US2343089A - Treatment of textiles and composition useful therefor - Google Patents

Description

Patented Feb. 29, 1944 UNITED STATES PATENT OFFICE TREATMENT OF TEXTILES AND COMPOSI- TION USEFUL THEREFOR Joseph Edward Smith, Wilmington, Del, assignor to E. I. du Pont de Nemours & Company, Wilmington, DeL, a corporation of Delaware No Drawing. Application August 3, 1940, Serial No. 351,083

Claims. (cl. 260-32) fibers and nylon. A further object is the preparation of resin dispersions useful for finishing textile fabrics which are substantive to animal fibers and nylon. Other objects will appear hereinafter.

These objects are accomplished by the following invention. A solution in water of a partially saponified polyvinyl acetate more particularly of the type described in copending application Serial No. 351,082, filed of even date herewith is agitated vigorously with an ester of methacrylic acid or vinyl alcohol ester containing a small amount of benzoyl peroxide. During agitation a positive charge is obtained on the emulsion particle by incorporating a water soluble polyvalent metal salt or a heavy metal salt. The emulsion is heated to produce polymerization of the methacrylic acid ester or vinyl alcohol ester and form a stable dispersion of the resin. The dispersion is substantive from a dilute aqueous dispersion to animal fibers, including wool and silk, and to nylon. As an a1- ternative, the heavy metal salt or multivalent metal salt ay be added to the polymerized resin dispersion to obtain a positively charged dispersion substantive to animal fibers and to nylon.

Aqueous dispersions of polymeric esters of methacrylic acid and vinyl alcohol can be prepared by emulsion polymerization. Emulsifylng and dispersing agents which may be used for this purpose include typical anionic surface active agents, as alkyl naphthalene sulfonic acid salts and fatty alcohol sulfates, as well as protective colloids, such as natural gums, starches and gelatin. Dispersions thus prepared are, by the nature of the colloidal system, negatively charged and have insufficient substantivity for animal fibers and nylon to be applied by a process of exhaustion from a dilute bath under practical conditions. Such dispersions have to be applied by dipping the fabrics to be treated in a bath followed by extraction of excess liquor from the surface of the fabrics and drying. The amount of resin absorbed by the fabric in such a process is directly proportional to the amount of liquor retained by the fabric from the bath.

It frequently is advantageous to apply resin ization of the emulsified monomer.

dispersions to textile materials by a process of exhaustion from the bath onto the fibers in order to obtain economical use of the resin. This is particularly true in establishments which process goods that cannot conveniently be treated on the quetsch, For example, it is desirable in treating hosiery of nylon, wool or silk, as well as knitted goods in general, to exhaust the resin dispersion from a long bath onto the goods. In an application of this nature the greater part of the resin is entirely removed from the bath by the goods, regardless of the amount of water absorbed by the goods. Hence, in this process the amount of resin absorbed by the goods is directly proportional to the amount of resin dispersed in the bath regardless of the bath volume.

In carrying out the invention, an aqueous solution of a partially saponified polyvinyl acetate is agitated vigorously with a monomeric methacrylic acid ester or vinyl alcohol ester containing a small amount of benzoyl peroxide. Aluminum acetate or barium chloride and acetic acid are added while continuing the agitation. A stable emulsion is obtained. The emulsion is heated to a temperature above C. to induce polymer- The benzoyl peroxide acts as an oxidation catalyst to promote the polymerization of the monomer. The resin dispersions produced by this invention are stable. As an alternative, the polyvalent metal salts or heavy metal salts can be added to the resin dispersions following polymerization.

Partially saponified polyvinyl acetate is highly soluble in water, but is difflcult to dissolve rapidly since the material tends to form lumps surrounded by a gelatinous film on contact with water. The gelatinous film retards the rate of penetration into the mass and it is necessary to agitate for several days to obtain a solution. However, if the water contains 1% of a surface active agent, as for example, technical dodecyl diethylcyclohexylamine sulfate, on the weight of the partially saponified polyvinyl acetate, a much more rapid rate of solution is obtained, particularly at elevated temperatures. A concentrated solution of a polyvinyl alcohol derivative can be prepared in 30 minutes at F. with good agitation, provided the wetting agent is present. The inclusion of a small amount of technical dodecyl diethylcyclohexylamine sulfate with the polyvinyl alcohol derivatives in the emulsion has no detrimental effect on the ultimate stability of the dispersed product. It is advantageous to use a small amount of technical dodecyl diethylcyclohexylamine sulfate in the preparation of the emulsions to assist in dissolving the polyvinyl alcohol derivative.

It frequently is advantageous to use plasticizers with methacrylic acid ester and vinyl alcohol ester polymers to obtain the desired effects. Satisfactory plasticizers are discussed by Strain, Kennelly, Dittmar, Ind. and Eng. Chem, 31, 382 (1939).

Plasticizers, which are particularly of value in the compositions of this invention, are di-(butoxy ethyl) phthalate, butyl phthalyl butyl glycolate, and di(methylcyclohexyl) adipate.

The resin dispersions prepared according to this invention have the common property of bein po i ively charged as shown by movement of the dispersed particles from the positive to the negative pole in an electric field. The resin particles are substantive to wool, silk and nylon and are absorbed from a dilute bath by fabrics made of these materials. The degree of substantivity for the different fibers varies considerably; the substantivity of the dispersed resin particles for wool, silk and nylon is a variable that is strongly influenced by the pH and temperature in the bath. Generally speaking, the substantivity is greater the higher the temperature and pH in the bath. It has been found in practice that the pH range most suitable for use in applying the dispersions to silk is 4.0 to'7.0; to wool, 4.5 to 7.0; and to nylon 4.8 to 7.0. The dispersions have a high affinity for silk, wool or nylon in baths more alkaline than 7.0 but the dispersions are in a metastable state and frequently are absorbed so rapidly that the particles are not deposited on the fibers uniformly. The dispersions have some affinity for the fibers at pH values smaller than those given above, but the rate of absorption of the dispersion is frequently too slow to be practical. The dispersions are highly substantive to wool and silk at temperatures as low as 75 F.; temperatures above 90 F. are frequently required for satisfactory application to nylon.

The resin dispersions described herein may be used to advantage in combination with positively charged wax dispersions in the finishing of wool, silk and nylon textiles and more particularly in the finishing of hosiery. The combination of resin and wax dispersions is applied by the same methods as described for the resin dispersions alone.

The following examples are illustrative of the invention but are not intended as limiting, it in any way. Parts are given by weight except where it is otherwise indicated.

ExArnLn 1 g parts of methyl methacrylate monomer containing 0.2 part of benzoyl peroxide were mixed with 2.0 parts of a partially saponifled P lyvinyl acetate, 0.02 part of technical dodecyl diethylcyclohexylamine sulfate, and 73.68 parts of water by means of a high speed mixer. The saponifi cation number of the partially saponifled polyvinyl acetate was 109 and the viscosity of a 4% aqueous solution at 20 C. was 20 c. p. 3.8 parts of a 32% basic aluminum acetate solution and 0.5 part of acetic acid were added while continuing the agitation. After agitating for a total of 3 minutes, a stable emulsion was obtained. The emulsion was heated for 4 hours at 67 C. to obtains dispersion of a resinous polymer. The dispersion obtained was stable.

Emu: 2

1.0 gram of the product from Example 1 was dispersed in 200 cc. of soft water and the pH of the bath adjusted to 4.0 by the addition of acetic acid. The bath was placed in a pint Mason jar and a 10 gram strip of silk piece goods added to the jar. The bath was agitated for 10 minutes at F. and for 5 minutes at F. At least 80% of the resin disersion was absorbed by the silk from the bath. This was determined by comparison of the opacity of the exhausted bath with standard dispersions of known concentrations. The silk was hydro-extracted and dried at 200 F. to obtain a full, delustered fabric.

Similar results were obtained in applications from baths adjusted by the addition of either acetic acid and/or ammonia to a pH of 5.0, 6.0 and 6.6.

EXAMPLE 3 EXAMPLE 4 One gram of the product from Example 1 was dispersed in 200 cc. of soft water and the pH of the bath adjusted to 4.5. A ten gram skein of wool yarn was entered in the bath at 100 F. and agitated. The dispersed phase was absorbed by the yarn in about 15 minutes. The skein was hydro-extracted and dried at about 200 F. Considerable fullness was added to the yarn.

EXAMPLE 5 The monomer of n-butyl methacrylate was substituted for methyl methacrylate monomer in A stable resin dispersion was obtained.

The dispersed resin was applied to wool, silk and nylon as in Examples 2, 3 and 4. Considerable fullness, body and stiffness were added to the textiles.

EXAMPLE 6 Iso-butyl methacrylate was substituted for methyl methacrylate in Example 1. A stable resin dispersion was obtained.

The dispersed resin was applied to wool, silk and nylon as in Examples 2, 3 and 4. Considerable fullness, body and stiffness were added to the textiles.

Exnlru: 7

10 parts of methyl methacrylate monomer and 10 parts of n-butyl methacrylate monomer containing 0.2 part of benzoyl peroxide were mixed with 2.0 parts of a partially saponified polyvinyl acetate, 0.02 part of technical dodecyl diethylcyclohexylamine sulfate, and 73.68 parts of water by means of a high speed mixer. The saponiflcation number of the partially saponified poLvvinyl acetate was and the viscosity of a 4% aqueous solution at 20 C. was 20 c. p. 3.8 parts of a 32% basic aluminum acetate solution and 0.5 part of acetic acid were added while continuing the agitation. After agitating for a total of 3 minutes, a stable emulsion was obtained. The emulsion was heated for four hours at 67 C. to obtain a dispersion of a resinous polymer. The dispersion obtained was stable to storage. The dispersed resin was substantive to silk, wool and nylon when applied under the conditions described in Examples 2, 3 and 4. A full, crisp hand was acquired by the treated fabrics on drying at 200 F.

EXAMPLE 8 15 parts of methyl methacrylate monomer and parts of di(methylcyclohexyl) adipate were substituted for the methyl methacrylate in Example 1. A stable dispersion of a polymerized resin was obtained. The material was substantive to wool, silk and nylon as shown in application tests made under the conditions described in Examples 2, 3 and 4. The treated fibers acquired a fuller hand without greatly increasing the stiffness. The finish on the nylon stocking improved the resistance of the stocking to snagging. The di(methylcyclohexyl) adipate of this example may be replaced by di(butoxy ethyl) phthalate, di-butyl phthalate, or butyl phthalyl butyl glycolate.

The methyl methacrylate of the example may be substituted by n-butyl methacrylate or isobutyl methacrylate or by mixtures of the diner-- ent methacrylic acid esters. Finishes obtained from dispersions prepared with these substitu tions for methyl methacrylate are fuller and crisper than those prepared with methyl methacrylate.

EXAMPLE 9 Composition A Per cent Refined paramn wax 16.7 Acetate of deacetylated chitin 1.3 Basic aluminum acetate 3.0 Acetic i 0.5

Technical dodecyl diethylcyclohexylamine sulfate 0.09 Water 78.41

A 10 gram silk stocking was entered in the bath, contained in a pint Mason jar, at 80 F. The pH of the bath was 5.5. The jar was agitated in a Launderometer for 10 minutes. About 80% of the. dispersion was absorbed by the stocking. The bath was heated to 100 F. and agitated for an additional 5 minutes. The dispersion was completely removed from the bath. The stocking was hydro-extracted and boarded on an electrically heated drying form at about 220 F. The treated stocking was highly delustered and water repellent. A soft hand and considerable fullness were added to the stocking. The finish was resistant to removal by laundering.

(b) 1.0 gram of the composition from Example 5 and 0.5 gram of Composition A were applied to a 10 gram silk stocking as in (a). The treated stocking was highly water repellent and the hand of the stocking was considerably crisper and fuller "compared with the untreated stocking. The finish was resistant to removal by laundermg.

(c) 0.3 gram of the composition from Example 1, 0.7 gram of the composition from Example 5 and 0.3 gram of Composition A were applied to a 10 gram silk stocking as in (a) The treated stocking was highly delustered and water repellent and had a full hand. The finish was resistant to laundering.

(d) 0.25 part of the composition from Example 5 and 0.25 part of Composition A were dispersed in 199.5 parts water and applied to a wool serge fabric as in Example 4. The fabric was dried on a mangle at 220 F. The dried fabric had a full hand and was highly water repellent. The finish was resistant to removal by laundering.

(e) 0.7 gram of the composition containing nbutyl methacrylate plasticized with di(methylcyclohexyl) adipate from Example 8 and 0.3 gram of Composition A were dispersed in 199 cc. of water and applied to a ten gram nylon stocking as in Example 3. A full, firm hand with considerable surface lubrication was obtained. The stocking was highly water repellent. The finish was resistant to removal by laundering.

EXAMPLE 10 Twenty-five parts of vinyl acetate monomer containing 0.25 part of benzoyl peroxide were mixed by high speed agitation with 70.70 parts of an aqueous solution containing 2.5 parts of a partially saponified polyvinyl acetate (saponification No. 180; viscosity in a 4% aqueous solution at 20 C., 40 c. p.) and 0.025 part of technical dodecyl diethylcyclohexylamine sulfate. 3.8 parts of a 32% basic aluminum acetate solution and 0.5 part of glacial acetic acid were added while continuing the agitation. After agitating for a total of 3 minutes, a stable emulsion was obtained. The emulsion was heated for 6 hours at 67 C. to obtain a stable dispersion of a resinous polymer.

EXAMPLE 1 l 6.25 parts of vinyl acetate monomer and 18.75 parts of methyl methacrylate monomer were substituted for the 25 parts of vinyl acetate monomer in Example 10. The partically saponified polyvinyl acetate used had a saponification number of 108 and a viscosity of 20 c. p. for a 4% solution at 20 C. A stable dispersion of a resinous polymer was obtained.

EXAMPLE 12 20 parts of vinyl acetate monomer and 5 parts of di(butoxy-ethyl) phthalate were substituted for the 25 parts of vinyl acetate monomer in Example 10. A stable dispersion of a resinous polymer was obtained.

EXAMPLE 13 5 parts of vinyl acetate monomer, 15 parts of methyl methacrylate monomer and 5 parts of di- (butoxy-ethyl) phthalate were substituted for the monomers in Example 11. A stable dispersion of a resinous polymer was obtained.

EXAMPLE 14 EXAMPLE 15 One gram of the composition from Example 13 was applied to a 10 gram nylon stocking as in Example 3. A full, firm hand was obtained and the stocking was markedly improved in snag resistance. The finish was highly resistant to laundering.

EXAMPLE 16 One gram of the composition from Example 11 was applied to a gram silk stocking as in Example 2. The stocking was boarded at 220 F. on a hoisery form. A full, firm hand was obtained. The finish was highly resistant to laundering.

Exlmru: 17

One gram of the composition from Example 12 was applied to a 10 gram silk stocking as in Example 2. The stocking was boarded on a hosiery form at 220 F. A full, crisp hand was obtained. The finish was highly resistant to laundering.

Exsurtr: 18

The aluminum acetate of Example 1 was replaced by an equal weight of barium chloride. A\stable dispersion was obtained. Similar results were obtained on applying the product to wool, silk and nylon as in Examples 2, 3 and 4.

Exam 19 The aluminum acetate and acetic acid of Example 1 were replaced by equal weights of aluminum formats and formic acid. A dispersion was obtained. Similar results were obtained on applying the product to wool, silk, and nylon as in Examples 2, 3, and 4.

The processes for preparing positively charged dispersions substantive to silk, wool, and nylon described in this invention are applicable not only to the methacrylates and vinyl acetate but to polymerizable water insoluble hydrocarbon derivatives and particularly to vinylidene compounds. Typical vinylidene compounds are styrene, butadiene viny1 chloride, vinyl acetate. acrylates, methacrylates, acrylonitriles, acrylamides, methacrylonitriles and methacrylamides. The vinylidene compounds may be used separately or as mixtures to form interpolymers. The resinous polymers may be plasticized; typical plasticizers are described by Strain, Kennelly, and Dittmar, Ind. Eng. Chem. 31, 382, 1939.

The positive charge on the dispersed particles may be obtained by the addition of water soluble heavy metal or multivalent salts instead of aluminum acetate to the emulsions. For example. salts of Ba, Cd, Co, Fe, Ni, Mn, Zn, Sn, Pb, Sb, Bi, and Cr can be used. Formic, propionic, hydrochloric, sulfuric and other acids may be used to replace acetic acid in the emulsions. It is preferable to add the heavy metal salts during the process of emulsification; however, satisfactory substantive emulsions can be obtained by adding the heavy metal salts or salts of multivalent metals to the aged dispersions.

Other substantially non-polar high molecular weight water-soluble protective colloids may be used in place or partially saponified polyvinyl acetate. In place of partially saponifled polyvinyl acetate there may be used cellulose derivatives such as water-soluble methyl cellulose, the ethylene oxide reaction product of oleyl alcohol, etc.

Compositions described herein are useful in the treatment of silk hosiery. When products of the invention are applied to nylon hosiery, knit goods and flat goods good bodying effects are obtained.

stable 1 to those specified in the subjoined claims, which Products covered by the invention may be applied with positively charged substantive wax dispersions, and combinations of the products with wax emulsions impart excellent bodying and water-repellent properties to wool fabrics.

The primary advantages of the invention are the economical and uniform treatment of silk, wool, and nylon textile materials with resin finishes. The compositions described are particularly adapted to the treatment of knitted fabrics which cannot be handled satisfactorily on the quetsch.

Resin dispersions described herein when applied alone or with positively charged substantive wax dispersions produce finishes on silk hosiery that greatly improve the appearance and durability of the stockings. The finishes are much more durable and faster to washing than th finishes which have been previously used.

(1) Excellent delustering is obtained which is effective for the life of the stocking. The delustering is not characterized by the chalkiness obtained with opaque pigment delustrants.

(2) The application of a resin dispersion with a positively charged substantive wax dispersion produces a water repellent, spot resistant finish that is more durable than the effect obtained from the wax finish alone.

(3) The stockings show a regularity of stitch that is improved in comparison with untreated stockings. The treated stockings are more sheer in appearance.

(4) The resin dispersions or combination resin and positively charged substantive wax dispersions applied as described in this invention produce a more uniform, reproducible finish. The fact that the finish is completely exhausted from the bath makes it possible to obtain the same amount of finish on stockings from batch to batch, regardless of the size of the batch and the ratio of bath to goods. The regulated exhaustion of the finish makes possible the uniform application over the surface of the stockings throughout the batch.

(5) The resin finish improves the resistance of the stocking to snagging.

(6) The application of a resin finish with a positively charged substantive wax dispersion produces stockings that board andhandle more easily than stockings finished with the finishes previously used.

(7) The application of the resin dispersions alone or in combination with positively charged (8) The application of the resin dispersions with positively charged substantive wax dispersions makes it possible to obtain an economical,

uniform and reproducible water repellent and bodying effect on wool fabrics.

The subjoined claims are intended to cover not only the products described herein but to generically cover certain products which are described and specifically claimed in my copending applications, Serial Numbers 351,084, 351,086, 351,087, and 351,088, filed on this same day. to which reference may be made for further disclosure. The resin dispersions described and specifically claimed in the aforesaid copending applications contain other ingredients, in addition modify the properties of the resin dispersions or change the finishing effects which these dispersions impart to fabrics.

The above description and examples are intended to be illustrative only and not to limit the scope of the invention. Any departure therefrom which conforms to the spirit of the invention is intended to be included within the scope of the appended claims.

I claim: a

1. A substantive textile finishing composition adapted for application to textile fibers by a process of exhaustion from a dilute aqueous bath comprisinga stable aqueous dispersion of a poly merized vinylidene compound containing as the dispersing agent a substantially non-polar high molecular weight water soluble protective colloid of the group consisting of partially saponified polyvinyl esters, water soluble methyl celluloses and the water soluble ethylene oxide reaction product of oleyl alcohol, and containing as an agent which renders the dispersed polymerized vinyl compound substantive to textile fibers. a water soluble salt of a multivalent metal.

2. A substantive textile finishing composition adapted for application to textile fibers by a process of exhaustion from a dilute aqueous bath comprising a stable aqueous dispersion of a polymerized vinyl acetate containing as the dispersing agent a su fitantially non-polar high molecular weight water soluble protective colloid of the group consisting of partially saponified polyvinyl esters, water soluble methyl celluloses and the water soluble ethylene oxide reaction product of oleyl alcohol, and containing as an agent which renders the dispersed polymerized vinyl acetate substantive to textile fibers, a water soluble salt of a multivalent metal.

3. A substantive textile finishing composition adapted for application to textile fibers by a process of exhaustion from a dilute aqueous bath comprising a stable aqueous dispersion of a polymerized alkyl methacrylate containing as the dispersing agent a substantially non-polar high molecular weight water soluble protective colloid of the group consisting of partially saponified polyvinyl esters, water soluble methyl celluloses and the water soluble ethylene oxide reaction product of oleyl alcohol, and containing as an agent which renders the dispersed polymerized alkyl methacrylate substantive to textile fibers a water soluble salt of a multivalent metal.

4. A substantive textile finishing composition adapted for application to textile fibers by a process of exhaustion from a dilute aqueous bath comprising a stable aqueous dispersion of a polymerized methyl methacrylate containing as the dispersing agent a substantially non-polar high molecular weight water soluble protective colloid of the group consisting of partially saponified polyvinyl esters, water soluble methyl celluloses and the water soluble ethylene oxide reaction product of oleyl alcohol, and containing as an agent which renders the dispersed polymerized methyl methacrylate substantive to textile fibers a water soluble salt of a multivalent metal.

5. A substantive textile finishing composition adapted for application to textile fibers by a process of exhaustion from a dilute aqueous bath comprising a stable aqueous dispersion of a polymerized butyl methacrylate containing as the dispersing agent a substantially non-polar high molecular weight water soluble protective colloid of the group consisting of partially saponified polyvinyl esters, water soluble methyl celluloses and the water soluble ethylene oxide reaction product of oleyl alcohol, and containing as an agent which renders the dispersed polymerized butyl methacrylate substantive to textile fibers a .water soluble salt or a multivalent metal.

6. A substantive textile finishing composition adapted for application to textile fibers by a process of exhaustion from a dilute aqueous bath comprising a stable aqueous dispersion of a polymerized vinylidene compound containing as the dispersing agent a partially saponified polyvinyl acetate, and containing as an agent which renders the dispersed polymerized vinyl compound substantive to textile fibers a water soluble salt of a multivalent metal.

7. A substantive textile finishing composition adapted for application to textile fibers by a process of exhaustion from a dilute aqueous bath comprising a stable aqueous dispersion of a polymerized vinyl acetate containing as the dispersing agent a partially saponified polyvinyl acetate, and containing as an agent which renders the dispersed polymerized vinyl acetate substantive to textile fibers a water soluble salt of a multivalent metal.

8. A substantive textile finishing composition adapted for application to textile fibers by a process of exhaustion from a dilute aqueous bath comprising a stable aqueous dispersion of a polymerized alkyl methacrylate containing as the dispersing agent a partially saponified polyvinyl acetate, and containing as an agent which renders the dispersed polymerized alkyl methacrylate substantive to textile fibers a water soluble salt of a multivalent metal.

9. A substantive textile finishing composition adapted for application to textile fibers by a process of exhaustioi from a dilute aqueous bath comprising-a stable aqueous dispersion of a polymer-' ized methyl methacrylate containing as the dispersing agent a partially saponified polyvinyl acetate,.and containing as an agent which renders the dispersed polymerized methyl methacrylate substantive to textile fibers a water soluble salt of a multivalent metal.

10. A substantive textile finishing composition adapted for application to textile fibers by a process of exhaustion from a dilute aqueous bath comprising a stable aqueous dispersion of a polymerized butyl methacrylate containing as the dispersing agent a partially saponified polyvinyl acetate and containing as an agent which renders the dispersed polymerized butyl methacrylate substantive to textile fibers a water soluble salt of a multivalent metal.

11. A substantive textile finishing composition adapted for application to textile fibers by a process of exhaustion from a dilute aqueous bath comprising a stable aqueous dispersion of a polymerized vinylidene compound containing as the dispersing agent a partially saponified polyvinyl acetate and as an agent which renders the dispersed polymerized vinyl compound substantive to textile fibers a water soluble aluminum salt.

12. A substantive textile finishing composition adapted for application to textile fibers by a process of exhaustion from a dilute aqueous bath comprising a stable aqueous dispersion of a polymerized vinyl acetate containing as the dispersing agent a partially saponified polyvinyl acetate and as an agent which renders the dispersed polymerized vinyl acetate substantive to textile fibers a water soluble aluminum salt.

13. A substantive textile finishing composition adapted for application to textile fibers by a proces of exhaustion from a dilute aqueous bath comprising a stable aqueous dispersion of a polymeriized alkyl methacrylate containing as the dispersing agent a partially saponifle p lyvinyl acetate and as an agent which renders the dispersed polymerized alkyl methacrylate substantive to textile fibers a water soluble aluminum salt.

14. A substantive textile finishing composition adapted for application to textile fibers by a proc-- ess of exhaustion from a dilute aqueous bath comprising a stable aqueous dispersion of a polymerized methyl methacrylate containing as the dispersing agent a partially saponifled polyvinyl acetate and as an agent which renders the dispersed polymerized methyl methacrylate substantive to textile fibers a water soluble aluminum sal 15. A substantive textile finishing composition adapted for application to textile fibers by a process of exhaustion from a dilute aqueous bath comprising a stable aqueous dispersion of a polymerized butyl methacrylate containing as the dispersing agent a partially saponifled polyvinyl acetate and as an agent which renders the dispersed polymerized butyl methacrylate substantive to textile fibers a water soluble aluminum salt.

JOSEPH EDWARD SMITH.

CERTIFICATE OF commonon.

Patent No. 2,515,089. 7 February 29, 19141;.

JOSEPH EDWARD SMITH.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page I, sec 0nd column, line 19, after "-acetate'i insert --mo reiparticu larly of the type described in copending application Serial No. 551,082 filed of even date herewith--; and that the said Letters Patent should be read withv this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 16th d of ma A. 1). 191m.

Leslie Frazer (Seal) Acting Commissioner of Patents.