US2499653A

US2499653A - Treatment of protein-containing textile materials and products thereof

Info

Publication number: US2499653A
Application number: US703708A
Authority: US
Inventors: Edward L Kropa; Arthur S Nyquist
Original assignee: American Cyanamid Co
Current assignee: Wyeth Holdings LLC
Priority date: 1946-10-17
Filing date: 1946-10-17
Publication date: 1950-03-07
Anticipated expiration: 1967-03-07

Description

Patented Mar. 7, 1950 TREATMENT OF PROTEIN- CONTAINING TEXTILE MATERIALS AND PRODUCTS THEREOF Edward L. Kropa, Old Greenwich, and Arthur S. Nyqnist, Cos Cob, Com, minors to American Cyanamid Company, New York, N. 1., a corporation of Maine No Drawing. Application October 17, 1940 Serial No. 703,708

13 Claims.

This invention relates to the treatment of protein-containing textile materials and to the products thereof. More particularly, the invention is concerned with a process of treating protein-containing textile materials, for example wool and wool-containing fabric and other textile materials, to impart improved properties thereto by treating, more particularly impregnating or coating and impregnating, the textile material with a composition comprising a reactive product of polymerization of a polymerizable mixture including, by weight, from about 2 to 20% of maleic anhydride and from about 98 to 80% of a lower alkyl ester of acrylic acid that contains from one to four carbon atoms, inclusive, in the alkyl grouping thereof, e. g., ethyl acrylate. The resulting textile material is heated at a temperature (e. g., at about 200 to 300 F. or slightly above) and for a period of time sufilcient to cure the said polymerization product substantially completely. The cured polymerization product is substantially water-insoluble.

Protein-containing textile materials, for instance wool-containing textile materials such as loose wool itself and yarns, threads and woven, felted and knitted cloth composed of or containing wool have a very undesirable tendency to felt and shrink when subjected to ordinary washing operations. The tendency of these protein-containing textile materials to felt and shrink is generally due to curling and intertwining of the protein fibers as the fabrics are wetted and subjected to the mechanical movements of the washing process. As a result, the textile material becomes more closely compacted, thicker and has a considerably reduced area.

A number of different methods have been proposed for the treatment of textile materials formed of or containing wool or other protein fibers in order to prevent or decrease felting and shrinking. In many cases such reduction in felting and shrinking tendencies has been obtained at the sacrifice of some other desirable property of the material. Some treatments damage the fiber and reduce the wearing qualities while others impart an undesirable harshness to the fabric. Other treatments are not permanently efiective and may even cause an ultimate increase in shrinkage. Still other shrink-proofing methods are diflicult to apply with uniformity and create hazards to the workers involved in their applications.

The present invention is based on our discovery that protein-containing textile materials, e. g., wool and wool-containing textile materials, when treated with a composition comprising a reactive product of polymerization (or copolymer) of a polymerizable mixture including maleic anhydride and a lower alkyl ester of acrylic acid, e. g., ethyl acrylate, in the proportions by weight set forth in the first paragraph of this specification. yield a treated material which has excellent shrinkage resistance, increased tensile strength, a soft feeling to the touch, and a permanent finish which remains after laundering. For example, when a toluene solution of a soluble copolymer of maleic anhydrlde and ethyl acrylate (10 parts by weight maleic anhydride and parts by weight ethyl acrylate) was applied to a piece of woolen goods and the treated goods was heated to evaporate the solvent and to cure the copolymer substantially completely, the treated cloth had a soft hand, a substantially permanent finish, and even after five launderings (10 minutes each in a soap solution followed by drying) and a final washing of 1 hour in a soap solution showed a shrinkage of only 8.3%. In marked contrast, untreated woolen cloth when similarly laundered for the same number of times showed a shrinkage of 39.4%. Furthermore, the tensile strength of the treated cloth was considerably enhanced, being at least about 35% stronger than the untreated fabric. It was quite unexpected and unpredictable that such copolymer compositions would impart such improved shrinkage resistance and tensile strength to a protein-containing textile material, specifically a woolen fabric. Even more surprising was the fact that this shrinkage resistance was imparted to the woolen goods without materially lessening its softness to the touch.

By employing the maleic anhydride-acrylate copolymer compositions of the kind with which this invention is concerned, it is possible to obtain equally as good or better control of the shrinkage oi, for example, wool than is possible by the use of conventional treating materials and at a lower cost since the copolymer used is relatively inexpensive. Our copolymer compositions have the further advantage that protein-containing textile materials, more particularly wool-containing textile materials, which have been treated therewith quickly reach a point of maximum shrinkage upon repeated launderings, whereas the same textiles when untreated or when treated with some of the prior treating materials show increasingly higher percentage increases in shrinkage upon further laundering. This also was quite surprising and unexpected and in no way could have been predicted.

spaces Another advantage from the use of our copolymer compositions in practicing the present invention is that, if desired, a somewhat lesser amount of treating material may be employed than is cutomarily required in the treatment of wool-containing textiles with most conventional treating materials. For instance, in the case of wool as much as about 16% of conventional treating material may be required in order to obtain satisfactory shrinkage and crease control of the woolen fabric, whereas with our copolymer compositions satisfactory results usually are obtained with about 8 or 10% or less of the copolymer. The use of higher amounts, however, for example as much as or by weight of the untreated material, or even higher (e. g., or of the copolymer is not precluded, and in some cases even may be desirable, for instance when it is desired to provide a weighted proteincontaining fabric.

The reactive copolymers used in practicing this invention are prepared by mixing maleic anhydride with a lower alkyl ester of acrylic acid that contains from one to four carbon atoms, inclusive, in the alkyl grouping thereof, e. g., methyl acrylate, ethyl acrylate, propyl acrylate, isopropyi acrylate, butyl acrylate, isobutyl acrylate, etc., in the percentage proportions hereinbefore given. The mixed ingredients are copolymerized under anhydrous conditions. Copolymerization may be eilected under, for example, the influence of ultra-violet light, with or without heat and with or without a polymerization catalyst such, for instance, as benzoyl peroxide or other organic peroxide. If desired, the mixed ingredients may be copolymerized in solution state, for example, in solution in an inert organic solvent, e. g., toluene, benzene, xylene, dioxane, ethers (e. g., dibutyl ether), esters (e. g., butyl acetate), chlorobenzene, ethylene dichloride, ketones (e. g., methyl ethyl ketone), etc. The temperature of copolymerization may be varied as desired or as conditions may require, but ordinarily will be within the range of from about 20 to about 150 0. when copolymerization is effected in the absence of a solvent. When the mixed ingredients are copolymerized in solution state, then copolymerization generally is effected at the boiling temperature of the solution. In all cases, the temperature of copolymerization is below the decomposition temperature of the monomeric materials.

In copolymerizing the maleic anhydride with the lower alkyl ester of acrylic acid, we prefer to use heat and a catalyst for accelerating the polymerization. Illustrative examples of catalysts that may be employed, in addition to benzoyl peroxide, are inorganic peroxides such, for example, as barium peroxide, etc.; dialkyl peroxides, e. g., lauryl peroxide, stearyl peroxide, di-(tertiary butyl) peroxide, etc.; symmetrical diacyi peroxides, e. g., acetyl peroxide, lauroyl peroxide, stearoyl peroxide, etc.; unsymmetrical or mixed diacyl peroxides, e. g., acetyl benzoyl peroxide, etc. We prefer to use benzoyl peroxide as the polymerization catalyst. Any suitable amount of catalyst may be used but in general the catalyst concentration will be within the range of about 0.05 to 2 or 3% by weight 01' the mixed copolymerizable materials. The amount of maleic anhydride in the polymerizable mixture should not exceed about 20% by weight of the mixed ingredients since with higher proportions greater difiiculty is encountered in producing the copolymer and the resulting copolymer when applied to the protein-containing textile material yields a finished material which is more water sensitive than when the amount of maleic anhydride is 20% or less. Although satisfactory results are obtained when the polymerizable mixture contains as little as about 2 or 3% by weight thereof of maleic anhydride better results are obtained when the maleic anhydride is present in larger amount, for example, about 5 to 15% by weight of the polymerizable mixture. Particularly good results have been obtained with copolymers produced from a polymerizable mixture of, by weight, about 10% of maleic anhydride and about of a lower alkyl ester of acrylic acid, specifically ethyl acrylate.

In eifecting copolymerization of the mixed ingredients it is desirable to avoid the use of any compounds, for example, water, which are reactive with the maleic anhydride. In the case 0! the higher molecular weight, soluble copolymers they may be dissolved in an organic liquid which is insoluble in water and an emulsion then formed of the organic solution of the copolymer. The presence of the organic liquid appears to act as a barrier to prevent water from coming into contact with the copolymer. In order further to impede the transfer of liquid water and water vapor one can introduce into the initial solution or dispersion, a small amount (e. g., from about 0.01 to 10% by weight of the copolymer) of a material which is known to impede the transfer of water vapor, e. g., polyethylene, crystalline products, e. g., paraflln, microcrystalline waxes, etc.

The reactive copolymer composition may be applied to the protein-containing textile material in any suitable manner. The textlle material may be contacted with the copolymer in undiluted state or the copolymer may be applied in the form oi. a solution or dispersion thereof. In all cases the amount of copolymer which is deposited or incorporated in the protein-containing textile material, e. g., wool 01' a wool-containing textile material, is at least about 2% by weight, based on the dry weight of the textile material. The amount will vary depending, for instance, upon the particular protein-containing textile material that is undergoing treatment, the particular copolymer employed, the mode of applieation, the kind of emulsifying agent used if applied from a dispersion, whether or not a weighted textile is desired, etc. Ordinarily, however, the amount of copolymer that is incorporated in the textile material is from about 3 to 15% by weight of the dry, untreated material, but if a weighted textile is wanted it may be much more, for example as much as 30% or more by weight of the dry, untreated textile.

If the textile material to be treated contains fats, oils or other contaminants, it is first thoroughly cleaned in any suitable manner prior to treatment with the copolymer. Various methods may be used in applying the copolymer. For example, the dry textile material may be immersed and passed through suitable rolls, as in a padder or mangle, to insure uniform impregnation and to remove exces copolymer. However, the textile material may be impregnated or coated and impregnated by other methods, for example, by spraying or by brushing a solution or dispersion of the copolymer upon the material or by applying thereto a liquid copolymer in undiluated state. Or, the solid copolymer itself may be combined with the textile material as by passing a sheet or cloth of the same, having thereon or therein the copolymer in finely divided solid state, between hot rolls. The impregnating operation and the concentration of the copolymer (in solution, dispersion or other state) are ad- Justed so that the amount of copolymer which is taken up by the textile material will be most eii'ective and economical in producing the desired results.

If the reactive polymerization product or copolymer has been applied in dissolved or dispersed state to the textile material, the treated textile is heated to volatilize the inert, volatile organic liquid (11' the copolymer was applied as a solution thereof) or to volatilize the water and the inert organic liquid (if the copolymer was applied in the form of an inert organic liquid-water dispersion) and, also, to polymerize the reactive polymerization product or copolymer to a substantially completely cured condition or state, in which form it is water-insoluble. During this heat treatment the copolymer may react chemically with the textile material, more particularly with the protein molecules thereof or with free or combined water on or in the textile. The protein may react with the maleic portion of the copolymer to form an amide thereof.

Any suitable elevated temperature may be employed, but in no case should the temperature be so high as to char or otherwise detrimentally affect the textile material. For instance, with most protein-containing textiles temperatures within the range of about 200 to 300 F. may be used satisfactorily. Ordinarily, temperatures at or slightly above the boiling point of water or of the particular inert organic liquid employed are sufficient to effect the desired result. Of course, it will be understood by those skilled in the art that there is a time-temperature relationship involved: the lower the temperature the longer the time of heating, and the higher the temperature the shorter the heating period. The temperature also will vary somewhat with, for instance, the particular protein-containing textile which has been treated and the particular copolymer employed.

After the textile material, e. g., wool fabric, has been treated as above described, it may be given, if desired or necessary, a mild soaping for a short period before finishing. The textile material then may be given the usual finishing treatments required in a particular case, e. g., decatizr ing, brushing, shearing, pressing, etc.

In order that those skilled in the art better may understand how the present invention may be carried into eifeet, the following examples are given by way of illustration and not by way of limitation. All parts are by weight.

Example 1 Parts Maleic anhydride 10.0 Ethyl acrylate 90.0 Benzoyl peroxide 0.2 Toluene 33.0

The maleic anhydride and benzoyl peroxide were dissolved in the ethyl acrylate. Thirty-three parts dry toluene was added. This solution was transferred to a dropping funnel attached to a three-necked flask which was also fitted with a condenser and a thermometer. About parts of solution was run into the flask and heating on the steam bath was begun. After 1 minutes of heating, exothermic polymerization commeneed in the flask and after heating for an additional 15 seconds dropwise addition of the solution from the dropping funnel was started.

The addition of the solution was complete after 30 minutes had elapsed. Polymerization proceeded vigorously during most of this time, reaching a maximum temperature of 135 C. during this period. However, continued external heating after the addition resulted in further exothermic polymerization. Heating was discontinued after 52 minutes elapsed time and the reaction mass was allowed to cool. One hundred and fifty parts toluene was added after which parts of the solvent was distilled off at reduced pressure in order to remove any unreacted ethyl acrylate. A portion of the resulting solution of maleie anhydride-ethyl acrylate copolymer was diluted with additional dry toluene to obtain a composition containing about 10% of solids.

Part or the maleic anhydride-ethyl acrylate copolymer solution obtained prior to dilution with toluene to 10% solids content was coagulated by adding an excess of petroleum ether thereto. The coagulated coplyomer was separated, redissolved in toluene, and coagulated again by adding an excess of petroleum ether to the toluene solution. The coagulated copolymer was separated and washed with petroleum ether. By this treatment any unreacted maleic anhydride was removed from the reaction product. The acid number of the purified copolymer was found to be 108.0 The theoretical acid number of a copolymer of ethyl acrylate and maleic anhydride having a 9 to 1 weight ratio of the two components in the copolymer is 114.5. Since the acid number of the purified copolymer of this example was 108, this shows that the ethyl acrylate and maleic an hydride copolymerized in nearly the same ratio in which the monomers were present in the polymerizable mixture.

A piece of woolen goods was treated with the toluene solution (10% solids content) prepared as above described. The wool sample (9 inches by 23 inches in size) was immersed in the solution and passed through rolls to give about 8 or 9% wet pick-up. The sample was framed, air dried for a short period and then heated for 9 minutes at 290 F. After cooling to room temperature the sample was removed from the frame, allowed to remain undisturbed for about 16 hours and was then measured prior to laundering. The method or laundering was a modification of the standard method of the A. A. T. C. C. and involved heating for 20 to 30 minutes at 240 F, while drying after each washing. After a cycle of five Washing (10 minutes in soap solution) and drying operations and a final washing of 1 hour in a soap solution, the dried, treated cloth showed a shrinkage of only 8.3%. In marked contrast, untreated woolen cloth when similarly laundered for the same number of times showed a shrinkage of 39.4%. The laundered cloth was pliable and soft. The shrinksee data on the treated and untreated woolen sample are shown below:

When tested for tensile strength, the treated woolen cloth had a value of pounds as against '73 pounds for the untreated cloth (A. S. T. M. D-39-39 standard method of test, grab method).

aceacaa Brample 2 Cycle.... 1 2 3 4 5 6 Washing Time in Minutes 10 l i0 10 l0 10 Percent Shrinkage 0.1 4.4 6.4 6.7 7.2 7.2

Example 3 A maleic anhydride-butyi acrylate reactive copolymer was prepared in essentially the same manner as described under Example 1, using 10 parts maleic anhydride and 90 parts butyl acrylate, and dioxane as a solvent instead of toluene. A sample of wool was treated with a 10% dioxane solution of this copolymer as set forth under Example 1. The following shrinkage data were obtained upon laundering the treated sample:

Per cent shrinkage After five washing cycles of 10 minutes A maleic anhydride-ethyl acrylate reactive copolymer was prepared in essentially the same manner as described under Example 1, using parts maleic anhydride and 95 parts ethyl acrylate. and dioxane as a solvent instead of toluene. A sample of woolen cloth was treated with a dioxane solution of this copolymer as set forth under Example 1. After five washing cycles of 10 minutes each as described under Example 1, followed by heating. the dried, treated cloth showed a shrinkage of only 9.2%.

Example 5 Same as Example 4 with the exception that 95 parts butyl acrylate instead of ethyl arcylate was used in preparing the reactive copolymer. After five washing cycles of 10 minutes each as described under Example 1, followed by heating, the dried, woolen cloth containing the water-insoluble maleic anhydride-butyl acrylate copolymer showed a shrinkage of only 8.3%.

Example 6 Same as Example 3 with the exception that 10% tricresyl phosphate. based on the solids content of the soluton, was added to the 10% di: xane solution of the maleic anhydride-butyl acrylate reactive copolymer. The following shrinkage data were obtained upon laundering the treated sample:

Percent shrinkage After five washing cycles of 10 minutes each 8.0 After minutes washing 9.7

Example 7 Same as Example 6 with the exception that triphenyl phosphate was substituted for tricresyl phosphate. The following shrinkage data were obtained upon laundering the treated sample;

Percent shrinkage After five washin cycles of 10 minutes each 8.0

After 60 minutes washing 9.4

Example 8 In this example a treating solution was used containing approximately equal parts by volume of a 10% aqueous solution of methylated methylol melamine (prepared as described, for example, in Patent No. 2,329,622-Johnstone. Jr., et al.) and a 10% dioxane solution of a reactive copolymer of 10 parts maleic anhydride and 90 parts ethyl acrylate. The following shrinkage data were obtained upon laundering a piece of woolen goods which had been treated with this solution, and thereafter heated to volatilize the solvent and to cure the mixture of methylated methylol melamine and reactive maleic anhydride-ethyl acrylate copolymer to a substantially water-insoluble condition:

Percent shrinkage After five washing cycles of 10 minutes each 6.4 After 60 minutes washing 9.2

Example 9 In this example a treating solution was used containing approximately equal parts by volume of (1) a 10% solution of a butylated methylol melamine dissolved in a 50-50 mixture of butanol and xylene and (2) a 10% dioxane solution of a. reactive copolymer of 10 parts maleic anhydride and parts ethyl acrylate. (The butylated methylol melamine is prepared as described, for example, in the aforementioned patent of Johnstone, Jr., et al.) The following shrinkage data were obtained upon laundering a piece of woolen goods which had been treated with this solution, and thereafter heated to volatilize the solvent and to cure the mixture of butylated methylol melamine and reactive maleic anhydride-ethyl acrylate copolymer to a substantially water-insoluble condition:

Percent shrinkage After five washin cycles of 10 minutes each 4.7 After 60 minutes washing 6.9 After five washing cycles of 10 minutes each 9.4

The shrinkage resistance of the treated protrain-containing textile material is substantially less when hexyl and higher alkyl esters of acrylic acid are employed in making the copolymer. This is shown by the following example:

Example 10 A copolymer of 10 parts maleic anhydride and 90 parts hexyl acrylate was prepared in essentially the same manner as described under Example 1. After treating a. piece of woolen goods with a dioxane solution of this copolymer, followed by heating to evaporate the solvent and to cure the copolymer substantially completely, the following shrinkage data were obtained upon laundering the impregnated goods:

Percent shrinkage After five washing cycles of 10 minutes each- 15.0 After 60 minutes washing 31.4

The shrinkage resistance of the treated proteincontaining textile material also is substantially less when the amount of maleic anhydride used in making the copolymer is much above about by weight of the polymerizable mixture. This is shown by the following examples:

Example 11 A copolymer of 30 parts maleic anhydride and 70 parts ethyl acrylate was prepared in essentially the same manner as described under Example 1. After treating a piece of woolen goods with a toluene solution of this copolymer, followed by heating to evaporate the solvent and to cure the copolymer, the following shrinkage data were obtained upon laundering the treated goods:

Percent shrinkage After five washing cycles of 10 minutes each- 22.8 After 60 minutes washing 31.9

Example 12 Same as Example 11 with the exception that 40. parts instead of 30 parts maleic anhydride was used. The following shrinkage data were obtained upon laundering the treated woolen goods:

Percent shrinkage After five washing cycles of 10 minutes each- 24.4 After 60 minutes washing 32.8

It will be understood, of course, by those skilled in the art that our invention is not limited to the specific treating compositions described in Examples 1 to 9, inclusive. Thus, instead of using ethyl acrylate or butyl acrylate in preparing the reactive copolymer, we may employ any other lower alkyl ester of acrylic acid, e. g., methyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec.-butyl acrylate, tert.-butyl acrylate, etc. The acrylic ester and maleic anhydride should be present in the polymerizabie mixture in a ratio by weight corresponding to from about 80 to 98% of the former to from about 20 to 2% of the latter. Instead of benzoyl peroxide any other polymerization catalyst may be employed, numerous examples of which hereinbefore have been given.

Illustrative examples of inert, volatile, organic liquids (that is, volatile, organic liquids which are non-reactive with the copolymer composition) which may be used, if the copolymer is to be applied in solution state or in the form of an inert organic liquid-water dispersion to the textile material, are benzene, toluene, xylene, dioxane, ethers (e. g., di-isopropyl ether, dibutyl ether, etc), esters (e. g., butyl acetate, etc.), chlorinated hydrocarbons, for instance carbon tetrachloride, trichloroethylene, ethylene dichloride, chlorobenzenes (e. g., 1,3-dichlorobenzene. etc). ketones (e. g., methyl ethyl ketone, etc.) petroleum naphtha, etc. If applied in an inert organic liquid-water dispersion, the inert organic liquid is one which is immiscible with the water.

It the copolymer is to be applied to the textile material in the form of a dispersion, specifically an inert organic liquid-water dispersion, any suitable emulsifying agent may be employed, e. g., the sodium salts of the sulfates of a mixture of lauryl and myristyl alcohols, dioctyl sodium suifcsuccinate, sodium salts of aliiylaromatic sulfonic acids (e. g., the sodium salt of isopropylnaphthalene sulfonle acid), quaternary ammonium salts (e. g., cetyl dimethyl ammonium chloride), etc. However, the emulsion or dispersion should be such that the copolymer is adequately protected in the dispersion from the action of the water. In such an emulsion or dispersion the proportions of water and inert organic liquid may be varied as desired or as conditions may require, for example from, by volume, about 25 to parts water to about '75 to 25 parts inert, volatile organic liquid. The amount of copolymer based on the total amount of water and inert organic liquid may vary considerably, e. g., from about 5 to 20% or more by weight of the total weight of the water and inert organic liquid. Good results are obtained using a solution containing about 10 to 2 by weight thereof of the copolymer (e. g., a maleic anhydride-ethyl acrylate copolymer) dissolved in an inert, volatile organic liquid, speciflcally toluene, which solution is then emulsifled with about an equal weight of water using about 0.5%, by weight of the total water and toluene, of the sodium salts of the sulfates of a mixture of lauryl and myristyl alcohols as an emulsifying agent. The amount of emulsifying agent may be varied considerably, but ordinarily will be within the range of from about 0.5 to 10% by weight of the copolymer in the dispersion.

Our process may be applied in the treatment of various types of protein-containing textiles, for instance, those formed of or containing wool, silk, mohair, fur, leather, regenerated fibers or fabrice, e. g., those produced from casein, soya. bean, collagen, eta; mixtures of such protein-containing textiles, and mixtures of such protein-containing textiles with other types of textiles, for instance, those formed of cellulose or regenerated cellulose, e. g., cotton, linen, hemp, jute, ramie, sisal, cellulose acetate rayons, viscose rayons, cuprammonium rayons, etc. In the case of textiles containing mixtures of protein-containing and cellulose-containing fibers, the efiect of the treatment is mostly on the former but the latter also may be beneficially affected and the copolymer may combine therewith. Our process also may be applied in the treatment of colored textile materials as well as whites.

The maieic anhydride-acrylate copolymer may be applied alone to the textile material or it may be applied in combination with other modifying agents, numerous examples of which are given in our copending application Serial No. 694,156, filed August 30, 1946. The copolymer also may be used in combination with isocyanate copolymers of the kind. disclosed in our aforementioned copending application and also in our copending application Serial No. 694,157, filed August 30, 1946. If desired, the copolymer may be used to supplement or in combination with conventional treating agents in the treatment of textiles to impart improved properties thereto.

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

What we claim as new and desire to secure by Letters Patent of the United States is:

l. A process of treating protein-containing textile material to reduce the felting and shrinking tendencies thereof which comprises (1) treating said textile material solely with a composition comprising a reactive product of polymeri- 75 cation of a polymerizable mixture including, by

access:

11 weight, from about 2 to 20% of maleic enhydridc and from about 98 to 80% of a lower alkyl ester of acrylic acid that contains from one to four carbon atoms, inclusive, in the alkyl grouping thereof, and (2) heating the resulting treated material to cure the said polymerization product.

2. A process as in Claim 1 wherein the lower alkyl ester of acrylic acid is ethyl acrylate.

3. A process of reducing the felting and shrinking tendencies of wool-containing textile material which consists in (1) impregnating such a material with an inert, volatile organic liquid-water dispersion of a reactive product of polymerization of a mixture containing, by weight, from about 2 to 20% of maleic anhydride and from about 98 to 80% of a lower alkyl ester of acrylic acid that contains from one to four carbon atoms, inclusive, in the alkyl grouping thereof, the takeup of the said dispersion being such as to deposit in the said textile material at least about 2%. based on the dry weight of the textile material, of the said polymerization product and (2) heating the resulting treated material to volatilize the water and the organic liquid from the said dispersion and to cure the said polymerization product, said cured product being substantially water-insoluble.

4. A process of reducing the felting and shrinking tendencies of wool-containing textile material which consists in 1) impregnating such a material with a solution of a soluble copolymer dissolved in an inert, volatile organic liquid, said polymer being the product of polymerization of a mixture containing, by weight from about 2 to 20% of maleic anhydride and from about 98% to 80% of a lower alkyl ester of acrylic acid that contains from one to four carbon atoms, inclusive, in the alkyl grouping thereof, the take-up of the said solution being such as to deposit in the said textile material at least about 2% by weight, based on the dry weight of the textile material, of the said soluble copolymer and (2) heating the resulting treated material to volatilize the organic liquid from the said solution and to cure the said polymerization product, said cured prodnot being substantially water-insoluble.

5. A process of treating woolen textile material to reduce the felting and shrinking tendencies thereof which consists in (1) impregnating said textile material with a composition comprising a reactive product of polymerization of a mixture containing, by weight, from about 5 to of maleic anhydride and about 95 to 85% of ethyl acrylate and (2) heating the resulting treated material at a temperature within the range of about 200 to 300 F. to cure the said polymerization product, said cured product being substantially water-insoluble.

6. A process of treating woolen fabric material to reduce the shrinking tendencies thereof and to impart an improved finish thereto which consists in (l) impregnating said fabric material with a composition comprising a reactive product of polymerization of a mixture containing, by weight, from about 2 to of maleic anhydride and from about 98 to 80% of a lower alkyl ester of acrylic acid that contains from one to four carbon atoms, inclusive, in the alkyl grouping thereof, and (2) heating the resulting treated material at a temperature within the range of about 200 to 300 F. for a period sumcient to cure the said polymerization product substantially completely.

7. A protein-containing textile material which is resistant to felting and shrinking and which is impregnated with a substantially water-insoluble composition comprising a product of polymerization of a polymerizable mixture including. by weight. from about 2 to 20% of maleic anhydride and from about 98 to of a lower alkyl ester of acrylic acid that contains from one to four carbon atoms, inclusive, in the alkyl grouping thereof, said composition being free from any compound which is reactive with the said polymerization product.

8. A wool-containing textile material which is resistant to felting and shrinking and which is impregnated with a substantially water-insoluble composition comprising a product of polymerization of a polymerizable mixture including, by weight, from about 5 to 15% of maleic anhydrlde and from about '95 to of ethyl acrylate, said composition being free from any compound which is reactive with the said polymerization product.

9. A woolen textile material which is resistant to shrinking and which is impregnated with at least about 2%, by weight of the untreated material, of a substantially water-insoluble composition comprising a copolymer which is the product of polymerization of a mixture containmg, by weight, from about 2 to 20% of maleic anhydride and from about 98 to 80% of a lower alkyl ester of acrylic acid that contains from one to tour carbon atoms, inclusive, in the alkyl grouping thereof, said composition being free from any compoimdlwhich is reactive with the said polymerization product.

10. A woolen fabric materlabwhich is resistant to shrinking, has a soft feeling to the touch and which is impregnated with about 3 to 15%, by weight of the untreated material, of a substantially water-insoluble copolymer which is the product of polymerization of a polymerizable mixture of. by weight, from about 5 to 15% of maleic anhydride and from about 95 to 85% of ethyl acrylate.

11. Shrink-resistant wool which is impregnated and coated with about 3 to 15%. by weight of the untreated wool, of a substantially waterinsoluble composition comprising a copolymer which is the product of polymerization of a polymerizable mixture of, by weight, about 10% maleic anhydride and about ethyl acrylate, said composition being free from any compound which is reactive with the said copolymer.

12. A protein-containing textile material which is resistant to felting and shrinking and which is impregnated with a substantially water-insoluble composition consisting of a mixture, cured under heat in situ, of (l) a lower alkylated methylol melamine and (2) a reactive product of polymerization of a polymerizable mixture including, by weight, from about 2 to 20% of malelc anhydride and from about 98 to 80% of a lower alkyl ester of acrylic acid that contains from one to four carbon atoms, inclusive, in the alkyl grouping thereof.

13, A process of treating a woolen fabric to reduce the shrinking tendencies thereof and to impart an improved finish thereto, said process consisting of (l) immersing the said fabric in a solution of soluble copolymer dissolved in an inert volatile organic liquid, said copolymer being a reactive product of polymerization of a mixture of comonomers consisting of, by weight, about 10% of maleic anhydride and about 90% of ethyl acrylate and said solution containing about 10% by weight of the said copolvmer, (2) squeezing excess solution from the resulting fabric so as to obtain an impregnated woolen fabric which contains about 8 to 9% by weight, based on 13 the dry weight of the said fabric, of the said 00- polymer, and (3) heating the squeezed fabric at a temperature of the order of 290 F. for a period suflicientiy long to volatilize the organic liquid from the solution retained in the fabric and to cure the said copolymer, said copolymer in cured state being substantially water-insoluble.

- EDWARD L. KROPA.

AR'I'HUR S. NYQUIST.

REFERENCES CITED Number 14 UNITED STATES PATENTS Name Date Voss July 14, 1936 Voss May 30, 1939 Kaase Sept. 5, 1939 Johnstone Sept. 14, 1943 Drey-i'us Sept. 19, 1944 Watson Apr. 23, 1946 Atwood Apr. 8, 1947 Powers May 10, 1949

Claims

1. A PROCESS OF TREATING PROTEIN-CONTAINING TEXTILE MATERIAL TO REDUCE THE FELTING AND SHRINKING TENDENCIES THEREOF WHICH COMPRISES (1) TREATING SAID TEXTILE MATERIAL SOLELY WITH A COMPOSITION COMPRISING A REACTIVE PRODUCT OF POLYMERIZATION OF A POLYMERIZABLE MIXTURE INCLUDING, BY WEIGHT, FROM ABOUT 2 TO 20% OF MALEIC ANHYDRIDE AND FROM ABOUT 98 TO 80% OF A LOWER ALKYL ESTER OF ACRYLIC ACID THAT CONTAINS FROM ONE TO FOUR CARBON ATOMS, INCLUSIVE, IN THE ALKYL GROUPING THEREOF, AND (2) HEATING THE RESULTING TREATED MATERIAL TO CURE THE SAID POLYMERICATION PRODUCT.