US2780567A - Stabilization of protein-containing textiles - Google Patents

Description

United States Patent STABILIZATION OF PROTEIN-CONTAINING TEXTILES Benjamin B. Kine and Nathaniel A. Matlin, Levittown, Pa., assignors to Rohm & Haas Company,'Philadelphia, Pa, a corporation of Delaware No Drawing. Application March 22, 1954, Serial No. 417,979

Claims. (Cl. 117-141) This invention relates to the treatment of protein-containing textile materials and to the products thereof. It

relates more particularly to a process of treating textile materials comprising scale-surfaced proteinfibers, such as wool and wool-containing fabric, whereby the textile materials are stabilized against shrinking and felting.

An object of this invention is to provide aqueous dispersions of resins which are so stable that they can be stored and shipped, and which, when they are applied to protein-containing textile materials and are then heated, markedly reduce the tendency of the materials to shrink or render them substantially shrink-proof. Another object is to provide a process for shrink-proofing and feltproofing textiles containing scale-surfaced protein fibers, Whether of natural or artificial origin, through the use of the aforesaid dispersions. It is an object to shrink-proof and felt-proof the textiles without adversely affecting such other properties of the textile as wearing qualities, tensile strength, or hand. Still another object is to produce protein-containing textile materials, particularly woolen fabrics, which have :a much reduced tendency to shrink and which also retain the desirable characteristics which are associated with woolen fabrics. A

While this invention is principally concerned with improvements of, and more particularly the reduction of shrinkage and/or complete stabilization of textile materials of proteinaceous types, and while the invention is described primarily in terms of Wool-containing textiles, the invention embraces the treatment of other proteincontaining textile materials, such as those made of or containing silk, mohair, fur, Aralac and other synthetic fibers which are produced from casein, soybeans, collagen, et cetera, and especially scale-surfaced protein fibers of either natural or artificial origin. The terms textile and tex tile materials are used herein to include filaments, fibers, yarns, thread, plied yarns, rovings, and slivers'as such or in Woven, knitted, felted or otherwise formed fabrics, sheets, cloths and the like. Such textile materials may contain only one kind of proteinaceous fiber or a mixture of such fibers with other natural or synthetic fibers, such as of cotton, linen, rayon, nylon, or polymers of acrylonitrile.

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 effective and may even cause an ultimate increase in shrinkage. Still other shrink-proofing methods are difficult to apply with uniformity and create hazards to the workers involved in their applications.

Certain polymers of the linear type have also been recommended, such as those containing isocyanate groups and certain esters of acrylic or methacrylic acid, such as the glycidyl esters thereof. The types of polymers of this class that have been found effective for reducing the shrinkage and felting of pntein-containing textiles have so far been of rather limited scope. It has been found that many polymers of this type, which are quite similar to those which are effective have no effect or have so little effect as to be of no practical value. For example, polymers or copolymers of glyceryl methacrylate,

CH2=C(CH3)COOCH2CH(OH) CHzOH are of this character.

The process of treating the textile materials in accordance with the invention comprises impregnating them with an aqueous dispersion of the kind described in detail below and then heating the textiles at a temperature which isat least as high as 212" 'F., but which is lower than the charring point of the textile. During the treatment of the textiles in this Way, a chemical reaction is believed to take place between the proteinaceous portion of the textile and the copolymer in the dispersion. The copolymer appears to be chemically bound to the textile and not merely deposited as a dry coating on the fibers. As a result, the resinous copolymer is not leached or removed from the textile during subsequent wet-Washing or drycleaning operations.

In accordance with the present invention, it has been found that polymers of certain ethers and sulfides which contain a single terminal alcoholic hydroxyl group on the monomeric units of the polymer are capable of improving the abrasion resistance of protein-containing textiles and are highly effective for the stabilization of textiles comprising scale-surfaced protein fibers, such as Wool. More specifically, it has been found that marked reduction in the shrinking and felting properties of Wool-containing textiles can be obtained by the application thereto of an aqueous dispersion of a water-insoluble, linear polymer of at least 3% by weight in the polymer molecule, of a monoethylenically unsaturated monomeric compound having the following general formula:

CH2=CH AROH where A is O or S-, and R is a straight or branched chain alkylene group having fro-m 2 to 10 carbon atoms, C2H4AC2H4, C2H4N(R)C2H4-, or C2H4N(R (R (X)C2H4 where R is H, CH3, C2H5,

f or C2H4OH and R and R are methyl, ethyl, or hydroxyethyl(.CzH4OH) groups and X is a negative radical, such as OH, Cl, Br, I, CH3SO4, and tolyl sulfonate. A preferred group isthat of the ethers having the formula:

CH2=CH-O( CH2 a:OH

where x may be 2 to 10 but is preferably 3 to 6, the efiiciency generally beinglat a maximum when x is 5.

Examples of these monomers are:

Thiodiglycol monovinyl sulfide Diethyleneglycol monovinyl ether The higher hydroxyalkyl vinyl ethers may be made in the same way as the lower ones are by the Reppe processesdisclosed in various patents and publications.

The polymers must not be water-soluble. Where the hydroxy ether or hydroxy sulfide monomer that is polymerized is of such character that a homopolymer produced therefrom is appreciably water-soluble, it is necessary to copolymerize such a monomer with at least one other copolymerizable monoethylenically unsaturated monomer which is of a character that will render the final copolymer insoluble in water. Many of the hydroxyl-containing monomers have such a large proproportion of hydrophobic groups in their molecule that homopolymers thereof will necessarily be water-insoluble and in such cases, a homopolymer can be applied to the fabrics for accomplishing the purpose of the invention. Frequently, however, it is preferable from the cost standpoint to copolymerize the hydroxy monomer with a cheaper and more readily available comonomer. Preferred compositions of the invention are, therefore, those copolymers of from 3 to 30% of the hydroxyl-containing ether or sulfide monomer or of :1 mixture of such monomers, the balance of the copolymer being formed of other less expensive comonomers.

Other polymerizable compounds containing a single ethylenically unsaturated group that may be copolymerized with the ethers or sulfides to produce binary, ternary, etc. coploymers include the esters of acrylic acid or methacrylic acid with monohydric alcohols such as methyl, ethyl, butyl, octyl, dodecyl, cyclohexyl, cyanoethyl, benzyl, phenylethyl, and the like; diesters of itaconic acid and the above alcohols; esters of maleic, fumaric or citraconic acids, and the above alcohols; vinyl esters of carboxylic acids such as acetic, propionic, butyric, and the like; vinyloxyalkyl esters such as vinyloxyethyl acetate, etc.;vinyl ethers such as ethyl vinyl ether, butyl vinyl ether, octyl vinyl ether; methacrylonitrile or acrylonitrile; acrylamide, or methacrylamide, and N-alkyl-substituted amides of these types; vinyltoluene, vinylnaphthalenes, such as 4-chloro-l-vinylnaphthalene, vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene fluoride, vinyli-dene cyanide, l-chloro-l-fiuoroethylene, ethylene, and styrene.

The emulsifiers or dispersingagents that may be used for preparing the monomeric emulsions before copolymerization or dispersions of the polymer after polymerization are preferably of the non-ionic type and include the following: alkylphenoxypolyethoxyethanols having alkyl groups of about seven to eighteen carbon atoms and 6 to 60 or more oxyethylene units, such as heptylphenoxypolyethoxyethanols, octylphenoxypolyethoxyethanols, methyloctylphenoxypolyethoxyethanols, nonyl phenoxypolyethoxyethanols, dodecylphenoxypollyethoxyethanols, and the like; polyet-hoxyethanol derivatives of methylene linked alkyl phenols; sulfur-containing agents 7 such as those made by condensing 6 to 60 or more moles of ethylene oxide with nonyl, dodecyl, tetradecyl, t dodecyl, and the like mercaptans or with alkylthiophenols having alkyl groups of six to fifteen carbon atoms; ethylene oxide derivatives of long-chained carboxylic acids, such as lauric, myristic, palmitic, oleic, and the like, or mixtures of acids such as found in tall oil containing 6 to 60 oxyethylene units per'molecule; analogous ethylene oxide condensates of long-chained alcohols, such as octyl, decyl, lauryl, or cetyl alcohols, ethylene oxide derivatives of etherified or esterified polyhydroxy compounds having a hydrophobic hydrocarbon chain, such as sorbitan monostearate containing 6 to 60 oxyethylene units, etc.; also ethylene oxide condensates of long-chain or branched-chain amines, such as dodecylamine, hexadecylamine, and octadecylamine, containing 6 to 60 oxyethylene groups; block copolymers of ethylene oxide and propylene oxide comprising a hydrophobic propylene oxide section combined with one or more hydrophilic ethylene oxide sections.

Particularly valuable resin dispersions are obtained by emulsifying a mixture of (a) one or more of the ethers or sulfides above and (b) one or more monomeric esters of acrylic, methacrylic, or itaconic acid or mixtures of these acids in water and polymerizing the mixture while it is in the emulsified form. The monomeric esters which have proven to be most satisfactory are the alkyl esters in which the alkyl group contains one to eight carbon atoms and which are exemplified by the following: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secbutyl, tert-butyl, isoamyl, tert-amyl, hexyl, heptyl, n-octyl, and Z-ethylhexyl acrylates, methacrylates, and itaconates.

The polymerizable emulsions can be prepared at temperatures from 0 C. to about 100 C., but intermediate temperatures are much preferred. Thus, when the preferred copolymers with esters are made with the esters in which the alkyl group contains one to four carbon atoms, a temperature from about 10 C. to about 60 C. is employed whereas a higher temperature; e. g., 30 C. to C., is recommended when esters containing five to eight carbon atoms in the'alkyl group are copolymerized. Peroxidic free-radical catalysts, particularly catalytic systems of the redox type, are recommended. Such systems, as is well known, are combinations of oxidizing agents and reducing agents such as a combination of potassium persulfate and sodium metabisulfite. Other suitable peroxidic agents include the per-salts such as the alkali metal and ammonium persulfates and perborates, hydrogen peroxide, organic hydroperoxides such as tert-butyl hydroperoxide and cumene hydroperoxide, and esters such as tert-butyl perbenzoate. Other reducing agents include water-soluble thiosulfates, tertiary amines, such as triethanolamine, hydrosulfites, and the salts, such as the sulfates, of metals which are capable of existing in more than one valence state such as cobalt, iron, nickel, and copper. The most convenient method of preparing the dispersions of copolymers comprises agitating an aqueous suspension or emulsion of a mixture of copolymerizable monomers and a redox catalytic combination at room temperature without the application of external heat. The amount of catalyst can vary but for purposes of efliciency from 0.01% to 3.0%, based on the weight of the monomers, of the peroxidic agent and the same or lower proportions of the reducing agent are recommended. In this way, it is possible to prepare dispersions which contain as little as 1% and as much as 60% or even more of the resinous copolymer on a weight basis. It is, however, more practical, and hence preferred, to produce dispersions which contain about 30-50% resin-solids.

The proportion of the polymer that is applied to the fabric may vary widely, such as from 1 to 20% by weight of the fabric, a proportion of 3 to 7 /z% being preferred. The hand or feel of the fabric may be varied widely depending on the polymer selected. Thus polymers of ethers which contain a long-chain alkylene group between the terminal hydroxyl and the ether oxygen will generally have a softer hand than those with a shorter alkylene chain. The same applies when sulfide monomers are employed. The variation in hand may be controlled by the selection of the comonomer as well. Thus, for a given sulfide or ether monomer containing terminal hydroxyl groups, a softer and more lubricous hand may be imparted by copolymerizing with a comonomer or such character that it introduces long-chain fatty groups into the copolymer. For example, the hydroxylgroup-containing monomer may be copolymerized with acrylic, methacrylic, or itaconic esters of alcohols containing from 1 to 18 carbon atoms, the longer the chain of the alcohol, the more lubricous the hand.

The dispersion is deposited on the textile material by such means as exhausting, spraying, or dipping. What is required is that the textile material be saturated and impregnated by the dispersion. This can be done at any desired temperature short of the boiling point of the dispersion. Ordinarily the textile is padded at room temperature with a dispersion which has been adjusted to a resin-content of about 1% to 25%. The material being treated must pickppxor take up andptheniretainsuflicient dispersions to providefrom 1% to about 20%, 'and'preferably from 3% to 74/2% of the copolymer, based on the weight of the-dry textile.

The impregnated textile material must then be heated at .a temperature between 212 F. and 400 F. for a period of about one-half'minute to 30 minutes, the higher the temperature, the shorter the period required. A flash cure at temperaturesabove 400 F., even up to 700 F. for short periods of five to ten seconds, may be employed. In any event, the time and temperature should not be such as to damage the fabric. Preferably this heating is efiectedat aqtemperature from 240 F. (for about 1-0l5 .minutes) .t0.about13.10 F. .(for about 5-10 minutes'), .andjitis believed ithat it effects some chemical reaction involving the polymerand possibly the textile. In

anyevent, the, heating sets thepolymer on the textile, and

in the case of wool, reduces shrinkage and/or imparts full dimensional :stability thereto. Drying .of the treated textile and the .heat treatment which .eflfects the chemitcal reaction -.can be carried out simultaneously or. concurrently in one step, or theiextile can .be substantially or completely dried at a conveniently lower temperature and then heated later at the higher temperature. As will .be evident' toathose skilled -.in the art,-the optimal-length f theheatingperiod-depends on the;particular temperature which :is employed, :on the particular -copoiymer,

. andon the-quantity thereof which is on the textile. But

' ily determinedby heating pieces of theirnpregnated textile for =varying lengths of "time at a (given temperature and then measuring the resultant stabilization of the individual pieces by means of a wet-washing test.

In-sornecases, it may be advantageous toad'd an acid tothedispersion with which the textile is treated to accelerate the reaction and to bring about the stabilization or reduction in shrinkage "in'a shorter period of time at a. given temperature or atadower temperature in a,given time. .Strong ac'idssuch as formic, oxalic, .sulfuric, .and phosphoric acids are recommended. For *this purpose from 1.% to 12% .acid,-.based on the weight .of the pad liquor, is suggested. It has also been found that the use in conjunctionwith the dispersions of .such .acid catalyst with .an auxiliary reactive substance, .such (as formaldehyde, or materials which are equivalents of formaldehyde suc'h asg'lyoxal 0r 'formals,-or mixtures .ofiormaldehyde or the like with aminoplast-forming compounds, or low-molecular weight, .waterasolub'le, reaction products, preferably of formaldehydeor the like with such compounds-enhances the stabilization of'wool'en or pro- While such auxiliary reactive -subteina'ceous textiles. stances and the acid catalyst may be "employed as an added component -of--the dispersions, they may'also be employed-by applying-a solution of the auxiliary reactive substance and theacid catalyst'after the textile'has'been treatedwith the dispersion. The use :o'ftheauxiliary reactive substance is advantageous in some cases where it-becomes especially evidenton extended laundering of the textile. Also in combination fabrics, such as those containing fibers or yarns'of .silk or cellulosic type, such as cotton or rayon, as Well as fibers or yarns of proteinaceeus types, such .as wool, including :as an example rivatives thereof, such as N,N-e thyleneurea, N,N-ethyleneurea, N,N'-dimethylurea, NN'-diethylurea, N,N'-dimethoxymethylurea, -N,N-d-imethoxymethylurea, N,N- .diethoxyethylurea, tetramethoxymethylurea, tetraethoxyethylurea. Similar reaction ;products of formaldehyde with: triazines, :such .as melamine may also be: employed, .such as N,N-'dimethylmelamine and alcohol-modified melamine-formaldehyde thermosetting resin condensates e. g., of methyl and ethyl alcohols, for example, dimethoxymethyl-monomethylolmelamine.

The treated textiles are characterized bygreater resistance to abrasion and/ or reduced shrinkage and, in many cases, fully practical dimensional stability against laundering, by which is meant "that they are substantially shrink-proof. They do not stiffen, degrade or discolor on aging -or on exposure to ultraviolet light as do ,comparable textiles which have been treated, for example, with laticesof butadiene copolymers.

The effectiveness of the dispersions exemplified below in stabilizing wool 'wasdetermined by impregnating measured pieces of flannel with them, drying, and heating the impregnated pieces of flannel-ate temperature of 240 F. or higher, laundering thepieccs in hot water, then drying "them and measuringtheshrinkage. In these tests pieces of 'Botany .woolenflannel (style #405;.2/2 right hand 45 twill, 5'5 x 44; Setwist .in ends, Z in picks;

scoured, carbonized, neutralized .and bleached) were used. All pieceswere 10 inchessquare, with axesalong the yarn systems. The pieces of flannel were padded with a pad liquor of thexresin dispersion which was so adjusted .in solids-content ,as to provide the desired amountof resins-solids ,(.1-%'2i0% based on the weight of the ,dry flannel) at -,a pick-up of about that is,

:at a temperature of at least 240 F. The specimens were washed,*togetherwith-untreated pieces of flannel, in

a Cascade wheel washer containing '70 grams of soap :(Ivory) in 10 gallons of water for five hours. In all :cases the loadin the washer was made up to threepounds with :cotton towe'ling and the temperature was maintained at 140 F. The values of shrinkage are given as percentage reduction in the initial area after taking into account any inherent residual shrinkage in the initial fabric that may be presentasra result=of previous drying under tension and is achievable by-simply wetting and drying. In other words, the shrinkage values hereinbelow are obtained by subtracting relaxation shrinkage fromthe. actual shrinkage measured.

The following examples serve to illustrate this invention:

Example 1 A dispersion of a copolymer was prepared by emulsifying parts by weight of.n-butyl acrylate with l0 parts 'by weightof 8-hydroxyethyl vinyl sulfide in about 300 ,pa-rtsby'weight of waterv with about v6 parts by weight of an ethylene oxide condensation product of an octyl phenol containing between 30 and 50 oxyethylene units per molecule. To the emulsified monomers 0.3% by weight (on the total Weight-of monomers) of ammonium persult'ate, 1.0% of triethanolamine, and 0.06% of sodium .h-ydrosulfite were added locatalyze 'the-copolymerization which .was .carried -out for a period of seventeen minutes. lldringwthis period the temperature rose from 20 C. to 46 C.

The resin dispersion was'diluted to a 10% concentration. of the resin (copolymer) content and applied .to a woolfiannel as described above. After dryinglO minutes at 240 F., foliowedby curing for 10 minutesat 300 F., it was found that .the proportion vof copolymer applied to the fabric was about 7.5% of the weight of the fabric. The shrinkage of the treated .f-abric after the five-hour wash described hereinabove was zero.

Example 2 The procedure of Example 1 was followed except that only 7.5% of a copolymer of 95% of n-butyl acrylate and of fi-hydroxyethyl vinyl sulfide were applied to the fabric. After the five-hour wash test, the fabric showed a shrinkage of 6%. A control fabric (untreated) showed 63% shrinkage after washing under the same conditions.

Example 3 The procedure of Example 2 was followed except that after drying the fabric at 240 C., it was passed through an aqueous solution containing 1% sulfuric acid and 1% formaldehyde and then dried minutes at 240 C. and cured for a period of 10 minutes at 300 F. The resulting fabric showed no shrinkage after the five-hour wash test. Whereas the hand obtained in Example 1 was softer than that of the initial fabric, the formaldehyde treatment reduced the softness of the hand only slightly as compared to the product of Example 1.

Example 4 An aqueous dispersion was prepared of a copolymer of 95 parts by weight of n-butyl acrylate with 5 parts by weight of 'y-hydroxypropyl vinyl sulfide. The procedure of Example 2 was followed and the shrinkage after a fivehour wash was found to be 19% as compared to a 63% shrinkage of a control fabric after the five-hour wash test.

Example 5 The procedure of Example 3 was followed with the copolymer of Example 4. The resulting formaldehydetreated fabric had a shrinkage of 3% after the five-hour wash test.

Example 6 The procedure of Example 2 was followed with an aqueous dispersion of a copolymer of 95% by weight of n-butyl acrylate and 5% by weight of j8-hydroxyethyl vinyl ether. The fabric showed a shrinkage of 22% after the five-hour wash which compared favorably with the control fabric which shrunk 63% after the wash test.

Example 7 The procedure of Example 3 was followed with the copolymer of Example 6. The fabric showed a shrinkage of 4% after the five-hour wash test.

Example 8 The procedure of Example 3 was followed with a copolymer of Example 8. The formaldehyde treatment altered the hand only slightly and did not affect the shrinking which amounted to zero after the five-hour wash.

Example 10 The procedure of Example 2 was followed with an aqueous dispersion of a copolymer of 85% s-butyl acrylate with of B-hydroxyethyl vinyl ether. After the five-hour wash test, the fabric exhibited only 3% shrinka Example 11 The procedure of Example 3 was followed with the co- 8 polymer of Example 10 and the resulting fabric showed no shrinkage after the five-hour wash test.

Example 12 The procedure of Example 2 was followed with an aqueous dispersion of a copolymer of methyl methacrylate and 10% of 6-hydroxyhexyl vinyl ether. The fabric obtained showed a shrinkage of zero after the fivehour wash test. Both before and after the wash, the fabric had a sandy feel or hand and was of reduced luster as compared to that of the initial fabric.

Example 13 The procedure of Example 1 was followed with a copolymer of by weight of n-butyl acrylate with 5% by weight of diethylene glycol monovinyl ether. The fabric showed no shrinkage after a five-hour wash and both before and after the wash, it had an exteremely soft hand.

A similar copolymer containing 5% thiodiglycol monovinyl ether instead of the diethylene glycol monovinyl ether when only 5% was applied to the fabric showed 1.9% shrinkage after the wash test.

Example 14 The procedure of Example 1 was followed with a copolymer of 92% by weight of diethyl itaconate with 8% of S-hydroxyoctyl vinyl ether. The fabric obtained showed a shrinkage of zero percent after the five-hour wash and it was characterized by an extremely soft lu- Example 15 The procedure of Example 2 was followed with an aqueous dispersion diluted to 20% resin-content of a copolymer of 97% of ethyl acrylate with 3% of S-hydroxypentyl vinyl ether. The fabric after the five-hour wash test showed a shrinkage of 2%.

In the following examples, the nitrogen-containing polymers increased the capacity to take up many acid dyes.

Example 16 The procedure of Example 1 was followed with an aqueous dispersion of a copolymer of 95% n-butyl acrylate with 5% of B-hydroxyethylaminoethyl vinyl ether. The fabric obtained showed a shrinkage of zero after a five-hour wash.

The same procedure is carried out with a copolymer of 60% ethyl acrylate, 30% N-butyl methacrylamide, and 5% of the same ether. The fabric shows a somewhat stiffer hand and no shrinkage on washing.

Example 17 The procedure of Example 1 was followed with a copolymer of 95% n-butyl acrylate with 5% of N-fi-hydroxyethyl-N-methylaminoethyl vinyl other except that the dispersion was diluted to about 2% and only 1.5% of the copolymer was applied to the fabric. The treated fabric showed no shrinkage after the five-hour wash test.

The same procedure was followed with a copolymer of 20% styrene, 70% ethyl acrylate and 10% of the same ether. The fabric had a somewhat stiffer hand but showed no appreciable shrinkage on washing.

Example 18 The procedure of Example 1 was followed with a copolymer of about 95% n-butyl acrylate with about 5% of hydroxyethyldimethyl(vinyloxyethyl)ammonium hydroxide except that the dispersion was diluted to about 4.5% and only 3.5% of the copolymer was applied to the fabric. The treated fabric showed no shrinkage after the five-hour wash test.

It is to be understood that changes and variations may be made without departing from the spirit and scope of the invention as defined in the appended claims.

rated monomeric units comprising at least 3% by weight,

in the polymer molecule, of units of a monomer having the formula CH2=CH'A--ROH where A is selected from the elements and S, and R is selected from the class consisting of straight and branched chain alkylene groups having from 2 to carbon atoms, -C2H4AC2H4, C2H4N(R')C2H4- and C2H4N(R (R )(X)C2H4- where R is selected from the group consisting of H, methyl, ethyl, and C2H4OH, R and R are selected from the group consisting of methyl, ethyl, and C2H4OH, and X is a negative radical.

2. A composition for the treatment of protein-containing textile materials comprising an aqueous dispersion of a water-insoluble polymer of at least 3% by weight, in the polymer molecule, of a monomer having the formula where x is an integer having a value from 2 to 10.

3. A composition for the treatment of protein-containing textile materials comprising an aqueous dispersion of a water-insoluble polymer of at least 3% by weight, in the polymer molecule, of a monomer having the formula where x is an integer having a value from 2 to 10.

4. As an article of manufacture, a textile material comprising protein fibers carrying from 1% to of a polymer of at least 3% of a monomer having the formula where A is selected from the elements 0 and S, and R is selected from the class consisting of straight and branched chain alkylene groups having from 2 to 10 carbon atoms,

where R is selected from the group consisting of H, methyl, ethyl, and C2H4OH, R and R are selected from the group consisting of methyl, ethyl, and -C2H4OH, and X is a negative radical.

5. As an article of manufacture, a textile material comprising protein fibers carrying from 1% to 20% of a water-insoluble polymer of at least 3% of a monomer having the formula where x is an integer having a value from 2 to 10.

6. As an article of manufacture, a textile material comprising wool fibers carrying from 1% to 20% of a waterinsoluble copolymer of 3% to of (1) a monomer having the formula where A is selected from the elements 0 and S, and R is selected from the class consisting of straight and branched chain alkylene groups having from 2 to 10 carbon atoms,

and

and

10 insoluble polymer of at least 3% of (N-fl-hydroxyethyl- N-methyl)aminoethylvinyl ether. i

8. As an article of manufacture, a textile material comprising wool fibers carrying from 1% to 20% of a waterinsoluble polymer of at least 3% of hydroxyethyldimethyl(viny loxyethyl)ammonium hydroxide.

9. As an article of manufacture, a textile material comprising wool fibers carrying from 1 to 20% of a waterinsoluble polymer of at least 3% of diethylene glycol monovinyl ether.

10. As an article of manufacture, a textile material comprising wool fibers carrying from 1 to 20% of a waterinsoluble polymer of at least 3% of S-hydroxypentyl vinyl ether.

11. As an article of manufacture, a textile material comprising wool fibers carrying from 1 to 20% of a waterinsoluble polymer of at least 3% of B-hydroxyethylaminoethyl vinyl ether.

l2. A process for treating proteinaceous textile materials to reduce the shrinkage thereof comprising treating such a material with an aqueous dispersion of a waterinsoluble polymer of at least 3% by weight, in the polymer molecule, of a monomer having the formula where A is selected from the elements 0 and S, and R is selected from the class consisting of straight and branched chain alkylene groups having from 2 to 10 carbon atoms, -C2HAC2H4-, C2H4N(R)C2H4 and C2H4N(R (R (X)C2H4- where R is selected from the group consisting of H, methyl, ethyl, and -C2H4OH, R and R are selected from the group consisting of methyl, ethyl, and -C2H4OH, and X is a negative radical, drying and heating the treated textile at a temperature of 212 F. to 700 F. for a period of about 5 seconds to about 30 minutes but insufiicient to damage the fabric.

13. The process of claim 12 in which the polymer is a copolymer of (N-B-hydroxyethyl-N-methyl)aminoethyl vinyl ether with butyl acrylate.

14. The process of claim 12 in which the polymer is a copolymer of hydroxyethyldimethyl(vinyloxyethyl)- ammonium hydroxide with butyl acrylate.

15. The process of claim 12 in which the polymer is a copolymer of diethylene glycol monovinyl ether with butyl acrylate.

16. The process of claim 12 in which the polymer is a copolymer of S-hydroxypentyl vinyl ether with butyl acrylate.

17. The process of claim 12 in which the polymer is a copolymer of fi-hydroxyethylaminoethyl vinyl ether with butyl acrylate.

18. A process for treating proteinaceous textile mate rials to reduce the shrinkage thereof comprising treating such a material with an aqueous dispersion of a waterinsoluble polymer of at least 3% by weight, in the polymer molecule, of a monomer having the formula where A is selected from the elements 0 and S, and R is selected from the class consisting of straight and branched chain alkylene groups having from 2 to 10 carbon atoms, C2H4AC2H4, C2H4N(R')C2H4- and -C2H4N(R (R (X)C2H4-- where R is selected from the group consisting of H, methyl, ethyl, and C2H4OH, R and R are selected from the group consisting of methyl, ethyl, and C2H4OH, and X is a negative radical, drying the textile, then treating the textile with formaldehyde and an acid catalyst, and drying and heating the treated textile at a temperature of 212 F. to 700 F. for a period of about 5 seconds to about 30 minutes but insufiicient to damage the fabric.

19. The process as defined in claim 18 in which the polymer is a copolymer of diethylene glycol monovinyl ether with butyl acrylate.

20. The process as defined in claim 18 in which the 1 1 polymer is a 'copolymer of S-hydroxypentyl vinylether 2,477,218 with butyl acrylate. 2,563,586 2,633,460 References Cited in the file of this patent UNITED STATES PATENTS 5 1,959,927 Reppe May 22, 1934 2,160,375 Voss et a1 May 30, 1939 2,329,622 Johnstone, Jr., et a1. Sept. 14, 1943 12 Thompson July 26, 1949 'Dazzi Aug. 7, 1951 Neher et a1 Mar. 31, 1953 OTHER REFERENCES Vinyl and Re1ated Po1ymer's, by Schildknecht, Copr. Feb. 20, 1952, pages 615 to 619 relied on.

Claims (1)

12. A PROCESS FOR TREATING PROTEINACEOUS TEXTILE MATERIALS TO REDUCE THE SHRINKAGE THEREOF COMPRISING TREATING SUCH A MATERIAL WITH AN AQUEOUS DISPERSION OF A WATERINSOLUBLE POLYMER OF AT LEAST 3% BY WEIGHT, IN THE POLYMER MOLECULE, OF A MONOMER HAVING THE FORMULA