which the acid-rinsed textile is washed, e.g., with water, to remove the excess acid and water-soluble salts; or, the initial washing with water may be omitted. and merely a dilute acid rinse followed by a water wash may be used. The cycle of rinsing in dilute acid followed by water washing may be repeated numerous times, if necessary, in order to remove the excess alkaline material from the treated textile.

The preconditioning treatment herein described is applicable to both undyed and dyed wool-containing textiles. When applied to dyed woolcontainlng textiles there is usually some loss of dyestuif, but whether or not this occurs depends, of course, upon the resistance of the particular dyestuif to the alkaline solution of the peroxy compound.

The preconditioned textile may be dyed by any of the methods conventionally used in dyeing wool or wool-containing textiles without detracting from the benefits of the peroxy pretreatment. For instance, wool in yarn, skein, fabric or other form may be dyed by top-chrome, meta-chrome or bottom-chrome dyeing methods. Typcal of such dyeing processes are those briefly described below:

Top-chrome dveina-The dyestufl is applied first to the cloth in a boiling bath. The bath is cooled, a chrome salt (usually sodium or potassium dichromatel added, the bath brought to the boiling point, and then boiled for from 30 to 45 minutes.

Meta-chrome dyeina.-The chrome salt and dyestufl are applied to the wool in the same bath. Dyeing is started cold and finished at the boil.

Bottom-chrome dyeiniL-Wool cloth is first boiled with a chromate in an acidified bath, the chrome color going onto the wool to give a dark green shade. The cloth is then boiled in a bath containing the dyestuil. The finished cloth may be any shade. Or, the wool may be dyed with a metallized dyestuif or an acid dyestull' such as are commonly used in dyeing wool and in accordance with conventional practice. The wool also may be dyed with vat dyes.

The final operation in carrying our invention into effect is the treatment of the preconditioned, dyed or undyed, wool-containing textile with a curable (polymerizable) cationic aminoplast adapted to render the textile resistant to shrinking when the said aminoplast has been sumciently cured (polymerized) at normal or at an elevated temperature, more particularly a colloidal solution (e.g., an aqueous colloidal solution) of a curable (polymerizable) cationic product of reaction of ingredients comprising an aminotria-.

zine, e.g., melamine, ammeline, guanamine, acetoguanamine, etc., and an aldehyde, e.g., formaldehyde. Also suitable for use in practicing our invention are curable, cationic products of reaction of ingredients comprising (1) an aminotriazine, e.g., melamine. (2) urea, or an alcohol, e.g., methanol, ethanol or other mcnohydric alcohol,or both urea and an alcohol, and (3) an aldehyde, e.g., formaldehyde. Ordinarily we use an aqueous colloidal solution of a partially polymerized, positively charged (cationic) product of reaction of ingredients comprising melamine and formaldehyde, which solution has a glass electrode pH value within the range of about 0.25 to about 4.0 when the said reaction product, on a net dry basis, constitutes about by weight of the said colloidal solution. In this colloidal solution the degree of polymerization of the aforementioned positively charged product of reaction of ingredients comprising melamine and formaldehyde is less than that which characterizes gels and precipitates which are undispersible (that is, not permanently dispersible) by agitation with water but is suflicient to bring the particles thereof within the colloidal range. The colloidal solutions employed in the examples which follow have the aforementioned characteristics with respect to pH, degree of polymerisation of the reaction product contained therein, etc.

The colloidal solutions of curable. cationic aminoplasts used in practicing our invention and the cationic aminoplastic themselves are prepared by known methods. Such methods are described in, for instance, wohnsiedler et al. Pat ents 2,345,543 and 2,356,718, Pollard Patents 2,394,009, 2,417,014 and 2,423,428, and in the copending application of Henry P. Wohnsiedler and Walter M. Thomas, Serial No. 516,932, filed January 4, 1944, now Patent No. 2,485,079, and any of the cationic aminoplasts or colloidal solutions thereof disclosed (including those which are claimed per se or are a part of the claimed subject matter) in the aforementioned patents and application may be used in practicing our invention. Alkylated methylol melamines such as are disclosed in Johnstone. Jr. et al. Reissue Patent No. 22,566 may be rendered colloidal by treatment with an acid in a manner such as is described in the aforementioned wohnsiedler et a1. patents and applicat on and also. for example, in the aforementioned Pollard patents.

As is now known, certain aminoplasts including aminotriazine-aldehyde condensation products, when prepared in the presence of definite quantities of free acid (e. g., hydrochloric, phosphoric, pyrophosphoric, nitric, formic, acetic, chloroacetic, etc.) or subsequently reacted with these same quantities of acid after their preparation by other methods, can be converted into colloidal dispersions wherein positive electrical charges are carried by the colloidal particles of the resin. In this condition the resin solutions or colloidal dispersions exhibit the property of migration of the resin particles toward the cathode upon electrophoresis of the dispersion, and this property characterizes all the aminoplast compositions employed in practicing the present invention. (The cataphoresis is preferably carried out by passing a direct current of -120 volts through platinum electrodes immersed in the colloidal solution.) In general, such aminoplast resins or condensation products, which may be designated more specifically as acid-type" aminoplast resins or condensation products, and which include the acid-type aminotriazine-aldehyde condensation products, are readily identifled by the following characteristics:

(1) When freshly prepared they form clear solutions in both water and acids; and

(2) The clear solutions are converted upon aging first to hydrophilic colloids, then to a waterdispersible gel stage, and finally upon drying to a water-insoluble resin.

Other and more specific characteristics of colloidal aqueous solutions of a partially polymerized, positively charged melamine-formaldehyde condensation product are disclosed and included in the claims of the aforementioned Wohnsiedler et al. Patent No. 2,345,543; and characteristics of colloidal aqueous solutions of a partially polymerized, positively charged suanamine-formala dehyde condensation product, in Wohnsiedler et al. Patent No. 2,856,718. As pointed out in these patents, the iormation of a colloidal solution is shown in the first instance by the presence of a definite Tyndall efi'ect under the influence 01' a beam of light or in the dark field microscope. Although the colloidal solution is infinitely dilutable with water it is extremely acid-sensitive, and this constitutes a very delicate test to determine whether any colloidal acid-type resin is present. When a strong acid such as 6N hydrochloric acid is added to a clear, acidified resin solution that has not been aged noimmediate change occurs, but when the acid resin has been aged for a time sumcient to bring even a small part of the resin particles within the colloidal range these particles are precipitated by the addition of the acid. This reaction with strong acids can be used to estimate the degree oi polymerization of the resin solution since the amount of acid necessary for precipitation becomes less with increasing age of the solution.

Illustrative examples of other curable cationic aminoplasts that may be employed in practicing the present invention are given, together with methods of preparing such aminoplasts and colloidal solutions containing the same, in the aforementioned Wohnsiedler et al. copending application Serial No. 516,932. The colloidal solutions disclosed and claimed in this application may be described more particularly as being a colloidal aqueous solution of a resinous copolymer (or intercondensation product) of melamine, urea and formaldehyde, which copolymer contains at least 0.7 mole of melamine for each 4 moles of urea and about 1 to 4 moles of combined formaldehyde for each mole of melamine plus urea and the said copolymer having a degree of polymerization such that the dispersed particles thereof are colloidal in character and size. In such colloidal aqueous solutions a positive electric charge is carried by the dispersed colloidal particles of the copolymer or intercondensation product as shown by their migration toward the cathode upon the passage of a direct current through the solution.

For a more complete understanding of the preparation of colloidal solutions containing ourable cationic aminoplasts that may be used in practicing our invention, reference is made to the above-mentioned Wohnsiedler et al. copendi'ng application Serial No. 516,932 and the aforementioned Pollard Patents 2,394,009, 2,417,014 and 2,423,428 and Wohnsiedler et al. Patents 2,345,543 and 2,356,718, the cationic aminoplast compositions therein disclosed (including those which are claimed) being illustrative of those which can be employed in carrying the present invention into effect.

The curable cationic aminoplast may be applied to the wool-containing textile material in various ways. For example, if the cationic aminoplast is to be applied in the form of an aqueous colloidal solution containing the same, the dry or substantially dry textile to be treated may be immersed in the aqueous colloidal solution containing particles 01' cationic aminoplast of colloidal size, e. g., from, 0.01 to 1 micron in diameter, and then passed through pressure rolls, mangles or centrifugal extractors to secure uniform impregnation and a controlled removal of the excess material. The woolen fabric or other wool-containing textile, however, also may be impregnated by other methods, e. g., by spraying.

The liquid composition (e. g., an aqueous liquid r composition) containing the curable cationic aminoplast in the form of a colloid is diluted with a suitable diluent or dispersion medium (e. g., water), ii necessary, to yield a finishing composition having the concentration of solids desired tor textile application. Thus, the concentration of solids in the liquid composition may be, for instance, from about 1 to about 20% by weight of the composition depending, for example, upon the particular diluent or mixture of diluents employed, method of expression of the .1 wet, impregnated textile, etc. Ordinarily, however, the curable cationic aminoplast constitutes from about 3 or 4% to about 10 or 12% by weight of the liquid is. g., aqueous) finishing composition. The diluent or dispersion medium for the curable cationic aminoplast may be varied depending, for example, upon the characteristics of the said aminoplast, but in the case oi the preferred cationic aminoplasts it is usually water; or it may be, for instance, a mixture of water and an alcohol, e. g., ethyl alcohol, glycerol, etc.

The pick-up oi the liquid (e. g., aqueous) finishing composition by the wool-containing textile material should be adjusted so that the finished textile contains an amount of cured aminoplast sui'ficient to impart shrinkresistant characteristics thereto which at least are adequate to meet the minimum commercial requirements. This will vary somewhat depending, for instance, upon the particular wool-containing textile being treated, the particular preconditioning treatment which has been given to it, the particular aminoplast employed, the particular properties desired in the finished textile, etc. Ordinarily, however, the pick-up is adjusted so that the amount of aminoplast in the finished textile is not more than about (usually only about V: or less) as much by weight as that required to obtain the same shrinkage-resistant characteristics in the absence of the preconditioning treatment. For example, the pick-up of the liquid finishing composition by the woolcontaining textile material may be adjusted so that the finished textile contains from about 1 or 2% to about 6 or 8%. more particularly from about 3% to about 5%, by weight of the dry textile, oi the cured (polymerized) aminoplast which, prior to curing is a curable (polymerizable) cationic (positively charged) aminoplast. In some cases, as for instance in the case of those woolen or wool-containing textiles which normally are not amenable to treatment with a cationic aminoplast alone to yield a commercially satisfactory shrink-resistant textile, the pick-up oi the liquid finishing composition may be ad- Justed so that the finished textile contains as much as 10% or even about 15% or more, by weight of the dry textile, or the cured aminoplast. The amount of aqueous or other liquid finishing composition picked up by the textile. that is. the so-called "wet pick-up, may be varied as desired or as conditions may require and may range, for examplepfrom about 30 or 40% up to about 150% or more by weight of the dry textile depending, for example, upon the particular textile treated, method and conditions of treatment, concentration of solids in the impregnating bath, amount of solids and properties desired in the finished textile, etc. When the woolen fabric or other wool-containing textile material is impreghated with by weight of the dry textile, oi the textile-finishing composition, the impregnated textile will contain, after drying and ouring oi the curable cationic aminoplast, nearly may be varied the same of cured aminoplast as the percentage oi curable cationic aminoplast which is present in the textile-finishing composition.

The wet. impregnated woolen fabric or other wool-containing textile material is then dried and cured. The drying and curing temperatures considerably, but ordinarily temtherangeofaboutfib'or'id' F. up to about 225 or 250 F. are employed. In some casesdryingand curingmaybeeifectahif desired. at room temperature (65 l t-85 R). Thetlmeoi dryingandcuringmaybeshortened by increasing the temperature, for example to temperatures of the order of 180 F. to 212 F.

peratures within 300 F. or 350 F.orcvenashighas400F.or more. As has been pointed out hereinbeiore one of the main advantages accruing from the use oi a curable cationic aminoplast as herein described is the lower drying and curing temperature that can be employed as compared with the temperature required for similar aminoplasts which have not been rendered cationic. and still impart the same high order of shrink-resistant characteristics to the treated textile. In all cases the dryingandcuringtemperatureandperiodare sufllcienttodrytheh'eatedtextileandtoadvance the cure or polymerization of the curable or polymerizable cationic aminoplast contained therein substantially beyond the stage which characterizes a gel, the cured or polymerized amlnoplast being substantially water-insoluble and being incapable of yielding a stable. aqueous colloidal solution or dispersion.

The drying and curing operation is flexible and may be varied to suit the available equipment. Continuous methods are preferred. However,drying and curing also may be eflected by framing the impregnated fabric to width, as on a pin tender, drying the framed fabric, batching it upon a shell and then aLowing it to stand at normal or at an elevated temperature for a period sufllcient to advance the cure or polymerization of the solid impregnant in situ to its ultimate form. In some cases drying and curing for from 2 hours to about 100 hours at temperatures within the range of about 65 F. to about 200 F. may be required. Heating the dried fabrlc at higher temperatures ranging from a few seconds to a few minutes at highertemperatures of the order of 212 F. to 250 F. or 300 F. or even as high as 400 F. or higher may be employed, the shorter periods being used at the higher temperatures.

After the woolen fabric or other wool-containing textile material has been treated as above described, it may be given a mild soaping treatment to render it softer and more pliable. It then may be given the usual finishing treatments such as decatizing, brushing, shearing, pressing. etc. Our process may be applied to wool and wool-containing. textile materials, e. g., unwoven wool, yarns, worsteds, flannels, shirting, felts, knit or woven goods and others, and these may be composed of all wool or partly of wool and partly of another fibrous material, e. g., cotton. silk, any of the various rayons, any of the various other synthetic flbers inc.uding nylon, polyacrylonitrile fibers, fibers produced from casein, soya beans, etc.

In order that those skilled in the art better may understand how the present invention may be carried into eflect, the following examples are given by way oi illustration and not by way or and percentages are by Example 1 The textile material used in this example was 100% all wool, women's wear flannel weighing ll ounces per square yard. Pieces of this flannel, 9 inches by 23 inches in size, and which had been suitably marked for the purpose of measuring limitation. All parts weight.

shrinkage after washing, were treated as described below:

A. A sample of the flannel was immersed for 30 minutes in an aqueous alkaline solution containing 0.6% by weight of hydrogen peroxide and which had been rendered alkaline to a pH of about 10 with sodium silicate. The solution was maintained at a temperature of about 125 F. during the treating period. The treated flannel was removed from the bath, rinsed first in water. then in a dilute (about 1%) aqueous solution oi acetic acid and again in water, squeezed through a padder and then dried on a frame, while holding it to its original size of 9 inches by 23 inches, for about 6 to 10 minutes at about 225-2-i0 F.

8. Another sample oi the flannel was impregnated by immersing it for at least about 1 minute in an aqueous colloidal solution containing about 6% by weight of the acetic acid colloid of methylated methylol melamine, more particularly methylated trimethylol melamine. The solution also contained 0.01% of a, wetting agent, specifically a reaction product of an ethanolamide of a long chain fatty acid and ethylene oxide. The wet flannel was then squeezed through a. padder to yield an impregnated cloth in which the wet pick-up was about 100% by weight of the dry flannel. after which the sample was framed to size as in A, and then heated for 10 minutes at 225 F. to dry the fabric and to advance the cure or polymerization of the colloidal methylated methylol melamine to a substantially completely cured or polymerized state, in which state it is substantially water-insoluble.

The acetic acid colloid of the methylated methylol melamine, more particularly methylated trimethylol melamine, was prepared as follows:

1 Parts Commercial methylated trimethylol melamine (about solids, water constituting most oi. the remainder) Water 883 Glacial acetic acid 42 were mixed together and then allowed to stand undisturbed at room temperature (about B5- F.) for about 6 hours. The resulting aqueous colloidal solution contained about 6% by weight of the acetic acid colloid of methylated trimethylol melamine. The glass electrode pH value of the aqueous colloidal solution was 3.3.

C. A sample of the flannel was preconditioned as described under A, followed by treatment as described under B.

D. Same as C with the exception that the wet impregnated flannel was heated for 9 minutes at 290 F. to dry the fabric and to advance the cure of the acetic acid colloid oi. methylated methylol melamine as described under B.

After cooling to room temperature each of the samples of A, B, C, and D was removed from the frame and given 10 washings (soapings) oi 10 minutes each at F. in accordance with Federal Specifications CCC-T-l9la. After steam pressing and conditioning for about 16 hours at 70 F. and 65% relative humidity, the samples were measured tor shrinkage in inches per yard.

which values were then changed to percentages. Thewarpshnnkageinpercentcieachoi'the treated samples, together with that of the untreated sample which had been similarly washed, are shown below. Other shrinkage values given inotherexamplesweredeterminedinasimilar manner.

Thetextilematerialusedinthisexamplewas a Neolan dyed, 100% all wool flannel which weighed 8 ounces per square yard. It is typical of woolen fabrics which are less amenable to treatment with a methylated methylol melamine alone or with an acetic acid colloid a methylated methylol melamine than the flannel used in Example 1. The treatments were as follows:

A. SameasA 0! Example 1. B. SameasBoiExample 1. C. BameasCol Example 1. D. sameascotltxampleiwiththeexception that the aqueous colloidal solution oi the acetic acid colloid oi the methylated methylol melamine contained about 2% (instead 0! about 6% as in 1-0) 01' the said colloid.

E. same as C of Example 1 with the exception that the aqueous colloidal solution of the acetic acid colloid of the methylated methylol melamine contained about 4% (instead of about 6% as in 1-0) of the said colloid.

The treated flannels and a control sample were washed as described under Example 1. The shrinkage data on the treated and washed sampics are shown below, together with tensile strength data on the untreated sample and on the treated samples of A, B, and C.

Tensile fltrength in Warp Pounds Treatment Shrinkage inPerCent Warp Filling no 33.0 I10 trample 3 This example illustrates the results obtained when various temperature conditions are used in drying and curing the impregnated woolen textile. The woolen goods employed was a Neolan dyed woolen flannel such as was used in Example 2. The treatments were as follows:

14 thatthedyedi'abriaatterbeingimpreansted with the aqueous colloidal solution containim about 6% by weight oi. the acetic acid colloid oi' methylated methylol melamine, was dried and cured at room temperature (about 65'-85 1".) for about 18 hours.

B. Same as C of Example 1 wherein the impregnated textile was dried and cured for 10 minutes at 225' I C. sameascoinxamplelwiththeexcepticn that the temperature at which the imp snated 2utiiewasdriedandcuredifavrlliminuteswas D. samesscoinxamplelwiththeexception thattheimpregnatedtextilewasdriedandcured for 9 minutm at 290' I".

'lhe treated tunnels and a control sample were washed as described under Example 1. The shrinkage data on the treated and washed samples are shown 'below:

Treatment been:

Emple This example illustrate the diii'erences in the curing of polymerization conditions that can be used and the results obtained when a peroxide pretreated wool-containing textile is treated with an ordinary aqueous solution of a methylated methylol melamine and with aqueous colloidal solutions oi an acid colloid, more particularly an acetic acid colloid, of the same methylated methylol melamine. The textile was an undyed womenswear liannel, all wool. weighing 8 ounces per square yard. The treatments were as follows:

A. A sample of the flannel was preconditioned by treatment with an aqueous alkaline solution of hydrogen peroxide as described under A oi Example 1. The preconditioned fabric was impresnated by immersing it for about 1 minute in an aqueous solution containing about 5% by weight of methylated methylol melamine, more particularly methylated trimethylol melamine. The solution also contained, by weight, 0.155% of a curing catalyst. specifically diammonium hydrogen phosphate, and 0.03% o! a wetting agent, specifically dioctyl sodium sulfosuccinate. The wet flannel was then squeezed through a padder to yield an impregnated cloth in which the wet pick-up was about 100% by weight oi the dry. flannel, after which the sample was framed to size as in l-A, and then heated for 10 minutes at 225 F. to dry the fabric and to advance the cure oi the methylated methylol melamine as described under l-B.

Another sample was treated as above described with the exception that the impregnated flannel was heated for 9 minutes at 290 F.

B. Same as A oi this example with the exception that the preconditioned flannel was impregnated with an aqueous colloidal solution of an acetic acid colloid of the same methylated methyl- A. sameascoi Example lwiththeexception 5 olmelamineusedinA;als0,thcaqueollscollddll 15 solution contained about 4% by weight of the said colloid instead of about 5% of solids as in A of this example, and 0.01% 01' a non-ionic wetting agent, more particularly a reaction product of an ethanolamide of a long chain fatty acid and ethylene oxide. The wet impregnated textile was heated for minutes at 225 F. as described in the first paragraph of A oi the present example.

Other samples were treated as above described with the exception that each 01' the impregnated fabrics was heated under different conditions, via, 10 minutes at 250 F. and 275 F., and 9 minutes at 290 F.

C. Same as]; with the exception that samples of the woolen flannel were impregnated with the same acetic acid colloid in a concentration 0! about 6% by weight or the aqueous colloidal solution instead of about 4%. Each oi the impregnated flannels was heated under diil'erent conditions. vlz., 30 minutes at 180 F.. 10 minutes at 225 F. and 9 minutes at 290 F.

The treated fiannels and a control sample were washed as described under Example 1. The shrinkage data on the treated and washed samples are shown below:

Warp Shrinkage in Per Cent, Sample Dried and Cured atwhen undyed wool-containing textile materials are to be rendered resistant to shrinking in accordance with our invention, a preferred preconditioning treatment includes the step of rinsing the peroxy pretreated textile with a dilute acid solution as hereinbeiore described, followed by a water rinse. Under the usual conditions prevailing in a textile mill wherein the acid colloid is applied to a dyed textile, such an acid rinse is unnecessary since the wool is generally dyed in an acid (e. g., sulfuric or acetic acid) medium.

The following example illustrates the results obtained using a peroxy pretreating operation wherein, in one case, the peroxy-pretreated fabric was rinsed in a dilute acid solution and, in another case, the acid rinse was omitted.

Example 5 Varp Shrinkage Treatment in Per Cent It is not necessary that the wool-containing textile material be dried after completion oi the alkaline peroxy pretreatment. In other words the pretreated, washed and squeezed, impregnated textile may be treated while still wet with the aqueous colloidal solution oi the acid colloid. This is shown by the following example.

Example 6 The textile material used in this was a dyed woolen flannel such as was used in Example 2. The treatments were as follows:

A. Same as D of Example 2 with the exception that the woolen fabric, after treatment with the aqueous alkaline solution containing 0.6% by weight oi hydrogen peroxide and subsequent rinsing as therein described, was immersed directly, without being dried, in the aqueous colloidal solution containing about 2% by weight of the acetlcacid colloid oi methylated methylol melamine.

B. Same as A of this example with the exception that the aqueous colloidal solution contained about 4% by weight of the actetic acid colloid.

C. Same as A of this example with the'exception that the aqueous colloidal solution contained about 6% by weight of the acetic acid colloid.

The treated fiannels and a control sample were washed as described under Example 1. The shrinkage data on the treated and washed samples are shown below:

wargshrlnkage None A It will be noted that the shrink-resistant properties of the treated flannels are of the same order as those of the treated fabrics or C, D, and E 0! Example 2.

Example 7 This example illustrates the preparation and use, in accordance with our invention, of an aqueous colloidal solution containing a hydrochloric acid colloid of methylated methylol melamine, more particularly methylated trimethylol melamine.

A x. Parts 1581?, Ratio Commercial methylated trimethylol melamine gbout m soiids, water constituting most of e Aquarius hydrochloric acid (about 38% HCl)-.- Water 17 textile material resistant to shrinking as described below. The woolen material was a women's wear flannel such as used in Example 1.

A. Same a C of Example 1 with the exception that the above-described aqueous colloidal solution containing the hydrochloric acid colloid of methylated trimethylol melaminewas used instead of the corresponding acetic acid colloid. The wet, impregnated fabric was dried and cured for 10 minutes at 225 F. Another alkaline hydrogen peroxide pretreated sample (B) was dried and cured for 30 minutes at 180 F., while a third, similarly pretreated sample (C) was dried and cured for 9 minutes at 290 F.

The treated samples and a control sample were washed as described under Example 1. The shrinkage data on the treated and washed samplw are shown below, together with tensile strength data on the untreated sample and on the This example illustrates the preparation and use, in accordance with our invention, of an aqueous colloidal solution containing a phosphoric acid colloid of methylated methylol melamine, more particularly methylated trimethylol melamine.

Approx. Parts Molar Ratio Commercial meth lated trimetb lol melamine (about 80% soil water const tuted most of the remainder) 25 1. Phosphoric acid (85% H:P0|) l3 1. 4 Water- 102 were mixed together and then allowed to stand undisturbed at room temperature (about 65 F.- 85 F.) for about hours. The resulting aqueous colloidal solution contained about 10% of solids, which thereafter was diluted with water to a solution containing about 6% of solids, and used as described in the preceding example instead of the hydrochloric acid colloid of that example. The glass electrode pH value of the aqueous colloidal solution containing 6% solids was 1.5. One wet, impregnated sample (A) was dried and cured for 10 minutes at 225" F., while another sample (B) was dried and cured for 9 minutes at 290 F. After being washed ten times as described under Example 1, the warp shrinkage in percent of each of the treated samples was 4.7. The warp shrinkage in per cent of a control (untreated) sample, after having been similarly washed ten times, was 20.0.

Example 9 This example illustrates the preparation and use, in accordance with our invention, of an aqueous colloidal solution containing a hydrochlo ric acid colloid of a melamine-formaldehyde reaction product, more particularly trlmethyiol melamine.

were mixed together and then allowed to stand undisturbed at room temperature (about 65- F.) for about 8 hours. The resulting aqueous colloidal solution contained about 11.5% of solids. One part was diluted with water to yield a colloidal solution, (A) containing about 2% of a hydrochloric acid colloid of trimethylol melamine. Similarly, water was added to another part to form a colloidal solution (B) containing about 4% of the said colloid. Both solutions were applied to an alkaline hydrogen peroxide preconditioned woolen fabric as described under Example 8. The wet, impregnated fabrics were dried and cured for 9 minutes at 290 F. After bein washed ten times as described under Example 1, the warp shrinkage in per cent of the fabric which had been treated with the colloidal solution (A) containin 2% of the colloid was 4.2, while that of the fabric which had been treated with the colloidal solution (B) containing 4% of the colloid was 5.6. The warp shrinkage in per cent of a control sample, after having been similarly washed ten times, was 20.0.

Example 10 The process of our invention is applicable to a wide variety of woolen textile materials, as shown by the following results of treating six different woolen fabrics. The treatments were as follows:

A. Same as C of Example 1.

B. Same as D of Example 1.

(The treatments of A and B involved a pretreatment of the fabrics with an aqueous alkaline solution containing 0.6% hydrogen peroxide and a finishing treatment with an aqueous colloidal solution containing about 6% of the acetic acid colloid of methylated trimethylol melamine. In the A treatment the wet, impregnated textile was dried and cured for 10 minutes at 225 F., while in the B treatment it was dried and cured for 9 minutes at 290 F.) The warp shrinkage in per cent of the untreated and treated fabrics, after being washed ten times as described under Example 1, are shown below:

Warp Shrinkage in Per Cent oi Woolen Fabrics was doses:

Nora-Fabrics l, 2 and 3 were undyed women's wear flannel, all wool, weighing 8 ounces per square yard. Fabrics 4 and 5 were Palatine dyed and top-chrome dyed, respectively, sulfuric acid carbonized woolen fabrics (100% all wool weighing about 12 ounces for square yard, while Fabr c 6 was an undfed, all wool, sulfuric acid carbonized fabric which also we ghed about 12 ounces per square yard.

Optimum results in practicing our invention are obtained by using a peroxy pretreating so- 19 lution which not only is distinctly alkaline when the wool-containing textile material initially is immersed therein but which is maintained alkaline during the entire period the woolen material is in the pretreatin bath. This is shown by the following example.

Example 11 The general method of treatment was the same as described under C of Example 1.

The woolen fabrics treated in A and B were sulfuric acid carbonized woolen materials and contained excess sulfuric acid. In A the pH of the pretreating solution was not controlled. while in B additional sodium silicate was added to the hydrogen peroxide pretreating solution during the treating period so that the pH of the solution did not fall below 9.

Example 12 The woolen fabric which was treated in this example was a Neolan dyed, 100% all wool flannel which weighed 8 ounces per square yard. Instead of using hydrogen peroxide in the pretreating bath as in the previous examples, a different peroxy compound, via, sodium perborate, was employed. The treatments were as follows:

A. The woolen fabric was preconditioned by immersing it in an aqueous alkaline solution containing 1% by weight of sodium perbo'rate. No sodium silicate was added to the bath since the sodium perborate alone brought the bath to a pH of about 10. The flannel was allowed to remain in the bath for 30 minutes while maintaining, the solution at 125 F. The treated flannel was removed from the bath. rinsed in water to remove the excess alkali, squeezed through a padder and then dried on a frame, while holding it to its original size of 9 inches by 23 inches, for 10 minutes at 240 F. The dried flannel was impregnated by immersing it for at least about 1 minute in a textile-finishing composition comprising an aqueous solution containing about 5% by weight of methylated methylol melamine, more particularly methylated trimethylol melamine. The solution also contained, by weight, 0.155% of a curing catalyst, specifically diammoniu-m hydrogen phosphate, and 0.03% of a wetting agent, specificaliy dioctyl sodium sulfosuccinate. The wet flannel was then squeezed and framed as described under B of Example 1, after which it was heated for 9 minutes at 290 F. to dry the fabric and to advance the cure of the methylated methylol melamine as described under 113.

B. Same as A of this example with the exception that the textile-finishing composition comprised an aqueous colloidal solution containing 5% of an acetic acid colloid (prepared in a manner similar to that described under 1-3) of methylated trimethylol melamine. The solution contained no added curing catalyst, but did contain 0.01% of a non-ionic wetting agent, more particularly a reaction product of an ethanolamide of a long chain fatty acid and ethylene oxide.

The treated flannels and a control sample (un treated flannel) were subjected to washing in soap solution, more particularly five washing cycles of 10 minutes each followed by drying, and then were washed for 1 hour followed by drying. The data on shrinkage of the treated and washed samples are shown below:

Treatment Example 13 The woolen fabric treated in this example was a womens wear flannel such as was used in Example 1. The treatments were as follows:

A. The flannel, without any preconditioning treatment, was treated with an aqueous colloidal solution containing 5% of the acetic acid colloid of methylated trimethylol melamine and 0.01% of a non-ionic wetting agent as described under A of Example 12.

B. Same as A or this example with the exception that the aqueous colloidal solution contained 10% of the acetic acid colloid.

C. Same as B of Example 12 with the exception that the aqueous alkaline pretreating solution contained 0.6% hydrogen peroxide and had been rendered alkaline to a pH of about lo with sodium silicate. The textile-finishing composition comprised an aqueous colloidal solution containing 5% by weight thereof of an acetic acid colloid of methylated trimethylol melamine.

D. Same as C of this example with the exception that the aqueous colloidal solution contained 10% of the acetic acid colloid of methylated trimethylol melamine.

The treated flannels and a. control sample were washed as described under Example 12. The data on shrinkage of the treated and washed samples are shown below:

Warp Shrinkage in Per Cent Alter 5 Washin; O 0123 of 10 M utes Each of Additional Washing Example 14 The same woolen fabric was treated as was used in Example 13. The treatments were as follows:

A. Same as A of Example 12 with the exception that the aqueous alkaline pretreating solution contained 0.6% hydrogen peroxide and had been rendered alkaline to a pH of about 10 with sodium silicate; also, the textile finishing composition comprised an aqueous solution containing only about 2 /2% of methylated trimethylol melamine, about 0.08% of diammonium hydrogen phosphate and about 0.03% of dioctyl sodium sulfosuccinate as a wetting agent.

B. The pretreating solution and method were the same as A of this example, while the finishing treatment also was the same with the exception that the textile finishing composition contained 2i 2%% of an acetic acid colloid of methylated trimethylol melamine (see 1-8 for method of preparation) and the same kind and amount of wetting agent as described under B of Example 12.

The treated samples and a control sample were washed as described under Example 12. The shrinkage data on the treated and washed samples are shown below:

3 Warp Treatment B Cent 1 None.. 21.1 A ll. 8 B 3. 3

I After 6 Washing Cycles of 10 Minutes Each Followed by 1 Hour of Additional Washing.

Example A. Same as A of Example 12 with the exception that the aqueous alkaline pretreating solution contained 0.6% hydrogen peroxide and had been rendered alkaline to a pH of about 10 with sodium silicate; also, the preconditioning bath was maintained at a temperature of 100' l". for 8 hours instead of at 125 F. for minutes as in l2-A. The textile-finishing composition contained about 5% by weight of methylated trimethylol melamine and the same kind and amount of curing catalyst and wetting agent as in 12-A.

B. Same as A of this example with the exception that the textile-finishing composition comprised an aqueous colloidal solution containing 6% of an acetic acid colloid (prepared in a manner similar to that described under 1-3) of methylated trimethylol melamine. The solution also contained 0.01% of a non-ionic wetting agent such as described under 143.

C. Same as A of this example with the exception that the alkaline hydrogen peroxide pretreating bath was maintained at a temperature of about 80 F. for about 24 hours.

D. Same as B of this example with the exception that the preconditioning solution was maintained at about 80 F. for about 24 hours.

The treated flannels and a control sample were washed as described under Example 12. The shrinkage data on the treated and washed samples are shown below:

I After 6 Washing Cycles of 10 Minutes Each Followed by 1 Hour of Additional Washing.

Example 16 This example illustrates the use of other peroxy compounds, specifically sodium peroxide and potassium persulfate, as components of the pre- 22 conditioning bath. The woolen fabric was the sameasthatusedinExample 1. Thetreatmente were as follows:

A. Same as D of Example 1 with the exception that the pretreating bath contained bi: by weight of sodium peroxide. The sodium peroxide alone brought the solution to a pH of about 10 and no other alkaline material was added.

B. Same as D of Example 1 with the exception that the preconditioning solution contained 1% by weight of potassium persulfate. Sodium silicate was added in an amount sumcient to bring the pretreating bath to a pH of about 10.

The treated flannels and a control sample were washed as described under Example 12. The shrinkage data on the treated and washed sampics are shown below:

The textile material used in this example was all wool, undyed women's wear flannel similar to that used in Example 1. The treatments were as follows:

A. Same as C of Example 1, which involved pretreatment of the fabric with an aqueous alkaline solution containing 0.8% by weight of hydrogen peroxide and rendered alkaline with sodium silicate to a pH of about 10, and subsequent treatment of the dried, undyed fabric with an aqueous colloidal solution containing 6% by weight of an acid colloid of methylated trimethylol melamine.

B. Same as A of this example with the exception that after preconditioning the undyed fabric as in A but omitting the acetic acid rinse. it was dyed as follows: The dried, pretreated cloth was immersed for 1 hour in a dye bath maintained at boiling temperature and containing 3% of a dye (Calcocid Violet 4 Bx, Color Index No. 698) 4% of acetic acid (approx. 28% CHsCOOH) and 7% of Glaubers salt, the percentages of dye, acetic acid and Glaubers salt being by weight and being based on the weight of the dry fabric. After rinsing the dyed textile in water, followed by drying, the dyed and dried fabric was treated with an aqueous colloidal solution containing 6% by weight of an acetic acid colloid of methylated trimethylol melamine as in A of this example.

The treated ilannels were washed as described under Example 1, with the exception that each was given only 5 washings of 10 minutes each. The shrinkage data on the treated and washed After 5 Washing Cycles of 10 Minutes Eseb.

It will be understood, of course. by those skilled in the art that our invention is not limited to the particular preconditioning compositions, curable cationic aminoplasts and conditions of treating a wool-containing textile with these compositions as has been given by way of illustration in the above examples, since the pretreating solution, the ilnal textile-finishing composition and the application conditions may be widely varied as will be apparent from the description in this specification prior to the examples.

The terms textile" and textile material as used gen rally herein and in the appended claims include within their meanings filaments, fibers. rovings, slivers, threads, yarns, twisted yarns, etc., as such or in woven felted or otherwise formed fabrics, sheets, cloths and the like.

We claim:

1. A process of reducing the shrinking tendencies of a wool-containing textile material which comprises preconditioning the said textile material by first treating it with an alkaline solution of a peroxy compound and thereafter removing the excess alkaline material, impregnating the preconditioned textile with an impregnant comprising a colloidal solution of a curable cationic aminoplast, and advancing the cure of the said aminoplast in situ, the amount of the cured aminoplast with which the said textile material i impregnated being suiilcient to render it resistant to shrinking.

2. A process as in claim 1 wherein the alkaline solution of the peroxy compound is within a pH range of 8 to 12.

ii. A process as in claim 1 wherein the impregnant comprises a colloidal solution of a curable, cationic product of reaction of ingredients comprising melamine and formaldehyde.

4. A process of reducing the shrinking tendencies of a dyed woolen fabric which comprises preconditioning the undyed fabric by first treating it with an aqueous alkaline solution of hydrogen peroxide and thereafter removing the excess alkaline material, dyeing the preconditioned fabric, impregnating the dyed fabric with an aqueous colloidal solution of a partially polymerized, positively charged product of reaction of ingredients comprising melamine and formaldehyde, said colloidal solution having a glass electrode pH value within the range of 0.25 to 6.8 when the said reaction product, on a net dry basis, constitutes about 6% by weight of the said colloidal solution, and the degree of polymerization of the said reaction product being less than that which characterizes gels and precipitates which are undispersible by agitation with water but suiilcient to bring the particles thereof within the colloidal range, and polymerizing the said reaction product in situ to its ultimate form, the polymerized reaction product being substantially water-insoluble, and the amount or the said reaction product in polymerized state with which the fabric is impregnated being from 1 to by weight of the dry fabric.

5. A process oi. reducing the shrinking tendencies of a dyed, wool-containing textile which comprises immersing the undyed textile in an aqueous solution rendered alkaline to a pH of between 8 and 12 and containing hydrogen peroxide in an amount corresponding to from 0.05% to 3% by weight of the said solution and thereafter removing the excess alkaline material thereby to precondition the undyed textile, dyeing the preconditioned textile, impregnating the 24 dyed textile with an aqueous colloidal solution of a partially polymerized, positively charged alkylated methylol melamine, said colloidal solution having a glass electrode pH value within the range or about 0.25 to about 4.0 when the said alkylated methylol melamine, on a net dry basis, constitutes about 6% by weight of the said colloldal solution, and the degree of polymerization oi the said alkylated methylol melamine being less than that which characterizes gels and precipitates which are undispersible by agitation with water but suiilcient to bring the particles thereof within the colloidal range, drying the wet imnregnated textile and polymerizing the said alkylated methylol melamine contained in the impregnated textile to its ultimate degree of polymerization, said drying and polymerization being efiected at a temperature not exceeding 400 F., and the amount of the said alkylated methylol melamine in polymerized state with which the textile is impregnated being from 1 to 15% by weight of the dry textile.

6. A process as in claim 5 wherein the colloidal solution contains methylated methylol melamine rendered colloidal with acetic acid.

7. A process as in claim 5 wherein the alkylated methylol melamine is methylated methylol melamine, and the wet impregnated textile is dried and the methylated methylol melamine contained in the impregnated textile is polymerized to its ultimate degree of polymerization at a temperature within the range of about 65 F. to about 300 F.

8. The method of reducing the shrinking tendencies of a woolen textile material which comprises immersing the said material in undyed state i'or from Y; to 3 hours in an aqueous solu-,

tion rendered alkaline to a pH of between 9 and 11 and containing hydrogen peroxide in an amount corresponding to from 0.5 to 2.5% by weight of the said solution thereby to precondition the said textile material, said solution being maintained at a temperature of from 70 F. to F.; removing the excess alkaline material from the preconditioned textile; impregnating the preconditioned textile from which the excess alkaline material has been removed with an aqueous colloidal solution of a partially polymerized, positively charged methylated methylol melamine rendered colloidal with acetic acid, said solution containing from about 2% to about 12% by weight of the said methylated methylol melamine and having a glass electrode pH value within the range of about 0.25 to about 4.0 when the said methylated methylol melamine, on a net dry basis, constitutes about 6% by weight of the said colloidal solution, and the degree of polymerization of the said methylated methylol melamine being less than that which characterizes gels and precipitates which are undispersible by agitation with water but suiilcient to bring the particles thereof within the colloidal range; adjusting the pick-up of the said aqueous colloidal solution by the said preconditioned textile so that the amount of cured methylated methylol melamine in the finished textile is not more than about three-fourths as much by weight as that required to obtain the same shrinkprooiing characteristics in the absence of the aforedescribed preconditioning treatment; drying the wet impregnated textile and polymerizing the said methylated methylol melamine contained in the impregnated textile to its ultimate degree oi polymerization, said drying and polymerization 25 29 being eflected at a temperature within the range Number Name me of about 65 F. to about 225 F. 2,329,651 Powers Sept. 14, 1943 LBTION A. FLUCK, JR. 2,395,724 Cowley Feb. 28, 1946 JOHN E. LYNN. 2,395,791 Ptetl'er Feb. 28, 1948 ELEANOR L. MCPHE'E. 5 2,423,429 Pollard July 1, I947 REFERENCES CIT D 2.467.293 Rust Apr. 12, 1949 The following references are of record In the FOREIGN PA H 8 me or this mm: 10 33305 o 1 3 121 A 2519 rea r n pr. UmDNmAm 553,923 Great Britain 1943 Number lime be assen Schweitzer Aug. 30, 1921 OTHER mm 2,070,210 Mason Feb- 9, 1937 Matthews: Bleaching and Related Processes, 2,107,297 Kaufl'mann Feb. 0, 1939 15 Chemical Catalog Co., New York, 1921, pages 2,238,949 Schlack Apr- 1941 187-145. (Book in Division 48;) 2,329,622 Johnsfone flept. 14, 1943

Claims (1)

1. A PROCESS OF REDUCING THE SHRINKING TENDENCES OF A WOOL-CONTAINING TEXTILE MATERIAL WHICH COMPRISES PRECONDITIONING THE SAID TEXTILE MATERIAL BY FIRST TREATING IT WITH AN ALKALINE SOLUTION OF A PEROXY COMPOUND AND THEREAFTER REMOVING THE EXCESS ALKALINE MATERIAL, IMPREGNATING THE PRECONDITIONED TEXTILE WITH AN IMPREGNANT COMPRISING A COLLOIDAL SOLUTION OF A CURABLE CATIONIC AMINOPLAST, AND ADVANCING THE CURE OF THE SAID AMINOPLAST IN SITU, THE AMOUNT OF THE CURED AMINOPLAST WITH WHICH THE SAID TEXTILE MATERIAL IS IMPREGNATED BEING SUFFICIENT TO RENDER IT RESISTANT TO SHRINKING.