US3268465A - Composition and method of treating fabrics - Google Patents

Description

United States Patent "ice 3,268,465 COMPOSITION AND METHOD OF TREATING FABRICS John W. Gilkey and Richard W. Alsgaard, Midland, Mich., assignors to Dow Corning Corporation, Midland, Mich., a corporation of Michigan No Drawing. Filed May 15, 1961, Ser. No. 109,868 11 Claims. (Cl. 260-291) This invention relates to a mixture of siloxanes suitable for rendering fabrics water repellent and is a continuation-in-part of applicants copending application Serial No. 10,577, filed February 24, 1960, now abandoned, which is in turn a continuation-in-part of applicants copending application Serial No. 662,336, filed May 29, 1957, now abandoned.

Organosiloxanes, particularly those containing methyl groups and hydrogen atoms bonded to the silicon have become widely used as a treatment for textiles, These siloxanes impart many desirable properties to the textile such as water repellency, stain resistance, improved handling, improved abrasion resistance and improved sewability. The siloxanes have been used on all types of fabrics. However, the use of such siloxanes on cotton fabrics has been held back by the fact that heretofore employed siloxane treatments of cotton did not give durable water repellency with respect to laundering. In general, cotton treated with heretofore employed siloxanes has an initial spray rating of 100, but this spray rating generally drops to zero after from one to two washings at 160 F. Because of this feature organosiloxanes have not been widely employed on cotton except for expensive cotton fabrics which are normally dry cleaned.

As a result of this a large potential use of organosiloxanes has been left untouched. Since washable cottons represent the largest single textile now in use, it would be highly desirable to have a siloxane material which would be durable to laundering and which would have all the other desirable features of the heretofore employed siloxanes.

It is the object of this invention to provide a novel composition of matter capable of imparting durable water repellency to cellulosic fabrics. Another object is to provide a composition which decreases the shrinkage of wool. Another object is to provide a composition which is useful on all types of organic fabrics. Other objects and advantages will be apparent from the following description.

This invention relates to a composition of matter comprising a mixture of (1) from 1 to 40 percent inclusive by weight of a siloxane of the formula in which 0 has a value from 0 to 3 inclusive, R is an aliphatic hydrocarbon radical of less than 4 carbon atoms, a has a value from 1 to 2 inclusive, R is a divalent or trivalent saturated aliphatic or cycloaliphatic hydrocarbon radical of at least two carbon atoms, Y is a monovalent hydrocarbon radical or a fluorinated monovalent hydrocarbon radical =and m has a value from 0 to 2 inclusive,

*A spray rating of 100 shows that the fabric is completely water repellent. A spray rating of 50 means that the entire surface of the fabric is wet but no water has soaked through. .3 spgraylrating of zero means that the water soaks through e a r e.

which siloxane may contain up to mol percent of a copolymerized siloxane of the formula in which Z is a monovalent hydrocarbon radical or a fluorinated monovalent hydrocarbon radical and b has an average value from 1 to 3 inclusive and (2) from 60 to 99 percent by weight of a siloxane having an average of from 1 to 3 substituents of the group monovalent hydrocarbon radicals, halogenated monovalent hydrocarbon radicals and hydrogen atoms, per silicon, in siloxane (2) there being an average of at least one of said organic radicals per silicon, siloxanes (1) and (2) being in such proportion that in the total mixture there is at least .7 percent by weight of (A).

Siloxanes (1), both with and without copolymerized siloxane (B), are prepared in accordance with the methods set forth in U.S. Patent No. 2,838,423, issued June 10, 1958, the disclosure of which is hereby incorporated in this application by reference.

Briefly, siloxane '(A) is prepared by reacting a siloxane amide of the unit formula Elf... rnNoc)..1 .'sio

in which a, R, Y and m are asabove defined with formaldehyde and a hydrochloride of pyridine or an alkylated or alkenylated pyridine. The reaction is best carried out in the presence of pyridine or the defined pyridine derivatives as a solvent. These products are generally viscous water-soluble materials.

When siloxane (1) contains copolymerized (B) the copolymers can be made by any of the methods described in US Patent No. 2,838,423. Briefly, the best method of this preparation comprises copolymerizing a chlorosilane of the formula in which R" is an 'alkyl radical, with a chlorosilane of the formula Z SiCl in the conventional manner and thereafter bombing the ester copolyrner with ammonia to produce the corresponding siloxane amide. This copolymer is then reacted with formaldehyde and a pyridine hydrochloride as described above.

Siloxane esters of the type which are suitable as starting materials for the compounds of this invention are described in US. Patent 2,723,987 and in the copending application of Leo H. Sommer, Serial No. 522,826, filed July 18, 1955, now abandoned. For the purpose of this invention siloxane (2) can be any of the standard siloxanes now employed in rendering fabrics water repellent. The best water repellency is obtained when siloxane (2) contains a substantial portion of methylhydrogensiloxane. However, any siloxane having an average of at least 1 monovalent hydrocarbon radical or halogenated monovalent hydrocarbon radical per silicon atom can be employed in this invention.

Siloxane (2) can be a single homopolymeric siloxane or a mixture of two or more homopolymeric siloxanes. It can be a single copolymer of two or more siloxanes or a mixture of two or more of such copolymers and it can be a mixture of homopolymeric and copolymeric siloxanes.

.repellency in the shortest time.

trifluorovinylmethylsiloxane, bis-trifiuoropropylsiloxane, chloromethylmethylsiloxane, 2,4 dichlorophenylsiloxane,

a,a,a-trifluorotolylsiloxane, octafiuorocyclopentylsiloxane,

monomethylsiloxane and monooctadecylsiloxane. Siloxane (2) can also contain some copolymerized SiO HSiO and H SiO units.

The compositions of this invention are prepared by merely mixing siloxanes 1) and (2). These mixtures can then be applied to the fabric by any suitable means. For example, they may be employed in the form of solutions or emulsions. After application of the siloxane mixture to the fabric the fabric is then heated in order to fix the siloxane and to develop the maximum water The precise degree and extent of heating depends on the fabric employed and the type of siloxane mixture. In general, heating times varying from 1 minute to minutes and temperatures ranging from 110 to 350 F. are suitable. After the fabric has been so treated it is ready for use and the water repellency is highly durable to laundering especially on cellulosic fabrics.

For the purpose of this invention siloxanes (1) and (2) can be emulsified by any of the conventional techniques for preparing siloxane emulsions employing any of the conventional emulsifying agents.

The composition of this invention is applicable to any kind of organic fabric such as cotton, viscose, acetate, linen, silk, wool, polyacrylonitrile fibers, polyester fibers and vinyl chloride-vinylidene chloride fibers.

The amount of siloxane applied to the fabric is not critical although in general it is desirable to have at least .5 percent by weight siloxane. For practical application from 1 to 5 percent siloxane is desirable although more or less may be employed if desired.

The treatment of textiles with the compositions of this invention can be carried out in one step or two steps. That is, a mixture of siloxanes 1) and (2) may be applied to the fabric in any suitable fashion. Alternatively, the fabric may be first treated with siloxane 1) and subsequently with siloxane (2). It is desirable, but not essential, that the fabric be cured after each step. Alternatively the fabric may be treated first with siloxane (2) and then treated with siloxane (I In siloxane (1) (A) employed in this invention R can be any divalent saturated aliphatic hydrocarbon radical of at least 2 carbon atoms such as ethylene, propylene, butylene, or octadecylene, or any trivalent saturated =hydrocarbon radical of at least 2 carbon atoms such as and or any cyclic divalent aliphatic hydrocarbon radical such as cyclohexylene, cyclopentylene, or methylcyclohexenylene and and any trivalent cycloaliphatic saturated hydrocarbon radical such as S t CH. and L0H.

Y can be any monovalent hydrocarbon radical such as alkyl radicals such as methyl, ethyl, butyl and octadecyl; any alkenyl radical such as vinyl, allyl, and hexenyl; any

cycloaliphatic hydrocarbon radicals such as cyclopentyl, cyclohexyl and cyclohexenyl; any alkaryl hydrocarbon radical such as benzyl and fi-phenylethyl and any aryl hydrocarbon radical such as phenyl, tolyl, xenyl and naphthyl. Y can also be any fiuorinated hydrocarbon radical such as tritiuorovinyl, tetrafiuoroethyl, 3,3,3-trifluoropropyl, decafluorocyclohexyl, 0L,Ot,0L-l'.l'lfill0lOtOlYl and C F CH CH R in this invention can be methyl, ethyl, propyl, vinyl or allyl.

In component (B) of siloxane 1) employed in this invention Z can be any monovalent hydrocarbon radical or any fiuorinated monovalent hydrocarbon radical. Thus specific examples of siloxane (B) are dimethylsiloxane, ethylmethylsiloxane, octadecylmethylsiloxane, divinylsiloxane, allylrnethylsiloxane, hexenylmethylsiloxane, monoethylsiloxane, diphenylmethylsiloxane, monophenylsiloxane, xenylrnethylsiloxane, naphthylmethylsiloxane,

trifluorovinylmethylsiloxane, 1,1,1 trifluoropropylsiloxane, bis trifluoropropylsiloxane, octafiuorocyclohexylsiloxane, a,a,u trifluorotolylsiloxane and monooctadecylsiloxane. If desired, the (B) component of siloxane (1) can contain two or more different types of siloxane units. The (B) component can also contain some SiO units.

In general, siloxanes (1) which contain at least 30 mol percent of the (A) component are water soluble. These water soluble components can be added without further modification to an emulsion of siloxane (2). Preferably these emulsions are diluted with water until they contain from 1 to 5 percent by Weight total siloxanes (1) and (2). The dilute emulsion is then employed to impregnate the fabric.

The mixture of siloxanes (1) and (2) operate well as a water repellent treatment for fabric. If desired, however, an additional curing or fixing agent may be added to the siloxane mixture. Typical catalysts are dibutyltindiacetate, lead Z-ethylhexoate, zinc hexoate, dibutyltindilaurate and other metal salts of carboxylic acids. These additional catalysts can also be used when (1) and (2) are applied separately to the fabric. In this case the added catalyst is generally added to (2) before application.

The compositions of this invention can be employed on fabrics with other types of resins which are normally employed on organic fabrics for specific purposes such as imparting crease resistance and the like. Specific examples of such resins are melamine formaldehyde resins and urea formaldehyde resins.

The compositions may also contain other additives which are employed on fabrics for the purpose of decreasing slip of the fibers or imparting soil resistance. Agents commonly used for these purposes are colloidal silicas. It should be understood that these additional materials can be applied to the fabric either simultaneously with, before, or after treatment with the siloxanes of this invention.

The following examples are illustrative only and should not be construed as limiting the invention which is properly delineated in the appended claims.

Example 1 This example shows the contrast between the compositions of this invention and previous commercial silicone treatments with respect to durability on cotton.

The fabric was removed from the solution, pressed between rolls and then cured 3 minutes at 300 F. The fabric was then dipped into an emulsion containing 3 percent by weight of (2) a mixture of 40 percent by weight of a dimethylpolysiloxane fluid containing SiOH groups and 60 percent by weight of a trimethyl endblocked methylhydrogenpolysiloxane fluid, which emulsion contained a small amount of zinc octoate and dibutyltindiacetate as a catalyst. The fabric was then removed from the emulsion, dried and cured by heating minutes at 300 F. The spray rating of each sample was then determined and each sample was then subjected to the laundering schedules shown below. In each washing Ivory soap was used. After the designated number of washings the spray rating was again determined as shown in the table.

By contrast cotton treated with siloxane mixture (2) alone under identical conditions gave a zero spray rating after five washings under any of the above conditions.

Example 2 Siloxane (1) of Example 1 was added to an emulsion of siloxane (2) of Example 1 in varying amounts so that the percent by weight siloxane (1) based upon the combined weights of (l) and (2) in the emulsion were as shown in the table below. Samples of cotton fabric were dipped into each of these emulsions and the samples were then dried and cured minutes at 250 F. The percent by weight gain of the sample was then determined and the initial spray rating determined. Each sample was then washed five times at 160 F. with Ivory soap and the spray rating was again determined. The results are recorded in the table below.

This example shows the effectiveness of the treatment of this invention on various types of fabrics. Each of the fabrics shown below were dipped into an emulsion containing 2.4 percent by weight of a mixture of 40 percent by weight of a trimethyl endblocked dimethylsiloxane fluid and 60 percent by weight of a trimethyl endblocked methylhydrogensiloxane fluid and .3 percent by weight of a copolymer of 34 rnol percent dimethylsiloxane and 66 rnol percent 6 Each sample was then removed from the emulsion, dried and cured by heating at 300 F. for 1) minutes. The initial spray rating was determined and each sample was then washed 5 times at 160 F. with Ivory soap. The spray rating after these 5 washings was also determined.

Initial spray Spray rating rating after 5 Fabric washings Cotton 70 Viscose 80 Acetate 100 70 50% Viscose, 50% Acetate 100 80 Nylon 100 80 Wool 100 *80 *The wool sample was dry cleaned 5 times rather than washed.

Example 4 Cotton fabrics were treated with each of the siloxane samples having the compositions shown below by dipping the fabric into the siloxane emulsion samples and thereafter drying the fabric and curing for 10 minutes at 350 F. The initial spray rating was determined and each fabric was then washed at F. with Ivory soap for the number of times indicated and the spray rating was again determined. These results are shown in the table below. The sample compositions are:

1 g. of

35.6 g. of the siloxane emulsion of sample 1 7.1 g. of the catalyst emulsion of sample 1 .75 g. of

01+N05H5CHgNHQCCmHgoSlO These ingredients were diluted with water to a total weight of 500 g.

III.

4.5 g. of the siloxane emulsion of sample 1 .9 g. of the catalyst emulsion of sample 1 .2 g. of a copolymer of 50.3 mol percent (13H; (3H -Cl+NC5H5CI-IZNHOCCHCHzSiO and 49.7 mol percent 3,3,B-trifluoropropylmethyl siloxane This mixture was diluted with water to a total of 74.4 g.

A mixture of 32 g. of a 506 cs. viscosity diphenylmethyl endblocked propylmethylsiloxane fluid 48 g. of a trimethyl endblocked methylhydrogenpolysiloxane 20 g. of a mixture of 60% toluene and 40% perchloroethylene was emulsified with 98 g. of water using 17.4 g. of a mixture of 10.8 percent by weight polyvinyl alcohol, .7 percent by weight sodium lauryl sulfate and 88.5 percent water as the emulsifying agent.

36.5 g. of this emulsion were mixed with 7.1 g. of the catalyst emulsion of sample 1 and .75 g. of a copolymer of 36.5 mol percent dimethylsiloxane and 63.5 mol percent of the amidomethyl siloxane (3H CPI; -C1+NC H CH2NHO CCHCHzSiO The total mixture was then diluted to 500 g. with water.

36.5 g. of a 40% aqueous emulsion of a trimethyl endblocked methylhydrogenpolysiloxane fluid 7.1 g. of the catalyst emulsion of sample 1 .75 g. of the amidornethyl copolymer of sample 4 The mixture was diluted to 500 g. with water.

47.5 g. of a 30% emulsion of a hydroxyl endblocked dimethylpolysiloxane fluid of 1000 cs. viscosity 9.5 g. of the catalyst emulsion of sample 1 .75 g. of the amidomethyl copolymer of sample 4 This mixture was diluted to 500 g. with water.

VII.

47.5 g. of a 30% emulsion of a 1,000 cs. trimethyl endblocked dimethylsiloxane fluid 9.5 g. of the catalyst emulsion of sample 1 .75 g. of the amidornethyl copolymer of sample 4 This mixture was diluted to 500 g. with water.

A siloxane emulsion was prepared containing 40 percent by weig-ht of a mixture of 75 percent by weight of a hydroxyl endblocked dimethylpolysiloxane of 12,500 cs. viscosity and 25 percent by weight of a trimethyl endblocked met-hylhydrogenpolysiloxane. To 5 parts by weight of this emulsion was added 1 part by weight of the catalyst emulsion of sample 1 of Example 4 and sufficient of (1) a copolymer of 68 mol percent and 32 mol percent dimethylsiloxane, that (l) amounted to percent by Weight of the total siloxane in the emulsion.

This emulsion was diluted with water to a concentration of about 5 percent by weight total siloxane and applied to wool fabric. The fabric was then dried and cured minutes at 257 F. The total percent by weight pickup was 4 percent. The fabric was then washed 5 times with the water at 140 F. using Ivory soap. The area shrinkage was 21.1 percent.

By contrast a sample of the same Wool which had not been treated with any siloxane had an area shrinkage of 44.8 percent and a sample of wool which was treated with the emulsion that contained no siloxane (1) (but was otherwise identical) had an area shrinkage of 32.8 percent.

Example 6 Results equivalent to those of Example 1 are obtained when a copolymer of 50 mol percent dimethylsiloxane and 50 mol percent A E f CHzNHOCCHCHgSiO c1 is substituted for siloxane (1) of that example.

Example 7 Improved resistance to laundering is obtained when the following siloxanes are mixed with the emulsion of siloxane (2) of Example 1 in amount so that they are present in amount of 5 percent by weight based on the weight of siloxane (2), and the emulsion is then applied to cotton fabric and cured 10 minutes at 300 F.

armcnzwnmnooOsw H3C\N/ CH3 CH3 3 01 OHzNHGOOOHCHsSiO GH=C a CH CH3 I l OHzNHOCOHOHzSiO Example 8 Improved laundering resistance is obtained when the following copolymers are mixed with the emulsion of siloxane (2) of Example 1 in amount such that the amidemethyl siloxane units in the copolymers make up 5 percent by weight of the total siloxane in the emulsion and the emulsion is then applied to cotton fabric and cured 10 minutes at 300 F.

COMPOSITION OF COPOLYMER IN MOL PERCENT 50(05115) (CH3) S10 iH5) s)S1O 25 CHNC6H5CH2NHOOCHCH2S1O 0 H3 CH3 (2) 10C HgCa lg i 1.5

20 C H 7 i0 C H 10C aHuS iO C 4 9) 2Si 0 CH CH 50 'CPN 05115 C HzNH O C JHGHQS i O Example 9 Improved laundering resistance is obtained when siloxane (1) of Example 1 is added .to an emulsion of the following siloxanes in amount so that there is 5 percent by weight of (1) based on the total weight of siloxanes in the emulsion, together with 20 percent by weight based on the weight of the siloxanes infra, of a mixture of 40 percent by weight triethanol amine titanate and 10 percent by weight zinc acetate, and the resulting emulsion is applied to cotton fabric and cured 10 minutes at 300 F.

(C F CH CH SiO Copolymers in mol percent of (3) 10(C2H (CHs)SiO 1QC5H11SiOL5 IOSiOz 70(C,H9)2sio A mixture of 50 percent by weight of a copolymer of 10CH C H SiO lCF C H SiO and 50% by weight (C H )HSiO Example 10 Cotton was saturated with an aqueous solution of 0.9 percent by weight of a copolymer of 55 mol percent dimethylsiloxane and 45 mol percent (llHa ([lHs c1+Nc5H5oH NHoCCHcH si0 squeezed to an 80 percent wet pickup and then heated 3 minutes at 350 F. The treated cotton was then saturated with a 3.6 percent by Weight solution of in methylisobutyl ketone. The ketone solution contained .11 percent by weight of a curing catalyst of the formula H NCH CH NH(CH Si(OCH and .28 percent by weight stannous octoate. The cotton was then air dried and cured minutes at 250 F.

The resulting cloth had a spray rating of 100 and has good oil repellency. The spray rating was 80 after one washing at 160 F.

That which is claimed is:

1. A method which comprises applying to an organic fabric a dispersion in a liquid carrier of (1) a siloxane of the formula from 1 to 18 inclusive carbon atoms and is selected from the group consisting of monovalent hydrocarbon radicals and fluorinated monovalent hydrocarbon radicals and m has an average value from 0 to 2 inclusive in which (A) contains up to mol percent copolymerized siloxane of the formula in which Z contains from 1 to 18 inclusive carbon atoms and is selected from the group consisting of monovalent hydrocarbon radicals and fluorinated monovalent hydrocarbon radicals and b has an average value from 1 to 3 inclusive and a dispersion in a liquid carrier of (2) an organosiloxane having an average of from 1 to 3 inclusive substit'uents per silicon atom, said substituents being selected from the group consisting of hydrogen atoms, monovalent hydrocarbon radicals of from 1 to 18 inclusive carbon atoms and halogenated monovalent hydrocarbon radicals of from 1 to 18 inclusive carbon atoms and there being an average of at least one of said organic radicals per silicon, in such a manner that the weight ratios of the siloxane shall range from 1 to 40 percent by weight of (1) and from 60 to 99 percent by weight of (2), and said siloxanes being in such proportion that at least .7 percent by weight of the total of siloxanes (1) and (2) on the fabric is (A) and heat curing the siloxanes.

2. The method in accordance with claim 1 wherein the fabric is a cellulosic fabric.

3. A method which comprises applying to an organic fabric a dispersion in a liquid carrier of (1) from 1 to 40 percent by weight of a siloxane of the formula which contains up to 90 mol percent (B) copolymerized dimethylsiloxane and a dispersion in a liquid carrier of (2) from 60 to 99 percent by weight of a mixture of methylhydrogensiloxane and dimethylsiloxane in such a manner that at least .7 percent by weight of the total siloxanes (1) and (2) on the fabric is siloxane (A) and heat curing the siloxanes.

4. The method in accordance with claim 3 wherein the fabric is a cellulosic fabric.

5. A composition of matter comprising a mixture of (1) from 1 .to 40 percent by weight inclusive of a siloxane of the formula A) Ru in which R is an aliphatic hydrocarbon radical of less than 4 carbon atoms, c has a value from 0 to 3 inclusive, R is selected from the group consisting of divalent and trivalent saturated aliphatic radicals of from 2 to 18 inclusive carbon atoms and divalent and trivalent saturated cycloaliphatic hydrocarbon radicals of no more than 18 carbon atoms, a has a value from 1 to 2 inclusive, Y contains from 1 to 18 inclusive carbon atoms and is selected from the group consisting of monovalent hydrocarbon radicals and fluorinated monovalent hydrocarbon radicals and in has an average value from 0 to 2 inclusive which siloxane contains up to 90 mol percent of (B) a copolymerized siloxane of the formula Z SiO in which Z contains from 1 to 18 inclusive carbon atoms and is selected from the group consisting of monovalent hydrocarbon radicals and fluorinated monovalent hydrocarbon radicals and b has an average value from 1 to 3 inclusive and (2) from 60 to 99 percent by weight inclusive of a siloxane having an average of from 1 to 3 substituents per silicon atom, said substituents being selected from the group consisting of hydrogen atoms, monovalent hydrocarbon radicals of from 1 to 18 inclusive carbon atoms and halogenated monovalent hydrocarbon radicals of from 1 to 18 inclusive carbon atoms, in said siloxane (2) there being an average of at least one of said organic radicals per silicon, the proportions of (i) and (2) in said mixture being such that in the total weight of (l) and (2) there is at least .7 percent by weight of siloxane (A).

6. A composition of matter comprising a mixture of (1) from 1 to 40 percent by Weight inclusive of a siloxane of the formula CH3 on;

which contains up to 90 mol percent (B) copolymerized dimethylsiloxane and (2) from 60 to 99 percent by weight inclusive of a mixture of methyl-hydrogensiloxane and dimethylsiloxane, in said mixture the proportions of (1) and (2) being such that there is at least .7 percent by weight of siloxane (A) based on the total weight of (1) and (2).

7. An article of manufacture comprising a fabric having applied thereto the composition of claim 5.

8. An article of manufacture comprising a fabric having applied thereto the composition of claim 6.

9. A method which comprises applying to an organic fabric a dispersion in a liquid carrier of (1) from 1 to 40 percent by weight of a siloxane of the formula (A) CH3 CH3 C1+NCsHaGHzNHO G lHCHzs iO which contains up to 90 mol percent (B) copolymerized dimethylsiloxane and a dispersion in a liquid carrier of (2) from 60 to 99 percent by weight of a 5,5,5,4,4,3,3- heptafiuoropentylsiloxane in which any remaining organic groups attached to the silicon are methyl, in such a man- CH CH which contains up to 90 mol percent (B) copolymerized dirnethylsiloxane and (2) from to 99 percent by Weight inclusive of a 5,5,5,4,4,3,3-heptafluoropentylsiloxane in which any remaining organic groups attached to the silicon are methyl, in said mixture the proportions of (1) and (2) being such that there is at least .7 percent by weight (A) based on the total weight of (1) and (2).

References Cited by the Examiner UNITED STATES PATENTS 2,588,366 3/1952 Dennett. 2,838,423 6/1958 Gilkey. 2,947,771 8/1960 Bailey 26029.1

OTHER REFERENCES Pierce et al., Fluorine-Containing Elastomers, Wright Air Development Center, T.R. 52-191, part 2, October 1953, page 43.

ALLAN LIEBERMA-N, Acting Primary Examiner.

LEON I. BERCOVITZ, MORRIS LIEBMAN,

Examiners.

K. B. CLARKE, I. S. WALDRON, Assistant Examiners.

Claims (1)

1. A METHOD WHICH COMPRISES APPLYING TO AN ORGANIC FABRIC A DISPERSION IN A LIQUID CARRIER OF (1) A SILOXANE OF THE FORMULA