US3150000A - Method and means for treating textiles - Google Patents

Description

United States Patent 3,150,000 METHOD AND MEANS FOR TREATING TEXTILES Heinz Enders, Stadtbergen, near Augsburg, Hans Ruile, N eusass, near Augsburg, Hans Karl Wiest, Gersthofen, and Hans Deiner and Eugen Kurz, Augsburg, Germany, assignors to Chemische Fabrik Pfersee G.m.b.H., Augsburg, Germany, a firm of Germany No Drawing. Filed Aug. 8, 1961, Set. N0.129,952 7 Claims. (Cl. 117-139.5)

This invention relates to a method of treating textiles, and is more particularly concerned with textile finishing methods.

Tex-tile materials can 'be made stain repellant, and particularly oil and grease repellant, by treating them with aqueous solutions or dispersions of organic compounds which contain a plurality of perfluoroalkyl radicals, each radical'having'at least four carbon atoms. The stain and oil resistance of such treated textiles and other fibrous material are impaired by laundering at elevated temperatures. The aforementioned perfluoroalkyl compounds also impart some water repellency to the treated material, but'the water repellency achieved does not satisfy the usual commercial requirements. -It is anadditional shortcoming of textile treating baths prepared from known solutions or dispersions of perfluoroalkyl compounds that they tend to form coatings on the rolls of padding ma- :chines and similar apparatus employed in the impregnation of textiles with the solution. Such coatings must be removed from time to time to avoid staining of the treated goods, and continuous operation is very difficult if at all possible.

It has now been found that the aforementoined disadvantages of the known perfluoroaikyl compounds can be overcome while fully retaining their favorable effects on textiles by adding additional materials to the aqueous solutions or dispersions of these compounds. The aqueous textile treating baths of the invention contain as active ingredients a first organic compound having a plurality of perfiuoroalkyl radicals, each radical having at least four carbon atoms; a secondorganic compound which is .an amine derivative having at least two urea radicals connected by alkylene radicals having two to four carbon atoms, a plurality of methylol radicals, and at least one alkyl radical of at least ten, and preferably of eleven to twenty-two carbon atoms, the methylol radicals and the last mentioned alkyl radical being bound to the nitrogen atoms of the urea radicals; and a third organic compound which is-a water insoluble precondensate of an aminotriazine having at least two amine radicals on the triazine ring which is free of directly attached hydroxyl groups, with formaldehyde and a monohydric lower alkanol having one to five carbon atoms. The precondensate which is soluble in dilute monocarboxylic lower alkanoic acids contains for each triazine ring at least one alkyl radical having more than ten, and preferably 11 to 22carbon atoms, and at least 0.2 mol equivalent of the basic amino groups of an alkanolamine of the formula wherein .R is'hydrogen, an alkyl radical having one to four carbon atoms, a hydroxyalkyl radical having two to four carbon atoms, the radical --CH -CH -NR R droxyalkyl radical having two to four carbon atoms; and R is hydrogen or ahydroxyalkyl radical having twoto four.carbon atoms.

The lower aikanoic acids'in which the aforementioned precondensates are soluble include formic and acetic acids.

.tinuous; padding possible. -in the stain. and oil repellentproperties of the treated ma- .terial, and the finish produced has substantially increased .or vinyl radical.

integer between one and three.

3,150,000 Patented Sept. 22, 1 964 ice resistance to laundering.

In the treatment of textile materials with an improved treating bath of the invention, the material is saturated with the aqueous dispersions or solutions of the organic chemical compounds, the excess liquid is removed, the textile material is dried atabout C., and the resin forming materials are cured at temperatures of about t to C.

The known perfiuoroalkylcompounds which may be employed in the method of the invention include the water-soluble chromium coordination complexes of saturated perfluoroinated monocarboxylic acids or substituted carboxylic acids which contain at least one perfiuoroalkyl radical of at least four carbon atoms, and have been'disclosed in U.S. Patent No. 2,662,835; also the waterdispersible basic aluminium salts of saturated perfluorinated monocarboxylic acids or substituted carboxylic acids which contain at least one perfluoroalkyl radical with at least four carbon atoms; the water dispersible polymers or copolymers of esters of 1,1-dihydroperfluoroalkanols with acrylic acid as disclosed in US. Patent No. 2,642,416; aqueous dispersions of polymers or copolymers, the monomer units having the formula RrS0zN-R"CHg-OZ wherein R is a perfluoroalkyl radical having at least four carbon atoms, R is hydrogen or an aliphatic hydrocarbon radical having one to six carbon atoms, R is an aliphatic hydrocarbon radical having one to twelve carbon a atoms, and Z is a radical of acrylic or methacrylic acid; and aqueous dispersions of polymers or copolymers, the monomer units having the formula R -SOgN-R"C 0 OX wherein-R R", and R represent the above radicals, and X is a polymerisable radical such as an allyl, methallyl The expression copolymer means that at least 50 mol percent of the monomer units have a periluoroalkyl group of at least 4 carbon atoms.

The amine derivatives suitable for the method of the invention may be prepared by reacting an amine having at least two basic nitrogen atoms carrying each at least one hydrogen atom, and connected by saturated divalent alkylene radicals having two to four carbon atoms, to gether with at least one mol of urea for each mol of the amine at about 130 C. until between 1.0 and 1.3 mols ammonia are liberated per mol urea, disolving the reaction product in water, and mixing the aqueous solution at about40 C. with an alkyl isocyanate the alkyl radical -of which has more than ten, and preferably eleven to twenty-two carbon atoms, the quantity of isocyanate employed being at least one molfor each mol of the reaction product. Finally, at least two mols formaldehyde are added in the form of a neutral aqueous solution.

The amine employed in preparing the amine derivative has the formula wherein): is aninteger between two and four, and y is an Diethylene triamine is the preferred amine employed, but all alkylene diamines and polyalkylene :po;lyamines :which satisfy the above formula are operative.

triazine such as melamine is heated to 110 to 140 C. to-

gether-with one to two mols of an aliphatic monocarboxylic acid having more than ten, and preferably 15 to 19 carbon atoms; 6 to 18 mols, and preferably 915 moles paraformaldehyde; 0.2 to 1.2, and preferably 0.5 to 1.0 mol of an alkanolamine, preferably of the formula wherein R is a hydroxyalkyl radical having 2 or 3 carbon atoms, and R is hydrogen, or a hydroxyalkyl radical having two or three carbon atoms; and with a monohydric lower alkanol having one to five carbon atoms. The volatile ingredients are permitted to distill off during heatting, and the residue is further heated until a sample becomes clearly soluble in a dilute monocarboxylic lower alkanoic acid, and more specifically in hot 5 to percent aqueous acetic acid.

The aliphatic monocarboxylic acid having more than ten carbon atoms may be replaced in the above reaction by an equavalent amount, that is, by one half to one mol of the corresponding anhydride.

The same precondensates are arrived at when the aminotriazine and the aliphatic monocarboxylic acid having more than then carbon atoms or the anhyride of the latter are replaced by an aminotriazine derivative in which one to three hydrogen atoms of the amino groups are replaced by aliphatic acyl radicals having more than ten, and preferably to 19 carbon atoms.

According to another method, a methylolaminotriazine, and particularly a methylol melamine is etherified with a lower alkanol having one to four carbon atoms. One mol of the etherified methylol melamine is reacted with one to two mols of a monocarboxylic aliphatic acid having more than ten carbon atoms, preferably 15 to 19 carbon atoms, at a temperature of 130 to 200 C. Heating is preferably continued until substantially the entire fatty acid is present in the combined form. This reaction may be performed at ambient pressure or in a vacuum. The intermediate product obtained is heated with 0.2 to 1.2 mols, preferably 0.5 to 1.0 mol of an alkanolamine which preferably has the formula wherein R, and R represent the radicals indicated above, to a reaction temperature of 100 to 130 C., until the condensation product formed is soluble in a dilute aqueous monocarboxylic alkanoic acid such as acetic acid.

According to yet another method, one mol of a 2,4- diamino-6-alkyl-1,3,5-triazine 1 is heated with paraformaldehyde preferably in amounts of 5 to 8 mols, with 0.2 to 1.2 mols, and preferably with 0.4 to 1.0 mol of an alkanolamine which is preferably of the formula wherein R, and R have the same meaning, and with a lower monohydric alkanol having one to five carbon atoms. The volatile constituents are permitted to distill from the reaction mixture, and heating is continued until the product is soluble in a dilute monocarboxylic acid, and

V particularly in hot five to ten percent aqueous acetic acid.

The alkyl radical has more than 10, particularly 1122 carbon atoms.

A further method of synthesizing the pre-condensates of the invention starts with an aminotriazine derivative which is obtained by reacting one mol of a compound of the formula wherein E is hydrogen, amino radical, alkyl radical with 1 to 22 carbon atoms; with at least 1 mol of an alkyl isocyanate per mol of said aminotriazine derivative and at most one mol of said alkyl isocyanate per equivalent amino radicals. Especially used are derivatives obtained by heating one mol of melamine with 1.2 to 2 mols of said alkylisocyanate.

The alkyl radical of said alkyl isocyanate has more than ten, and preferably fifteen to nineteen carbon atoms.

The reaction is performed at 200 to 260 C. until a clear liquid is obtained.

One mol of this intermediate aminotriazine derivative obtained is heated to to C. with six to eighteen (preferably nine to fifteen) mols paraformaldehyde, 0.2 to 2.0 (preferably 0.7 to 1.5) mols of an alkanolamine, preferably of the formula wherein R,, and R have the same meaning, and a lower monohydric alkanol having at most five carbon atoms and preferably four carbon atoms. The volatile constituents are permitted to evaporate from the solution, and heating is continued until the product is soluble in dilute monocarboxylic acids, such as hot five to ten percent aqueous acetic acid.

The test for completion of the precondensation reaction may be performed most conveniently with 5 to 30 percent aqueous solutions of formic or acetic acid. The test is carried out by adding the precondensation product to the hot aqueous solution of the carboxylic acid, or by adding the pre-condensate to the acid solution in the cold, and by heating the mixture.

In making up a textile treating bath, we prefer to employ 6 to 10 gr. per liter of the perfiuoroalkyl compounds. A concentration of 2 to 15 gr. will be satisfactory in most instances.

The amount of the amine derivative may be between 1 and 15 gr. for best results although these limits are not critical, and the concentration of the water-insoluble precondensate is preferably of the order of 1 to 10 gr. per liter. Those skilled in the art will appreciate that these concentration figures do not constitute limits of operativeness, but are merely provided for guidance while the nature of the material treated will determine optimum values of concentration for the effect which may be desired. Amounts of the precondensate as small as 0.2 percent based on the weight of the amine derivative present have a clearly observable beneficial effect on the storage life of the treating baths, and reduce the tendency of the bath to coat squeeze rolls on processing machinery.

The water insoluble precondensates are preferably premixed with approximately equal weights of substantially water insoluble liquid organic solvents such as hydrocarbons andhalogenated hydrocarbons, or with materials of similar chemical composition such as waxes and paraffin which themselves are finishing agents that make fabric water repellent.

It is generally more convenient to prepare a textile treating bath from pre-mixed concentrates of the amine derivatives with the solvent diluted precondensates in the manner described in our copending application Serial No. 127,903, filed July 31, 1961, now US. Patent No. 3,116,-

263. Such concentrates are distinguished by their stability in storage.

Finishing treatment with the baths of the invention can be combined with conventional wrinkle proofing treatments which are commonly applied to fibrous cellulosic materials made both from native cellulose and from rayon. The treating baths then contain not only the combination of organic compounds of the invention, but also the conventional polymerizable resin forming compounds and suitable polymerizaiton catalysts. The simultaneous presence of wrinkle proofing resins on the treated cellulosic fibers further enhances their resistance to staining and to water. The combined treatment is also beneficial to fibrous materials which do not essenitally consist of cellulose.

The resin forming polymerizable compounds which are compatible with the treating baths of the invention include the usual precondensates of formaldehyde with urea, melamine, ethylene urea, triazones, and the like, their ethers, and mixtures thereof.

The catalysts that may safely be employed for curing the precondensates in the presence of the combination of compounds of the invention include the ammonium salts of strong acids, and such divalent metal salts as magnesium chloride, zinc chloride, Zinc nitrate, as well as salts of multivalent metals, for example, aluminium or zirconium. The textile materials are treated in the combined treating baths in the same manner as described hereinbefore.

Where a particularly soft hand and exceptional draping qualities are desired, the treating method of the invention may be further modified by adding to the treating baths of the invention small amounts of dispersions of N- alkyl-N,N-alkylene ureas having an alkyl radical of more than ten, preferably of 11 to 22 carbon atoms, and most conveniently of 15 to 18 carbon atoms and whose alkylene radicals have two or three carbon atoms. The dispersions may be stabilized by added non-volatile, strongly basic compounds, or volatile bases in combination with quaternary ammonium compounds of the formula wherein A is an alkyl radical having more than 10 carbon atoms, B is pyridine or hydroxyethyl morpholine, and D is the monobasic anion of an acid. The dispersions are added to the treating bath in an amount to make the concentration of the N-alkyl-N',N'-alkylene urea about one to five grams per liter.

The dispersions of the N-alkyl-N',N'-alkylene ureas are more convenient to handle and have better shelf life when they contain the afore-described preco-ndensates, as has been more fully disclosed in U.S. Patent No. 2,302,- 283.

The term, textiles and other fibrous materials as used herein, will be understood to include woven and knitted fabrics as Well as felt and other non-woven fabrics, paper and the like, yarns and threads, as well as loose fibers and the intermediate agglomerations of fibers produced in the course of the transformation of fibers into fabrics. The term will also be understood to cover fiber forming materials of natural or synthetic origin.

The textiles and other fibrous materials treated according to the invention are dstinguished by their water and oil repellency, but also by their stain resistance. Surface stains produced by alcoholic beverages including red wine, by coifee, meat sauces, butter, oils, and tar can be wiped olf with a rag moistened with water or a conventional stain removing solvent. The solvent is not absorbed by the treated textile material, and thus doesnot form unsightly rings.

The invention will be further illustrated by examples of specific embodiments thereof, but the invention is not limited to the examples. In these examples, reference Will be had to water repellency and oil repellency ratings of treated materials. Water absorption is reported as tested on the Bundesmann apparatus, and water repellency ratings are assigned asfollows:

Excellent water repellency means no sign of wetting after ten minutes testing on the Bundesmann apparatus:

Good water repellency means that signs of incipient wetting are shown after ten minutes;

No Water repellency is the rating applied to fibrous material wetted after ten minutes.

Oil repellency is reported as tested by placing drops of different mixtures of purified mineral oil (Nujol) and n-heptane on the fabric or fibrous material. The drop containing the highest percentage n-heptane which does not wet the tested materials determines the rating on an arbitrary scale as follows.

Parts and percentages in the examples are by weight unless stated dilferently. All temperatures are in degrees EXAMPLE 1 103 partsof diethyiene triamine and parts of urea are mixed in a flask. The mixture is heated with stirring to about When the temperature exceeds 95 to 100, the mixture becomes a clear liquid. At the same temperature evolution of ammonia begins. The ammonia liberated is absorbed in an amount of 5 N sulfuric acid equivalent to 40 parts ammonia. As soon as the acid is neutralized by the ammonia, the contents of the flask are poured on a plate and solidify on cooling. 50 parts of this reaction product are dissolved in 505 parts of water at about 40. parts of octadecyl isocyanate are added over a period of fifteen minutes with continuous stirring. A dispersion is formed and is stirred fifteen minutes longer at 40, and then for an hour at 70. parts of a neutral, aqueous 37 percent solution of formaldehyde are added with constant stirring, and the temperature is held at about 70 for 15 minutes. Upon cooling, a paste-like dispersion is obtained.

EXAMPLE 2 The procedure of Example 1 is repeated, but the amount of octadecyl isocyanate is increased to 190 parts. A similar dispersion is finally formed.

EXAMPLE 3 146 parts of triethylene tetramine and parts of urea are reacted by heating as in Example 1 until 60 parts of ammonia are developed. The condensation product is dissolved in 2660 parts of water at about 40 and reacted with 560 parts of heptadecyl isocyanate at that temperature for 15 minutes with vigorous agitation, and then further for about an hour at 70. 650 parts of 37 percent formaldehyde solution are added whereby a milky dispersion is obtained which is stirred for 20 minutes at about 70, and then cooledto room temperature.

EXAMPLE 4 60 parts ethylene diamine and 120 parts urea are reacted as described above until 34 parts of ammonia are evolved. 50 parts of the reaction product are dissolved in 500 parts of water, and are further reacted with 135 parts of octadecyl isocyanate, and then with 110 parts of 37 percent formaldehyde solution under the time and temperature conditions specified in the preceding examples.

7 EXAMPLE 370 parts of methanol, 69 parts of triethanolamine, 187 parts of paraformaldehyde, and 63 parts of melamine are mixed in a three neck flask equipped with a descending condenser, a stirrer, and a thermometer. The temperature is slowly raised with vigorous agitation. When the temperature reaches 40, 225 parts of technical stearic anhydride (acid number 3-7) are added, and the temperature is gradually raised to 120 over a period of 2 to 3 hours While the alcohol is permitted to distill ofi". The latter temperature is maintained until a sample of the product is clearly soluble in hot 6 percent acetic acid.

Respective parts of the melt poured from the flask are mixed with equal weights of paraffin and of trichloroethylene. Upon cooling to room temperature, the paraffin mixture is a yellowish brown waxlike mass, whereas the mixture with trichloroethylnee is a yellowish brown liquid.

EXAMPLE 6 182 parts of methanol, 35 parts of triethanolamine, 90 parts of paraformaldehyde, and 190 parts of a technical grade of l,3-diamino-5-hexadecyl-2,4,6-triazine which consists of 80 percent of the pure compound, the remainder being a mixture of fatty acid nitriles having an average molecular Weight of 255, are mixed in a flask as in Example 5, and heated to 140 to 145 in about two to three hours. The alcohol partly distils oif during heating. The maximum temperature is maintained until a sample of the product is clearly soluble in hot 6 percent acetic or formic acid.

Portions of the liquid contents of the reaction vessel are respectively, mixed while hot with equal Weights of parafiin, and of a mixture of one part by volume of tetrachlorethylene and three parts by volume of benzene.

EXAMPLE 7 One mol melamin and two mols heptadecyl isocyanate are heated to 240 in a three neck flask fitted with a stirrer, reflux condenser, and thermometer, until the reaction is completed. 150 parts of the reaction product are mixed in the flask with 525 parts isobutanol, 35 parts diethanolamine, and 90 parts paraformaldehyde, and are refluxed for three hours. The reflux condenser is replaced by a descending condenser and the temperature is slowly raised to 150 to 155 over a period of two to three hours. The excess of alcohol is permitted to distil off. When a sample of the contents of the flask becomes soluble in hot 6 percent acetic acid, heating is discon tinned.

Portions of the hot precondensate are mixed respectively with equal weights of paraflin and of toluene.

EXAMPLE 8 100 parts dipalmitoyl melamine, 55 parts paraformaldehyde, 200 parts propanol, and 20 parts triisopropanolamine are stirred and heated to about 140 to 145 in the same manner as in the preceding examples until the product is soluble in hot 6 percent acetic acid. The

product is mixed with 150 parts of monochlorobenzene.

EXAMPLE 9 Sample pieces of a cotton poplin are respectively saturated With different finishing baths, are extracted to a pick up of approximately 65 percent of a three roll padder, dried in an oven at 120, and cured five minutes at 150.

The cotton fabric which is of the type commonly employed for rain coats weighs 160 grams per square meter prior to the treatment, it has 58 yarn threads per cm. (Nm. 77), and 24 filling threads per cm. (Nm. 65).

Finishing Bath A 40 grams of the paste like dispersion of Example 1 are mixed with 2 g. of 60 percent acetic acid, then with approximately five volumes of water at 80, and finally with five volumes of cold water, and the mixture is added to a solution containing 200 g. water, 25 g. isopropanol and 15 g. isobutanol.

5 g. of the solution of the product of Example 6 in tetrachlorethylene and benzene is mixed with 2.5 g. of 60 percent acetic acid, and ten volumes of water are gradually added to the mixture With vigorous stirring. The emulsion obtained is added to the above solution. 25 g. of an aqueous 30 percent emulsion of a perfluoroalkyl compound are last added to the composition in small amounts with stirring, and the volume is finally adjusted to 1000 ml. by the addition of cold water.

The perfluoroalkyl compound is the polymerization product of the monomer of the formula Finishing Bath B The procedure used in preparing bath A is followed but g. of a formaldehyde melamine precondensate containing about 68 percent hexamethylolamine etherified about 80 percent with methanol is dissolved in the solution of isopropanol and isobutanol in water before the dispersion of Example 1 is added thereto. Before the final volume is adjusted to 1000 ml., ml. of a 10 percent solution of magnesium chloride hexahydrate are carefully added with agitation.

Finishing Bath C TABLE I B ath Initial After day After laundering cleaning Oil repellency Water absorption Water rcpeilency Recovery angle (average of warp and filling).

During application of baths A and B no desposits are formed on the rolls of the padder. During application of bath C a coating is formed on the rolls which make pad ding difiicult after a very short run.

EXAMPLE 10 A nylon fabric having a linen weave and weighing 48 g. per square meter (45 warp threads per cm, 38 filling threads per cm., both Nm. 207) is saturated with the finishing hath given below, extracted to a pick-up of 55 percent, dried at 120, and cured at for five minutes.

The bath is prepared as follows:

40 g. of the product of Example 2 are mixed by stirring with 4 g. of 60 percent acetic acid, then with five volumes of water at 80. The mixture is added to 500 g. water containing 25 g. isobutanol.

10 g. of the mixture of a precondensate with parafiin produced according to Example 1, and 10 g. water are jointly heated until the paraflin mixture is molten, 2 g. cold 60 percent acetic acid are added with vigorous agitation, and the dispersion formed is diluted with five times its volume of water of 70 to 80 added in small portions.

Five additional volumes of cold water are added, and the resulting diluted dispersion is added to the first prepared solution.

Alternately, g. of the solvent solution produced in Example 7 are directly stirred into 40 g. of the product of Example 2, and the mixture to which 4 to 5 g. cold 60 percent acetic acid are added, is diluted with small portions of hot water and then added to the mixture of water and isobutanol.

To each of the two dispersions so obtained, there are added 30 g. of an approximately 30 percent aqueous emulsion of a polymeric perfiuoroalkyl compound which is a co-polymer of 80 mol percent of the monomer of Example 9, and 20 mol percent butadiene.

When finished with either the paraffin mixture or the solvent solution of Example 7, the nylon fabric has an initial water repellency rating of excellen which is not changed by three laundry runs at 40 using a detergent solution containing 2 grams per liter of a fatty alcohol sulfonate.

The initial oil repellency rating is 100+++ with both finishes, and is not materially reduced by three launderings with soap. Neither finishing bath causes any difficulties on the padder in extended runs. No coatings are deposited on the rolls.

EXAMPLE 11 A cotton poplin of the type usually employed for rain wear is padded to 65 percent pick up on a three roll padder with a finishing bath, dried on a Dungler flat frame at about 120 to 130, and finally cured on a Haas curing machine at 150 in five minutes.

The finishing bath is prepared as follows:

24 kg. of a liquid formaldehyde precondensate containing about 35 percent dimethylol ethylene urea and 20 percent of a hexamethylol melamine etherified about 80 percent with methanol are mixed with 12 liters isopropanol and then with 72 liters of cold water. 16 kg. of the product of Example 1 are mixed with 0.8 kg. of 60 percent acetic acid, and then with a fivefold volume of water at 70 to 80 which is added in small portions with vigorous agitation, and is followed by another fivefold volume of cold water. The solution obtained is added to the solution of the precondensate.

4 kg. of the paraifin mixture obtained in Example 5 and an equal amount of water are jointly heated to 80 whereby the paraffin mixture is molten. 1.8 kg. of 60 percent cold acetic acid are added with strong agitation, then five volumes of water at 80 to 90 in small portions, and finally five volumes of cold water. The mixture obtained is combined with the previously mixed solutions.

24 kg. of an aqueous percent solution of magnesium chloride hexahydrate are added to the combined liquids, and 10 kg. of the co-polymer emulsion described in the receding example are admixed with good agitation. The total volume of the bath is adjusted to 400 liters.

Several thousand meters of the cotton poplin are padded with this bath at normal padding machine speeds in a continuous run without any difiiculties from deposits or coatings on the rolls.

After being dried and cured in the usual manner, the

" fabric has a water repellency rating of excellen which is not measurably affected by three laundry operations with soap. The original oil repellency is 100+-|-+, and is reduced by the laundry treatment only to a value of 100.

EXAMPLE 12 A finishing bath having the same processing characteristics is obtained when the bath of 400 liters of final volume is made up from the following materials:

8 kg. of the product of Example 3;

1.6 kg. of the solvent containing product of Example 5 emulsified by sequential admixture of 0.8 kg. cold 60 percent acetic acid and 24 liters of water added in small portions;

'10 40 kg. of a dilute aqueous dispersion of an alkylalkylene urea the preparation of which is described below;

36 kg. of a 50 percent solution of dimethylol ethylene .urea;

4 kg. magnesium chloridehexahydrate; and

10 kg. of the aqueous emulsion of a polymeric perfluoroalkyl alkyl compound of Example 9.

The procedure of Example 11 is followed in combining the above materials with each other and with water.

The finished cotton poplin has practically the same oil and water repellency properties as that treated in Exam- .ple, 11, but the addition of the alkyl-alkylene urea to the treating bath gives it a soft hand and excellent drape properties.

The afore-mentioned aqueous dispersion of an alkylalkylene urea is prepared in the following manner:

28.5 parts ethylenirnine are diluted with 125 parts distilled water and are mixed at 20 with a solution of 45 parts of a polyethylene glycol ether (obtained by reacting glycerol triricinoleate with 30 mol equivalents of ethylene oxide) in 126.5 parts distilled water and 15 parts ammonium hydroxide solution (d. 0.90). A solution is formed. While itis vigorously stirred and cooled, 200 parts octadecylisocyanate are slowly added drop by drop. Afterthe reaction is completed, 450 parts distilled water and 10 parts ammonium hydroxide solution are added, and the mixture is homogenized by means of a high speed agitator. The solution is .made up to 1000 parts by the addition of a solution of 66 parts octadecyloxymethylene-hydroxyethyl morpholinium chloride in 134 parts distilled water. The dispersion formed is diluted prior to use with an equal volume of .Water which is added carefully in small portions.

EXAMPLE 13 A wool gabardine having a twill weave, Weighing 300 g. per square meter, and having 27 warp threads (Nrn. 19) and 20 filling threads ('Nrn. 22) per cm. is saturated with the finishing bath described below, extracted to a pick-up of percent, dried at to and cured five minutes at The finished woolen fabric has a water repellency rating of excellen a water absorption of 19 percent, andan oil repellency of 100+. The water repellency rating is not changed by laundering the fabric three times at 40, and only little reduced by three dry cleanings. The oil repellency is not affected by laundering nor by dry cleaning.

The treating bath is prepared as follows:

100 parts of the product of Example 4 when freshly prepared and still at a temperature of 50 are mixed with one part ofthe product of Example 8. The mixture is cooledto room temperature. 3 g. thereof are mixed with 0.15 g. 60 percent acetic acid, diluted by gradual addition of 15 g. hot water of 80, and further with 15 g. cold water. The solution obtained is added to 700 g. water containing'25 g. isobutanol. 25 g. of the emulsion of the perfluoroalkylene polymer of. Example'9 are last added with good agitation.

The bath may be modified by substituting equal amounts of the solvent bearing products of Examples 5, 6, or.7 for the product of Example 8. The properties of the finished textile material are not'significantly altered by the substitution.

1 EXAMPLE 14 .additionof 3. got 60 .percent acetic acid, dispersed in fivevolumes of water at. .80", and finally added to.500. g. water containing .25. g. isobutanol. 5g. .of the paraffin bearing product of Example 7 are solubilized with 2.5 g.

60 percent acetic acid, diluted with hot and cold water and combined with the aqueous solution first prepared in the same manner as described in more detail in Example 10. Finally, 25 g. of the copolymer emulsion of Example are added.

The fabric is saturated with the bath, extracted to 65 percent pick-up, dried at 120, and cured five minutes at 150.

The water repellency after the treatment is excellent, the oil resistency 100+++. Both ratings deteriorate only insignificantly after repeated laundering and dry cleaning.

Practically the same water and oil repellency is obtained together with a firmed hand if so desired when the treating bath additionally contains 80 grams of a methylol melamine ether-ified with methanol as described in Example 9, and 12 g. magnesium chloride hexahydrate.

EXAMPLE 15 100 parts of the product according to Example 1 are mixed with 2 parts of the solvent containing product of Example 5 and homogenized afterwards. 5 gr. of this aqueous dispersion are mixed with 0.25 gr. of a cold aqueous 60% solution of acetic acid and with good stirring gr. of water of 70 C. are added in small portions and afterwards diluted with 25 gr. of cold water.

This diluted dispersion is stirred into a mixture of 40 gr. isobutanol and 400 gr. cold water. Thereafter are added 35 gr. of a solution of a chromium coordination complex obtained in accordance with Example 1 of the US. Patent 2,662,835 and cold water to make 1000 ml.

With this treating bath a woolen fabric is soaked, squeezed to a pick-up of 80%, dried at about 100 C. and cured for 5 minutes at about 130 C.

The finished fabric has initially a water absorption of 23.7% with good water repellency properties and an oil repellency of 100. These effects are only slightly diminished by laundering or dry cleaning.

It should be understood of course that the foregoing disclosure relates to only preferred embodiments of the invention and that numerous modifications or alterations may be made therein without departing from the spirit and the scope of the invention as set forth in the appended claims.

What we claim is:

1. A method of finishing a textile material and like fibrous material, which comprises, in combination, impregnating said material with an aqueous bath containing a first organic compound which is a polymeric compound having a plurality of repeating groups, at least 50 mol percent of said groups including perfluoroalkyl radicals having at least four carbon atoms; a second organic compound which is an amine derivative having at least two urea radicals connected by an alkylene group having two of four carbon atoms, a plurality of methylol radicals and an alkyl radical having more than ten carbon atoms, said methylol radicals and said alkyl radical being bound to V the nitrogen atoms of said urea radicals; and a third wherein R is selected from the group consisting of hydrogen, an alkyl radical having one to four carbon atoms, a hydroxyalkyl radical having two to four carthird organic compound has a concentration in said bath of 0.002 to 10 grams and is prepared by heating one mol of a 2,4-diamino-6-alkyl-1,3,5-trizine having a 6-alkyl radical of 15 to 19 carbon atoms, with 5 to 8 mols paraformaldehyde, 0.3 to 0.8 mol of an alkanolamine of the formula wherein R is a hydroxyalkyl radical having two to three carbon atoms, and R is selected from the group consisting of hydrogen and hydroxyalkyl radicals having two to three carbon atoms, and with a monohydric lower alkanol to a temperature of about 130 to 160 C. until the product formed is soluble in hot 5 percent acetic acid.

3. A method as set forth in claim 1, wherein said third organic compound has a concentration of 0.002 to 10 grams in said bath and is prepared by reacting 1 mol melamine with 1 to 2 mols of an alkyl isocyanate having an alkyl radical of 15 to 18 carbon atoms at a temperature of about 200 to 260 C. until the reaction mixture is a clear liquid, and heating said reaction mixture with 9 to 15 mols paraformaldehyde, 0.7 to 2.0 mols of an alkanoiamine of the formula Rr-IIT-Ih Rb wherein R is a hydroxyalkyl radical having two to three carbon atoms, and R is selected from the group consisting of hydrogen and hydroxyalkyl radicals having two to three carbon atoms, and with a monohydric lower alkanol to a temperature of about to 140 C. until the product formed is soluble in hot 5 percent acetic acid.

4. A method as set forth in claim 1, wherein said bath further contains a fourth organic compound which is an N-alkyl-N',N'-alkylene urea, the alkyl radical of said fourth organic compound having more than ten carbon atoms, and each of the alkylene radicals of said fourth compound having two to three carbon atoms.

5. A textile material treated according to claim 1.

6. A textile material treated according to claim 4.

7. A method as set forth in claim 1, wherein said first organic compound has a concentration of 2 to 15 grams per liter in said bath and is a polymeric compound having a plurality of repeating groups, at least 5 0 mol percent of said groups being radicals of a compound of the formula RF- O2NRCHrO-Z wherein R is a perfluoroalkyl radical having at least four carbon atoms, R is a member of the group consisting of hydrogen and aliphatic hydrocarbon radicals having one to six carbon atoms, R" is an aliphatic hydrocarbon radical having one to twelve carbon atoms, and Z is a member of the group consisting of acryloyl and methacryloyl radicals; said second organic compound has a concentration of one to fifteen grams per liter in said bath and is prepared by heating two mols urea with one mol diethylenetriamine to a temperature of approximately C. until 1.0 to 1.3 mols ammonia are driven off, dissolving the material obtained in water to produce an aqueous solution, mixing said aqueous solution with 1 to 2 mols of an alkyl isocyanate having an alkyl group of 15 to 18 carbon atoms, and reacting the reaction product so obtained with 3 to 5 mols formaldehyde in an aqueous medium; said third organic compound has a concentration of 0.002 gram to 10 grams in said bath and is prepared by heating one mol melamine with a reactant 13 14 selected from the group consisting of one to two mols to a temperature of about 110 to 140 C. until the product of a fatty acid and one half to one mol of a fatty acid formed is soluble in hot 5 percent acetic acid. anhydride, with nine to fifteen mols of paraformaldehyde, with 0.5 to 1.0 mol of an alkanolamine of the formula References Cited in the file Of this Patent 5 UNITED STATES PATENTS 2,314,968 Bestian et a1. Mar. 30, 1943 2,642,416 Ahlbrecht et a1. June 16, 1953 wherein R is a hydroxyalkyl radical having two to three 2,662,835 Reid Dec. 15, 1953 carbon atoms, and R is selected from the group consist- 2,803,615 Ahlbrecht et a1. Aug. 20, 1957 ing of hydrogen and hydroxyalkyl radicals having two to 10 2,864,781 Albrecht at 1958 three carbon atoms, and with a monohydric lower alkanol 3,006,896 Horst et a1. Oct. 31, 1961

Claims (1)

1. A METHOD OF FINISHING A TEXTILE MATERIAL AND LIKE FIBROUS MATERIAL, WHICH COMPRISES, IN COMBINATION, IMPREGNATING SAID MATERIAL WITH AN AQUEOUS BATH CONTAINING A FIRST ORGANIC COMPOUND WHICH IS A POLYMERIC COMPOUND HAVING A PLURALITY OF REPEATING GROUPS, AT LEAST 50 MOL PERCENT OF SAID GROUPS INCLUDING PERFLUOROALKYL RADICALS HAVING AT LEAST FOUR CARBON ATOMS; A SECOND ORGANIC COMPOUND WHICH IS AN AMINE DERIVATIVE HAVING AT LEAST TWO UREA RADICALS CONNECTED BY AN ALKYLENE GROUP HAVING TWO OF FOUR CARBON ATOMS, A PLURALITY OF METHYLOL RADICALS AND AN ALKYL RADIAL HAVING MORE THAN TEN CARBON ATOMS, SAID METHYLOL RADICALS AND SAID ALKYL RADICAL BEING BOUND TO THE NITROGEN ATOMS OF SAID UREA RADICALS; AND A THIRD ORGANIC COMPOUND WIHICH IS A WATER INSOLUBLE PRECONDENSATE OF AN AMINOTRIAZINE WITH FORMALDEHYDE AND A MONOHYDRIC LOWER ALKANOL, SAID AMINOTRIAZINE HAVING AT LEAST TWO AMINO RADICALS DIRECTLY BOUND TO THE TRIAZINE RING THEREOF, SAID RING BEING FREE OF DDIRECTLY BOUND HYDROXYL RADICALS, SAID PRECONDENSATE BEING SOLUBLE IN A DILUTE AQEUOUS MONOCARBOXYLIC LOWER ALKANOIC ACID AND HAVING FOR EACH TRIAZINE RING AT LEAST ONE ALKYL RADICAL OF MORE THAN TEN CARBON ATOMS, AND AT LEAST 0.2 MOL EQUIVALENT OF THE BASIC AMINE GROUP OF AN ALKANOLAMINE OF THE FORMULA