US3438925A

US3438925A - Stabilized oil- and water-repellent composition

Info

Publication number: US3438925A
Application number: US567049A
Authority: US
Inventors: Stuart Raynolds; Thomas K Tandy Jr
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 1966-07-22
Filing date: 1966-07-22
Publication date: 1969-04-15
Anticipated expiration: 1986-04-15

Description

United States Patent U.S. Cl. 26029.4 5 Claims ABSTRACT OF THE DISCLOSURE The addition of a compound of the structure CHzCHzO) 1H Cn 2n+1N -HZ (CH2CH20) H wherein n is 12 to 18, the sum of x and y is 20, each of x and y is at least 1, and Z is chloride or acetate, to a pad bath for applying fiuorinated oiland Waterrepellent polymers to textile fabrics has been found to stabilize the bath against the undesirable interaction of incompatible pad bath ingredients.

The present invention is directed to new surfactant adjuvants used to stabilize textile treating pad baths against the effect of foreign tramp reagents. More specifically, the present invention is directed to new surfactant adjuvants used to stabilize pad baths prepared for the application of fiuorinated oiland Water-repellent formulations to textile fabrics.

The pad bath formulations used to apply fiuorinated oil and water-repellent resins to textiles contain a number of components in addition to the fiuorinated resins themselves. Thus, one or more water repellents, permanent press resins, crease resistance resins, softeners, hand modifiers, antistatic agents, and the like may also be present in the pad bath. Each of these ingredients is a separate commercial product, and may be combined with its own dispersing agent. "In addition, the water repellents and crease resistance resins usually require curing catalysts in the form of amine hydrochlorides or heavy metal salts such as magnesium, zinc, or aluminum salts. The fiuorinated oiland water-repellent resins also require dispersing agents of their own.

When these many ingredients, dispersing agents and catalysts are brought together in one bath, stability is usually a serious problem. First of all, as is 'well known, dispersing agents occur in four general types-cationic, anionic, nonionic, and amphoteric and a number of these are not mutually compatible in the same system. For instance, instability exists when many anionic and cationic dispersing agents are combined in the same bath. Further, several types of dispersing agents lose their effectiveness in the presence of metal salts and other curing catalysts, thus causing coagulation to occur in the treating bath. Finally, textiles often contain wetting agents and metal salts remaining in the fabric from prior treatments. As these foreign tramp reagents are carried by the textiles into the pad bath, stability is seriously reduced.

Pad bath instability with resulting coagulation has been observed in the past when attempting to prepare certain formulations or to treat specific manufacturers textiles. In an attempt to stabilize such baths, nonionic surfactants such as the long-chain alkyloxy or alkaryloxy polyethyleneoxyethanols (ethylene oxide reaction products of fatty alcohols or alkylphenols) have been added. Bath stability has not been universally obtained with such additives, however.

3,438,925 Patented Apr. 15, 1969 There exists, therefore, a need for a new additive which will stabilize pad baths under a wide variety of conditions which normally leads to bath coagulation. It is to this need that the subject invention is directed.

More specifically, the present invention is directed to an improved pad bath for applying oil and water repellents to textile fabrics, the improvement being the addition to the bath of a stabilizing amount of a compound having the structure wherein n is from 12 to 18, the sum of x and y is from 10 to 20, and each of x and y is at least one, and Z is an anion selected from the group consisting of chloride and acetate.

The present invention is also directed to new compositions of matter comprising:

(A) A fiuorinated oiland water-repellent polymer derived from monomers such as (1) CH C (CH CO CH CH R;

wherein R, is a C to C perfluoroalky, (2) an alkyl acrylate or methacrylate, wherein the alkyl group contains from one to eighteen carbons, (3) N-methylolacrylamide, and (4) a hydroxyalkyl methacrylate,

(B) A non-fiuorinated polymer derived from monomers such as a C to C alkyl methacrylate and N-rnethylolacrylamide, and

(C) A stabilizing compound of the structure where n, x, y, and Z are as defined above.

The hydrochloride and acetate salts described above are particularly useful in pad baths containing a wide variety of fiuorinated polymers and interpolymers derived from the monomers CHFC (CH CO CH CH R wherein R; is a pet-fiuorinated alkyl group having 'from 4 to 14 carbon atoms. Such polymers are usually interpolymers containing units from (1) a C to C alkyl methacrylate or C to C -alkyl acrylate and (2) N- methylolacrylamide in addition to the fiuorinated monomer. The fiuorinated polymer is combined with nonfiuorinated polymers or copolymers of alkyl methacrylates, for example, the copolymer of 2-ethylhexyl methacrylate and N-methylolacrylamide. An aqueous dispersion of these polymers or other similar polymers, using at a cationic dispersing agent dimethyloctadecylamine acetate, is then combined with other adjuvants to form the pad bath. A typical formulation of this type is disclosed in Belgian Patent 645,697, containing 0.04% nonylphenoxypoly(ethyleneoxy)ethanol, 0.04% tartaric acid, 1.5% dispersed polyethylene, 5.0% resin finish Aerotex M23 (a water-soluble melamineformaldehyde condensate), 0.5% magnesium chloride 2.5% Phobotex f/t/c, a melamine formaldehyde condensate-paraffin wax dispersion (described more fully in US. Patent 2,783,231), and 3.33% of the fiuorinated and non-fiuorinated polymer mixture referred to above. The nonylphenol derivative is included in the bath as a stabilizer. The fiuorinated polymer mixture consists of 40 parts fiuorinated polymer and 60 parts methacrylic ester polymer, the fluorinated and ester polymers being those described hereinafter in the examples. Another typical oiland waterrepellent formulation is described in French Patent 1,414,110, differing only in that the methacrylic ester polymer is cross-linked. This cross-linked polymer is further described hereinafter in the examples.

While formulations of these types are quite useful and widely used for treating textile fibers, the pad baths are sensitive to addition of further foreign materials, particularly anionic surfactants or wetting agents and foreign metal salts. Although the mills using these formulations do not purposely add such agents to the pad baths, the textile fabrics being treated in the bath often contain considerable amounts of wetting agents such as long-chain alkyl sulfates or alkaryl sulfonates and occasionally metal salts as residues from previous treatments such as dyeing. These foreign agents are dissolved from the fabric into the bath, upsetting the dispersant balance and causing the bath to coagulate. In addition, mills will often use waterrepellent resins and adjuvants other than that indicated above which can and do cause trouble, particularly since these other adjuvants may contain dispersants or metal salt catalysts which upset the dispersant balance of the oil and water repellent and lead to bath coagulation.

It is known in the art that, if both cationic and anionic dispersing agents are to be used in the same system, coagulation may hopefully be prevented by addition of a nonionic agent, particularly of the polyethylene-oxide type. The nonylphenoxypoly(ethyleneoxy)ethanol used in the above-described oiland water-repellent formulations was added for that purpose. While such agents are often effective, rather large amounts are required if foreign materials enter the system, and such large amounts often destroy the effectiveness of the oil and water repellents. If these nonionic agents are generalized by the formula RO(CH CH O) H, were R is the hydrophobic hydrocarbon group, it has been found that compounds where x is less than ten are sometimes ineffective as pad bath stabilizers. On the other hand, when x is 20 or 30, the compounds are quite effective as pad bath stabilizers but quite equally effectively destroy oil repellency on the treated fabric at the required concentrations.

It has now been quite unexpectedly found that compounds of the structure wherein n is from 12 to 18, the sum of x and y is from to 20, and each of x and y is at least 1, and Z is either chloride or acetate, are quite effective stabilizers for pad baths containing fluorinated oil and water repellents based on fluorinated polymers of CH =C(CH )CO CH CH R;, as hereinabove described, without adversely affecting oil repellency of the fabrics. Moreover, on a comparative basis of ethylene oxide units, the compounds of this invention are superior stabilizing agents to those previously used in the art. The preferred agents are those where n is 18, the sum of x and y is 15, and Z is chloride, namely CHzCHzO) xH ia nN -HC1, x+y=15 (CHzCHzObH These useful compounds are the hydrochloride and acetate salts of the amines CH CHzO),H

CuH2u+1N which are derived from fatty amines C H NH by reaction with ethylene oxide. A number of such free amine products are commercially available under the trade name Ethomeen (manufactured by the Armour Industrial Chemical Company). These products are sold containing varying amounts of ethylene oxide and based on amines produced from cocoa acids, tallow acids, and commercial Stearic acid, i.e., containing 12 to 18 carbons. The hydrochloride and acetate salts are readily prepared by neutralizing the free amines with hydrochloric acid and acetic acid by methods well known to those skilled in the art. For example, a water dispersion of the free amine is prepared, followed by adding a sufiicient quantity of either hydrochloric or acetic acid to neutralize the amine. The solution is then heated to C. until a clear solution is obtained.

Both the size of the alkyl group, hence the value of n, and the number of ethylene oxide groups attached to nitrogen, hence the values of x and y and their sum, are critical in this invention. If n is less than 12, the compounds lose their stabilizing effect. Products wherein n is greater than 18 are not readily available. If each of x and y is not at at least one and their sum is less than 10, the compounds also lose their stabilizing effect. If the sum of x and y is greater than 20, the oil and Water repellency is seriously decreased. Furthermore, since oiland water-repellent baths are acidic, the hydrochloride and acetic salts are required, since the basic free amines, if used directly, would neutralize the acid in the bath forming a salt, and thus destroy the necessary acid conditions of the pad bath. It is not presently understood why these compounds are useful while others based on ethylene oxide are not.

The amount of the above amine hydrochloride compounds required to obtain stable pad baths can vary from situation to situation, depending on which and how much foreign agents are entering the system. In most cases, however, about 0.2% by weight or more, based on the weight of the solids of the fluoropolymer and non-fluorinated vinylidene polymer mixture making up the oil and water repellent is usually satisfactory. Larger amounts are occasionally necessary but, in general, 13% by weight on weight of polymer solids should not be exceeded due to the adverse effect on oil and water repellency. The most preferred range of concentration of stabilizer is from about 1.0% to about 5.0% by weight, based on the weight of the oiland water-repellent polymer solids.

The typical pad bath contains many active ingredients other than the oil and water repellents discussed above. For example, such baths usually contain additional water repellents, such as Phobotex f/t/c, a water-insoluble melamineformaldehyde condensation product which contains parafiin wax. The pad bath may also contain one or more of the following reagents: crease resistance resins such as Aerotex MW, a modified melamineformaldehyde condensate, and dimethylolethylene ureas; permanent press resins such as 1,5-dimethylol-3,4-dihydroxyethylene ureas as described in US. Patent 3,049,446; fabric softeners such as N-methylolstearamide and polyethylene emulsions; sewing lubricants such as polyethylene emulsions; antistatic agents such as fatty alcohol phosphates and alkylarylsulfonate salts; hand modifiers such as acrylic resins or polyvinyl acetate; and dispersing agents and catalysts as required by the individual constituents.

Representative examples illustrating the present invention follow. Parts and percentages are by Weight unless specified otherwise.

EXAMPLE 1 Two compounds given in Table I below were added to a 13.5% active ingredient dispersion of a fluorinated oiland water-repellent polymer mixture in water containing about 5%, based on the weight of polymer solids, of dimethyloctadecylamine acetate. The polymer mixture consisted of 40 parts of fluorinated polymer containing 97.5% fluorinated monomer units derived from a mixture of the structure wherein R, is a perfluoroalkyl group containing from 6 to 14 carbon atoms, 2.0% n-butyl acrylate and 0.5% N-methylolacrylamide as described in Example 1A of Belgian Patent 645,697, and 60 parts of a vinylidene polymer containing about 97.7% 2-ethylhexyl methacrylate, 0.5

ethylene dimethacrylate and 1.8% N-methylolacrylamide, as described in French Patent 1,414,110, Example 4. The concentration of added compound in each test listed in Table I below was 3.7% based on the above polymer solids. Each dispersion, stabilized with the indicated stabilizer, was then divided into three parts. To one part of the dispersion, an alkylbenzenesulfonic acid salt. Iberterge was added in suflicient quantity to provide one molecular equivalent for each mole of dimethyloctadecylamine acetate present, an amount suflicient to cause 6 EXAMPLE 3 Five pad baths containing the active ingredients enumerated in Table III below were prepared. Baths 1 through 4 were prepared containing the stabilizer of the present invention. Bath 5 was prepared using the stabilizers heretofore used in the prior art. The concentration in is the weight of the stabilizer based on the weight of the oiland water-repellent polymer solids in the bath composition.

coagulation of the dispersion. To the second part sufiicient 1O zinc nitrate was added to cause complete coagulation of the above polymeric dispersion in the absence of the added TABLE III compound. To the third part suflicient sodium bicarbonate Percent on Weight of Bath was added to cause complete coagulation in the absence Cllmpment of the added compound. These compounds are represen- Water repellent A 1. 44 1. 44 tatrve of the materials present in commercial pad bath s Water repellent]; 2 M M M which cause coagulation. The dberterge and sodium bicarbonate are representative of impurities carried into (03203103111 pad baths by the fabrics. Zinc nitrate is a typical curing CrsHznN .11 1 65 mm 0,01 0,013 catalyst for water repellents such as the melamineform- (3-4) (1-4) (3-7) (3-7) (CH2CH20)yH aldehyde condensates.

These mixtures were evaluated after 20 hours and given an arbitrary number rating from zero (no coagulation) C9H19C5H O(CH2CHzO)mH 0. 026

U (a 2) to 5 (complete coa ulation). The plus and minus signs are 26 CQHWOGHAO (CHZGHzOMH O 026 used to indicate greater or less coagulation than the num- 3.2

Oil/water repellent 3 3.6 4.8 3.6 3.6 6.0 ber 1nd1cates. The results are shown in Table I below. Washwear Resin A 4 4 8' 4 8' 4 8. 4 8. 4

%asg-wear gesin g 5. 7

as -wear esin 0 8.4 8.4 8.4 8.4 TABLE I Curing Catalyst 1 2.88 2.88 2.88 2.88 2.88 Surface Active Agent: 1 Water repellent A: 67 parts Phobotex f/t/c and 25 parts Catalyst RB. Phobotex f/t/c is a 25% petroleum wax-75% reaction product of (CHZCHZO) hexamethoxymethylmelamine +3 moles stearic acid +1 mole triethanolat n y Ralilng mine plus acetic acid, as more fully described in U.S. Patent 2,783,231. n ZlrH Catalyst RB is 2 parts aluminum glycollate plus one part glycollic acid. Water repellent B: a 27% active ingredient dispersion of solids in 2 2 water, the solids being 46% paraffin wax, 46% reaction product of hexaglethloxymethyfielaii aying +ilhrnol'es Claeheinici acid, t4? dimethyloctaecy amine ace a e. ime y te ra ecy am ne ace a e. 11 +1! Z Iber- K QZ NaHCOa 3 Oil/water repellent? a 13.5% active ingredient dispersion of polymer terse mixture consisting of 40 parts fluorinated polymer containing 97.5% units derived from a mixture of fluorinated monomers CH2=0(CH )CO2CH2- it 7,{" 15 C1 1 CHZRf, wherein R: is a perfluoroalkyl having from 6 to 14 carbon atoms, 00mml 5 C1 5 4 2.0% n-butyl acrylate, and 0.5% N-methylolacrylamide, and 60 parts of 10 C1 1 a vinylidene polymer consisting of 99.5% 2-ethylhexyl methaerylate, and

18. 1. 15 6O2CCH: 3 0.5% N -methylolacrylamide, Example 1B, Belgian Patent 645,697.

COCO?! 5 floiccHfl 3 Wash'wear Resin A: Permatresh 197-a dimethylol cyclic nitrogen 10 60200113 3'- compound 15 C1 5 Wash-wear Resin B: Durazone DC-a urea formaldehyde adduct. 10 C1 B Wash-wear Resin 0: "Aerotex MW"a modified melamineformalde- 5 C1 3 hyde condensate. 2 C1 5 Curing Catalyst: Magnesium chloride.

l Cocoa=alkyl groups contain an average of twelve carbons.

From the above table, it can be seen that the value of the sum of x and y is critical to the stabilizing effect of the salt.

EXAMPLE 2 In a manner similar to that of Example 1, the preferred compound of the present invention was compared with a series of other surface active agents derived from ethylene oxide as to the ability of these agents to stabilize oiland water-repellent compositions in the presence of reagents which normall cause coagulation. The results obtained are shown below in Table II.

TABLE II Stability Rating Surface Active Compound Each bath was applied to navy blue and tan cotton fabrics using one dip and one nip at F. The wet pickup for the navy blue fabric was 45%; for the tan fabric 50%. The fabrics were then dried at 250 F. and cured for 1.5 minutes at 340 F. The fabrics were then tested for oil and water repellency initially, after three standard launderings, and also after one dry cleaning, with the results shown in Table IV below.

The water repellencies of the treated fabric samples were measured by using A.A.T.C.C. Standard Test Method 22-1952 of the American Association of Textile Chemists and Colourists (ASTM D-583-63). A rating of 100 denotes no water penetration or surface adhesion; a rating of denotes slight random sticking or wetting, and

so on.

The oil repellency test used in the following examples comprises placing a drop of test solution carefully on the textile on a flat horizontal surface. After three minutes, any penetration or wicking into the fabric is noted visually. To aid in the observation, the test solution can contain a small amount of oil-soluble blue dye to improve visibility. The nature of the test solutions is shown below. Nujol, of course, is a purified petroleum oil. Anything with a rating of five or greater is good or excellent, whereas anything with a rating of two or over can be used only for certain purposes. As an example of the rating method, if a treated fabric repels solution No. 6 listed below, but not the seventh solution, its rating is 6.

7 Test solution: Oil repellency rating n-Heptane 9 n-Octane 8 n-Decane 7 n-Dodecane 6 n-Tetradecane 50-50 n-hexadecane-Nujol 4 25-75 hexadecane-Nujol 3 Nujol 2 Wet by Nujol 0 A standard laundering consists of immersing the fabric sample for 40 minutes with agitation in water at from 60 C. to 100 C. containing 0.1% by weight of a neutral chip soap with 0.05% of soda ash. The fabric sample is thereafter rinsed three times in 60 C. water, then the sampleis centrifuged for five minutes, and finally pressed 30 seconds on each face at 300 Fri-20 F.

The dry cleaning consists of agitating the fabric sample for 20 minutes with tetrachloroethylene at room temperature and then drying the fabric by first centrifuging one minute followed by drying for five minutes at 160 F. in the tumble dryer. The fabrics were then pressed seconds on each face at 300 F.: F.

TABLE IV.REPELLENCIES Pad Bath Oil 3 SL DC Water 3 SL* DC Initial Initial Navy Blue:

'SL=Standard Laundering; DC=dry cleaning.

As can be seen from the results set forth in Table IV above, the stabilizing compound of this invention does not destroy the effectiveness of the oil and water repellent.

EXAMPLE 4 Two pad baths were prepared with the formulations set forth in Table V below.

1 Same as Water Repellent A, Example 3, except that 62.5 parts Phobotex f/t/c and 37.5 parts "Catalyst BB were used.

1 An 11.6% active ingredient dispersion of equal weights of the fluorinated polymer and vinylidene polymer of Example 1.

3 Indicates weight based on the weight of the oiland water-repellent polymer solids.

A black fabric, dyed with a sulfur black dye and containing a high concentration of salts, was padded with bath 1 in a commercial mill at a rate of yards per minute at about 40% pickup. A total of 17,400 yards was padded without any difiiculty. The resulting fabric had Water repellencies of 80 and oil repellencies of 7 to 8.

When the same fabric was padded with bath 2 under identical conditions, pad-roll buildup began after a few hundred yards had been padded and the run had to be stopped after about 3,000 yards because the pad-rolls could no longer be kept free of intolerable pad-roll buildup.

8 EXAMPLE 5 A 13.5% active ingredient dispersion of a fluorinated oiland water-repellent polymer mixture in water is prepared containing about 5%, based on the weight of the polymer solids, of dimethyloctadecylamine acetate. The polymer mixture consists of 40 parts fluorinated polymer containing approximately 75% R being a mixture of C to C fluorocarbon alkyl groups, approximately 25 approximately 0.25% CHFC(CH )CO CH CH OH, and approximately 0.25% CHFCHCONHCH OH, and 60 parts of a vinylidene polymer containing about 97.5% 2-ethylhexyl methacrylate, 0.5% ethylene dimethacrylate, and 2.0% N-methylolacrylamide. The fluorinated polymer is prepared by aqueous polymerization techniques well known to those skilled in the art. A polymerization initiator such as azobis(isobutyramidine)dihydrochloride is used and the molecular weight of the polymer is controlled by use of chain transfer agents such as dodecyl mercaptan.

Two pad baths, similar to bath Nos. 1 and 2 of Example 4, are prepared, except that the above oil and water repellent is used. Padding results similar to those of Example 4 are observed in that the bath containing CHZCHZO) H raHu J10 (CHZCH20)yH is at least several times more stable than the bath which did not contain the stabilizing agent of this invention.

EXAMPLE 6 Four oiland water-repellent compositions were prepared using the following procedure. Dimethyl octadecylamine acetate was dissolved in water with agitation. Then the monomer CH =C(CH )CO CH CH (CF ),,F, n=6, 8, and 10 in weight ratio of 3:2:1 containing less than 10% n=12 and 14, and n-dodecyl methacrylate were added and homogenized with the aqueous solution. A large amount of water in a separate container was degassed with nitrogen and boiling, then added to the above monomer dispersion. Dodecyl mercaptan, a chain transfor agent, N-methylolacrylamide, and 2-hydroxyethyl methacrylate were then added in minor amounts, andthe mixture was heated to 60 C. with agitation. A polymerization initiator azobis(isobutyramidine dihydrochloride) was added. The polymerization was initiated and the heating of the mixture at 60 C. to 70 C. was continued until polymerization was complete (4 to 5 hours). The resulting aqueous dispersion contained approximately 25% solids. All four polymers contained approximately 0.25 N methylolacrylamide, 0.25 2-hydroxyethyl methacrylate, and 0.04% of the initiator. The other proportions are shown below:

Each of the four resulting polymer dispersions was blended with the non-fluorinated copolymer of Z-ethylhexyl methacrylate and N-methylolacrylamide to give four dispersions containing 13.5 solids and 40 parts CH =C(CH )CO CH CH (CF F per parts solids.

Two pad baths were prepared from each of these four dispersions, one series containing 4.0% on weight of bath (OWB) of the dispersions (0.54% OWB of polymer solids) and the other containing 5.0% OWB of the polymer dispersions (0.675% OWB polymer solids). All baths contained OWB of a 27% zinc nitrate solution, 28.0% OWB Permafresh 183, 60% of water repellent B of Example 3, and Ethomeen hydrochloride stabilizing agent of the structure CH2CH2O) H OIEHHN -HCl (CH2GH20)yH wherein the sum of x and y is 15. The amount of the stabilizing agent present was 3.9% based on the weight of the polymer solids.

Permafresh 183 is an aqueous solution (40% solids) of a permanent crease resin sold by Sun Chemical, believed to have the structure:

Samples of fabrics Chem. 119, a 65/35 Dacron polyester/ cotton poplin (tan) were treated to obtain 50% wet pickup, dried, cured, and tested for repellencies as described in Example 3. The results are shown in Table VI below.

'HLAD=Home laundering air dry;

HLTD=H0me laundering tumble dry.

The home laundering tests were conducted as follows: A Kenmore washer Model 600 is loaded with a 4-pound load, with 29 g. of "Tide. The wash is set at hot (12- minute cycle) and a warm rinse (12 minutes). The total washing and rinsing time is 40 minutes. In the home laundering air dry test (HIAD), the spun dry fabrics are dried at ambient temperatures. In the home laundering tumble dry test (HLTD), the spun dry fabrics are dried at 156 F. to 160 F. in a home drier with tumbling.

The above-described pad bath formulations were stable and resisted coagulation for long periods of time.

It is to be understood that the preceding examples are representative and that said examples may be varied within the scope of the total specification, as understood by one skilled in the art, to produce essentially the same results.

As many apparently widely difierent embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that this invention is not limited to the specific embodiments thereof except as defined in the appended claims.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. In a pad bath used to treat textile fabrics to obtain oil and water repellency which contains an aqueous dispersion of a fluorinated oiland water-repellent polymer and one or more of a permanent press resin, a crease resistance resin, a fabric softener, a hand modifier, an antistatic agent, a curing catalyst and a dispersing agent, some of which are incompatible causing instability of the pad bath, the improvement comprising adding an effective amount of a stabilizing compound having the structure omcmoprr CnH2u+lN -HZ CH CHzO) H wherein n is from 12 to 18, the sum of x and y is from 10 to 20 and each of x and y is at least one, and Z is an anion selected from the group consisting of chloride and acetate.

2. The pad bath of claim 1 wherein the stabilizing compound has the structure CHzCHzO) H Cm m -HC1 CHzCHgO) yH the sum of x and y 'being 15.

3. The pad bath of claim 1 wherein the amount of the stabilizing compound present is from about 0.2% by weight to about 13% by weight based on the weight of the polymer solids present.

4. The pad bath of claim 3 wherein the stabilizing compound has the structure cia eiN the sum of x and y being 15.

5. The pad bath of claim 3 wherein the fluorinated oil and water repellent is a mixture of (A) a fluorinated polymer comprising units derived from the monomer of CH =C(CH CO CH CH R wherein R is a C to C -perfluoroalkyl, and

(B) a non-fiuorinated polymer comprising units derived from the monomer CH C(CH )CO R, wherein R is an alkyl group having up to 18 carbon atoms.

References Cited UNITED STATES PATENTS 3,256,230 6/ 1966 Johnson et al 260900 3,277,039 10/ 1966 Morascia et a1.

3,282,905 11/1966 Fasick et a1. 260900 3,331,812 7/1967 Chai Lee 260-459 3,347,812. 10/1967 De Marco et al 260-900 3,350,314 11/1967 Dawtrey et a1. 260-307 3,352,709 11/1967 Gunnar et al 260567.6

MURRAY TILLMAN, Primary Examiner.

H. ROBERTS, Assistant Examiner.

US. Cl. X.R.