US2467233A

US2467233A - Treatment of wool and products therefor

Info

Publication number: US2467233A
Application number: US694675A
Authority: US
Inventors: John B Rust
Original assignee: Montclair Research Corp
Current assignee: Montclair Research Corp
Priority date: 1946-09-03
Filing date: 1946-09-03
Publication date: 1949-04-12
Anticipated expiration: 1966-04-12

Description

Patented Apr. 12, 1949 TREATMENT ()F WOOL AND PRODUCTS THEREFOR John B. Rust, East Hanover, N. .L, assignor to Montclair Research Corporation, a corporation of New Jersey No Drawing.

Claims. 1

The present invention relates to the treatment and shrinkproofing of wool and wool containing fibers, to the methods for obtaining such treated and shrinkproofed fibers, to the materials and products resulting from such processes and treatments, and to the baths and materials utilized to accomplish these results as well as methods of preparing such baths and materials.

Urea formaldehyde type resins under which there may be included such synthetic resins as monoor di-methylol urea or mixtures thereof,

urea formaldehyde or alkylated urea formaldehyde condensation products, melamine formaldehyde resins and their alkylated modifications, such as for instance, the types known to the trade as Lanaset or Resloom, have been utilized in the treatment of textiles and fabrics for the purpose of crease-proofing or improving draping qualities of fabrics and textiles. Such agents are very inferior as shrinkproofing agents for wool and have little effect per se on such shrinkproofing unless cured at high temperature, but such control is usually accompanied by a degree of harshening of the fabric.

In prior applications more particularly identified below, the art has been taught that butadime-1.3 and some of its copolymers produce superior shrinkproofing effects on wool and related materials. In some cases there is a slight sticky or greasy hand imparted to the goods which may be objectionable depending on the particular utilities for which the materials are employed.

Among the objects of the present invention is the treatment of wool and wool containing materials to render the treated material substantially resistant to fulling, felting, or shrinking without damage to the fabric or fibers, and at the same time preserving the desirable hand of such materials as well as retaining favorable wearing qualities.

Other objects of the present invention include shrinkproofed wool and wool containing fabrics.

Other objects include 'the treatment of wool and wool containing materials to improve their draping qualities.

Further objects include the treating baths and materials required for the purposes set forth above, as well as methods for producing such materials.

Still further objects and advantages of the present invention will appear from the more detailed description set forth below, it being understood that this more detailed description is given by way of illustration and explanation only, and

not by way of limitation, since various changes therein may be made by those skilled in the art without departing from the scope and spirit of the present invention.

In accordance with the present invention, the wool or wool containing fibers, which may be of Application September 3,1946, Serial No. 694,675

various types, is treated with an emulsion more particularly an aqueous emulsion or dispersion, of a synthetic butadiene-1.3 polymer or copolymer in combination with aqueous solutions or dispersions of synthetic resins, such asfor instance, monoor di-methylol urea or mixtures thereof, urea formaldehyde or alkylated urea formaldehyde condensation products, melamine formaldehyde resins or their alkylated modifications, such as for instance, the types known to the trade as Lanaset" or Resloom."

It has been found that the combination of these two classes of materials not only improves the hand of the goods, but also quite unpredictably that certain unexpected improvements in the shrinkproofing characteristics accrue and there are also additional important qualities obtained such as improved draping, etc.

The wool treated may be of any desired type, such as raw wool, yarn, knitted or felted fabrics, woven or mixed goods, or combination fabrics in-- cluding wool in various ways.

The wool may be treated with the treating emulsions, dispersions or solutions in any desired way, as by immersing-the wool in the treating bath, or padding the treating bath on the wool, or

' by exhaustion of the polymer onto the wool, etc.,

various methods being more particularly illustrated below. And the sequence of the application of the resin and polymer components may be altered depending on the results desired. Thus if a finish is desired which has a certain "tack to it, it may be desirable to treat the goods first with the resin and then with the polymer. 0n the other hand, if a stiffer finish is desired, the procedure may be reversed, first treating the goods with the polymer and then with the resin. 01 combinations may be employed in which the treating bath includes both the resin and the polymer. An exceedingly simple and rapid method consists in a padding operation whereby both the resin and the elastomeric components are applied simultaneously from the same bath, followed by the required amount of curing. Where the treatment is carried out by successive applicatreatment with resin with or without curing, the

treated material is then subjected to an intermediate step of acidification or treatment with an acid solution before the application of the polymer bath.

Any of the urea formaldehyde type resins under which all of the modifications set forth above are included, may be utilized so that at least one of the urea formaldehyde and'melamine formaldehyde resins is employed and in the final product is in cured condition. Such urea formaldehyde type resins are generally applied in the fabrics, these may be padded and the excess liquor removed by passing the impregnated fabric through squeeze rolls. The strength of the pad liquor is dependent upon and determined by the amount of resin which it is desired to deposit on the fabric, as well as by the amount of liquid pick-up of which the fabric is capable.

The amount of resin applied to the goods is determined by the desired effect but will be generally limited between 1 and 25% on the weight of the fabric treated. A suitable curing catalyst such as ammonium phosphate, ammonium sulfate, etc.,'is desirably added to the solution containing the resin in order to facilitate. curing. The fabric may then be dried at any suitable drying temperature ranging between room temperature and 100 C. and then cured. Altematively, the fabric may be exposed to the curing temperature at once. The curing temperature, as well as the time required to complete the cure differs for various resins, and is conditioned also by the presence, quantity and kind of catalyst used. The curing temperature may vary between room temperature and 150 C. and the time required may range from 5 minutes to several days. It is important to note that materials may be employed which cure at room temperatures in reasonable periods of time so that ele-. vated temperatures and long periods of treatment are not essential but may be employed.

The butadiene-1.3 polymer or copolymer-may be applied to the fabric in various ways. Thus the aqueous polymeric dispersion may be diluted to. such an extent that the finished fabric will contain from 1 to 25% of the polymer. The goods are simply padded through this liquor or the material is treated by immersion. The excess liquor is removed either by squeezing or by centrif-ugal extraction. The bath may be conditioned with ammonia, wetting agents including long chain alcohol sulfates such as sodium lauryl sulfate, soaps and the like. In some cases it may be both possible and advisable to adjust the pH of the pad liquor below 7 in order to cause partial agglomeration, using acetic acid, sulfuric acid, phosphoric acid and the like, for this purpose. After padding, it is only necessary to dry the fabric at any desired temperature in order to set the polymer, that is, to form a stable bond between it and the fiber. On the other hand, the dispersion may be discharged on the fiber from a suitable bath, such a bath consisting essentially of an aqueous dilution of the polymeric dispersion to which has been added suitable conditioning electrolytes and the pH of which has been adjusted below 7, such a bath being stable at room temperatures unless in contact with receptive fibers. As such conditioning electrolytes, water-soluble salts may be used. The treatment is carried out by immersing the fibers or fabrics in this bath until exhaustion is complete. The temperature of the bath may be at room temperature but more desirably is kept between 40 C. and boiling. The rate of exhaustion is regulated by the temperature as well as by the concentration of the electrolytes. has cleared up substantially'or completely, the goods may be removed, rinsed and dried.

In application Serial No. 537,537, filed May 26, 1944, now Patent 2,447,538, of which the present application is a continuation-in-part, and in After the bathdo not precipitate the polymer.

which there is more particularly claimed the shrinkproofing of wool by the utilization of aqueous baths containing a synthetic butadiene polymer, an emulsifying agent and a conditioning electrolyte, the bath desirably having apH below 7, there is disclosed the utilization of butadiene polymers and polymers of its homologues to give superior non-felting effects. It has been found that the use of straight butadiene polymers or butadiene homologue polymers, that is, those in which the butadiene or the butadiene homologue is the sole polymer, gives superior nonfelting and wool shrinkproofing than do the hutadiene copolymers. The polymeric butadiene derivatives are those of butadiene-1.3 and its lower homologues, such as butadiene-1.3, isoprene, dimethyl butadiene, ethyl butadiene, ethoxy and methoxy butadiene, cyanobutadiene, particularly such derivatives of butadiene-1.3. As there set forth, copolymers of butadiene or butadiene homologues as set forth above may be utilized as long as the added component in producing the copolymer is not present in an amount which interferes with the desired shrinkproofing effect. Such added copolymerizing maierials include the methacrylates and acrylates, such as methyl methacrylate and vinyl compounds generally including vinyl acetate, methyl methacrylate, ethyl acrylate, styrene, acrylo-nitrile, vinyl pyridine, methacrylonitrile, isopropenyl methyl ketone, vinyl phenyl ketone, vinyl methyl ketone. and the like.

As further set forth in said application, the electrolyte content of the bath emulsion or dispersion may vary over substantial limits but sufficient electrolyte should be present to condition the bath so that the bath although stable in the absence of wool fibers, will deposit the polymer in the presence of the conditioning electrolyte. Generally the electrolyte content for this purpose will vary between about 25% to about 5000% based on the weight of polymeric butadiene derivative present. As such electrolyte, water-soluble salts may be used, desirably such salts which The followin are exemplary: sodium sulfate, sodium chloride, sodium bromide, sodium iodide, sodium phosphate, sodium sulfamate, sodium sulfite, sodium bisulfate, sodium bisulfite, sodium nitrate, sodium acetate, and the like, and similar salts of the other alkali metal group including those of potassium, lithium, caesium, and 'so on. Salts like zinc chloride may also be used where the coagulation does not appear to be too serious since it occurs in small particulate form, and the particles may be redispersed by stirring. Neutral salts, specifically salts of strong bases and strong acids, particularly inorganic salts, are preferred. They may be generally characterized as substantially neutral highly ionizing salts.

The operation of applying the polymer is desirably carried out at temperatures ranging from 40 C. to the boiling point of the bath. The process may be applied before or after fulling, weaving, scouring and the like operations. In some cases it may be applied in the dye bath. Mixed goods including wool-cotton, wool-rayon, etc., can be treated by the methods without any deleterious effect. The wool may be subjected to a pretreatment of any desired type, as for example, chlorination or bromination before being treated; in accordance with the present invention.

As further set forth in said prior application, the emulsions containing the butadiene polymer ass-mes may include any anionic emulsifying agent which is stable at a pH below 7. Such emulsifying agents are exemplified by sodium lauryl sulfonate.

sodium alkyl naphthalene sulfonates, long chain alkyl sodium sulfonates, sodium dioctyl suliosuc-; cinate. etc. There may also be used neutral noncationlc emulsifying agents such as mannitol monolaura-te, the reaction product of protein degradation products with acid chlorides, ethylene oxide reaction products with fatty acid, fatty alcohols, and the like.

As further set forth in said application, the emulsions of the polymer used are desirably but not necessarily, those which have been carried to a 100% polymerization. When 100% polymerization is obtained, considerable cross-linking has occurred in the polymer with consequent insolubility in organic solvents. Thus a type of prevulcanization of the polymer has been obtained.

It is also possible to vulcanize the polymers with vulcanizing accelerators such as thiuram dis-ulfite, etc, vulcanizing agents such as sulfur, dinitrobenzene, alkyl phenol sulfide, etc., either previous or subsequent to deposition or..,dyeing, into the wool fibers.

As pointed out immediately above, th polymer employed is in a condition in which if deposited from the emulsion or dispersion, the polymer is in a substantially non-tacky condition and gives a non-tacky deposit. It is substantially insoluble in organic solvents but may be swollen to some extent with such solvents. It is in a condition in which it is totally unsuitable as synthetic rubher or rubber-like material since if coagulated by any suitable means it gives crumbly materials which cannot be milled on rubber milling equipment and which are entirely composed of crosslinked polymers. Any of the polybuta'diene-L3 compositions as set forth in said prior application may be utilized as the component for this phase of the treatment of the present invention.

While as pointed out in said prior application, straight butadiene polymers and but-adiene homologue polymers are preferred, in order to obtain special effects certain additions and modiiication may be made to a limited extent. These additions may consist of other polymers in the form of emulsions, dispersions, factices, etc., and may include chloroprene polymer, polyvinyl compounds, polyacryl-ates. such as polyethylacrylate,

1945, entitled Wool treatinB. products and-meth-' ods, now Patent 2,447,876, there is more particularly claimed the utilization of butadiene polymers in aqueous dispersions where soap is the es- 'sential or only emulsifying agent present, the pH of the bath being'at least 7 and the soap being an alkali salt of a long chain carboxylic acid. Such baths and wool treated in accordance therewith may be utilized as the polymer treatment phase of the present invention.

In application Serial No. 586,637, filedApril 4, 1945, for Pre-shrunk and shrink-proofed wool, there is more particularly described and claimed the treatment of wool to obtain shrinkproo'fing by the utilizationof butadiene-1.3 emulsions and related materials as set forth above in which operatiorls'the wool is subjected to a treatment to polyalkylmethacrylates, polystyrene and its derivatives such as alpha beta dimethylstyrene, di-- chlorostyrene, acrylonitrile, methacrylonitrile, etc. While it is understood that the addition of these auxiliary substances usually is limited to the extent where no substantial interference with the shrinkproofing characteristics is experienced, in special applications it may be desirable to exceed those proportions.

Thus in application Serial No. 563,791, filed November 16, 1944, entitled Treatment of-wool, now Patent 2,447,539, there is more particularly claimed the treatment of wool by utilization of-- copolymers of a but-adiene-l.3 and a methacrylate ester such as methyl methacryl'ate, ethyl methacrylate, and butyl methacrylate, in aqueous emulsions of the character set forth above, the amount or methacrylate polymer being about 5 to 20% of the interpolymer, of the ethyl methacrylate being about 5 to 50% of the interpolymer, and of the butyl metha-crylate being from about 5% to 40% of the interpolymer. Any of such materials may be utilized as the polymer component of the present invention.

In application Serial No. 586,293, filed April 3,

relax any stretched wool fibers to, produce a preshrunk wool and such pre-shrinking operations and polymer depositions for shrink-proofing may be utilized in any order of steps successively or simultaneously. Those operations in connection with the utilization of polymer for shrinkproofing and also pre-shrinking operations may also be employed in accordance with the present invention.

In application Serial No. 594,585, filed May 18; 1945, entitled Interpolymer treatment of wool, now Patent 2,447,540, there is more particularly claimed the treatment of wool utilizing a copolymer of butadiene and an acrylate ester, more specifically a methyl acrylate not exceeding 40% of the copolymer, an ethyl acrylate in an amount not exceeding about 50% of the interpolymer, and a butyl acrylate not exceeding about 60% of the interpolymer in the production of shrinkproofing treatments utilizing baths of the character set forth above. Anysuch compositions and baths and treatments may be employed in this phase of the invention of the present case.

In application Serial No. 613,200, filed August 28, 1945, entitled Elastomer production and utilization, now Patent 2,447,877, there is particularly claimed the production of shrinkproofed wool by the utilization of copolymers of butadiene-1.3 and a Z-methyl but'adiene-L3, specifically isoprene and 2.3 dimethyl butadiene-L3, the copolymer being in the cross-linked condition as set forth above in which it is unsuitable for utilization for rubber but in its crumbly condition as utilizable in accordance with the shrinkprooiing operations is particularly important for the treatment of wool. Such materials are described and claimed as employed in treating baths of the character set forth above. Any ofsuch materials may be employed in accordance with the present invention for that phase of'the treatment which includes the use of the polymer. Desirably as set forth in that prior case, the copolymer of butadiene-l.3 with isoprene is in the ratio of from 9:1 to 1:4 parts by weight, while that of the copolymer of butadiene with 2.3 dimethyl butadiene 1.3 is in the ratio desirably of 9:1 to 3:7- parts by weight. Such materials may be employed in the present inven- 9 tion.

atoms such as styrene and its derivatives, namely,

alpha, gamma-dimethyl styrene and dichlorostyrene as well as phenylacetylene, where the copolymers are more particularly of the crosslinked character and if deposited per se from the emulsions would be crumbly materials unsuitable. for rubber purposes. As set forth in such case, baths employing such materials of the character as set forth above may be utilized particularly where in the styrene copolymer, the amount of styrene does not exceed about-60% by v weight of the copolymer, with the alpha. gamma-dimethyl styrene it does not exceed about 40% oi the copolymer, whereas the dichlorostyrene does not exceed about 40% of the weight of the copolymer, but for phenylacetylene preferably not more than 20% by weight of the copolymer is present. Any of those materials may be utilized as the polymer phase of the present invention.

In application Serial No. 615,097, filed September 7, 1945, entitled Shrinkproofing wool and materials therefor, there is more particularly described and claimed the shrinkproofing of wool 20 by the utilization of cross-linked copolymers of a butadiene-1.3 and an unsaturated ketone containing not more than 12 carbon atoms, having the formula CH2=CRa-CO.R3, where R: is selected from the group consisting of hydrogen, alkyl and aryl groups, and R3 is selected from the group consisting of alkyl and aryl groups, including more particularly copolymers of butadiene-1.3 with isopropenyl methyl ketone, methylene n-amyl methyl ketone, methylene isobutyl methyl ketone, etc., and where more particularly for shrinkproofing purposes in such copolymers the amount of isopropenyl methyl ketone does not exceed about 30 by weight of the copolymer, where methylene n-amyl methyl ketone is the copolymerizing material it does not exceed about 40% by weight of the copolymer, and when methylene isobutyl methyl ketone is the copolymerizing material, it does not exceed about 20% of the copolymer. Such materials may be utilized in emulsions, dispersions and baths as more particularly set forth above. Any such materials may be utilized asthe polymer phase of the present invention.

In application Serial No. 615,098, filed September 7, 1945, entitled Woolshrinking copolymers, there is more particularly described and claimed the utilization of cross-linked copolymers of a butadiene-1.3 and an acrylonitrile, such as acrylonitrile itself, methacrylonitrile, etc., more particularly where the weight of the acrylonitrile material either acrylonitrile per se or methacrylonitrile does not exceed about 40% by weight of the, copolymer, such copolymers particularly being utilized in the cross-linked condition and employed in baths, aqueous emulsions and dispersions as set forth above. Any such materials may be utilized in the present invention for the polymer phase thereof.

In application Serial No. 631,483, filed November 28, 1945, entitled Elastomeric copolymers and their utilization, there is more particularly described and claimed the treatment of wool for shrinkproofin where there is utilized a copolymer of a butadiene-1.3 and a vinyl ester'which polymerizes to a hard resinous material, more particularly such esters as vinyl acetate and vinyl chloride, desirably the vinyl acetate when employed not exceeding about 40% by weight of the copolymer, and the vinyl chloride also notexceeding about 40% by weight of the copolymer when it is employed. Such materials may be utilized in the shrinkproofing of woolby employment in aqueous baths, dispersions and emulsions as set forth above. Any such materials may be er phase of the present inchloroprene polymer, either alone or with limited amounts of other materials such as not exceeding about 50% of ethyl acrylate polymer based on the total weight of polymers present, or a vegetable oil factice not exceeding about 40% by weight of the polymer together with factice, or with methyl methacrylate polymer not exceeding about 40% of the total weight of polymers when this is used, or where the chloroprene polymer is utilized with a synthetic butadiene-1.3 polymer, or with a natural rubber latex, the latter, however, not exceeding about 75% of the total weight of polymer together with the latex present. Any of these materials may be employed in the shrinkprooflng of wool in the form of baths dispersions and emulsions as set forth above. The chloroprene polymer may also be utilized in the form of copolymers such as with an acrylonltrile where the latter does not exceed about of the total weight of the polymers present or with an ethyl acrylate copolymer, where the latter does not exceed about of the total weight of the polymers present, or of a methacrylate polymer not exceeding about 40% of the total weight of polymerspresent and again any of these materials employed in dispersions, emulsions or aqueous baths as set forthabove. Any of these combinations may be utilized in accordance with 5 the present invention as .the polymer phase thereof.

In application Serial No. 603,406, filed July 5, 1945, entitled Textile andfiber treatment, compositions and methods, now Patent 2,447,772,

40 there is more particularly described and claimed the utilization of butadiene-1.3 polymers and combinations thereof with other materials as in aqueous baths, dispersions and emulsions for the shrinkproofing of wool where the butadiene com- 45 ponent, that is, the synthetic butadiene polymer is employed in the form of a prevulcanized or preoxidized material, where the treatment has been carried to a point so that the polymer is present in a condition in which it will not give a 5 tacky deposit on fibers treated therewith. It is in substantially insoluble condition although it will swell with organic solvents as set forth" above. Such prevulcanized or oxygen treated polymer emulsions, baths and dispersions may be employed in accordance with the present invention. Furthermore as set forth in that case and in other companion cases, antioxidants may be present not only to control any further oxidation or vulcanization which takes place and to check the latter, but also because it has been "found that antioxidants exert a very favorable effect of unexpected character on the shrinkproofing obtained. Thus antioxidants of the usual type may be employed in'the dispersions or 5 emulsions in order to obtain the effects set forth above and any such materials may be utilized in accordance with the present invention as the polymer phase thereof.

Accordingly, in accordance with the present invention, wool of substantially normal hand is obtained but which has been shrinkproofed with a synthetic butadiene-1.3 polymer which may be of any of the characters set forth above, either by itself or copolymers of the character described above, utilized, however, in combination with a cured urea-formaldehyde type resin. The amounts of polymer plus resin present in the treated material may vary from about 1 to 50% on the weight of the wool. Varying ratios of polymer to resin may be used, but in order to secure satisfactory shrinkage control, between 2 and 15% of polymer, based on the weight of the wool, should be utilized. A preferred ratio with urea formaldehyde resins varying from about 4-21 of urea formaldehyde type resin to polybutadiene to 1:12 of such resin to polybutadiene. Or preferred ratios with melamine type materials may run from about 3.121 of the melamine type resin to polybutadiene to 1:12 of the melamine or alkylated melamine type material. In all such cases where shrinkproofing is obtained, the amount of the polymer present should be generally at least 1% on the weight of the wool and. the amount of any other materials present should not interfere with the shrinkproofing sought while other desired characteristics may be enhanced as pointed out above by the presence of such added materials.

The following examples illustrate the invention, the parts being by weight unless otherwise set forth.

Example 1.A condensation product of ureaformaldehyde as well as butadiene polymer emul-e sion was applied to swatches of wool flannel, measuring 10" X 10" in size. The samples were immersed in the resin solution first and the excess pad liquor was removed by passing the fabric through squeeze rollers. The weight of the wool samples was noted before and after padding and from the weight increase the amount of resin applied to the fabric was calculated. The samples were dried at 60 C. and cured at this temperature for 12 hours. After curing the polybutadiene dispersion was applied in the same manner and the amount of polymer on the fabric was calculated as outlined above.

The solution of the urea-formaldehyde condensation product was prepared by dissolving equimolecular quantities of dlmethylolurea and urea in sufficient water to form a solution containing 10% solids. To this was added 5% of ammonium sulfate based on the weight of the solids.

The aqueous polybutadien-e dispersion was prepared as follows: butadiene was passed over calcium chloride and condensed in a pressure re-' actor cooled to below 5 C. parts of butadiene were then weighed out in the reactor. While the reactor was kept in the freezing mixture, the following solution was added. 6 parts of soap (Ivory Flakes) was dissolved in 125 parts of water and the pH of the water-soap solution was adjusted to 10 by the addition of a small amount of 5% sodium hydroxide solution. The following catalysts and regulators were then added to the soap solution, 0.1 part of dodecyl mercaptan, 0.01 part of potassium ferricyanide, 0.2 parts of potassium persulfate. The reactor was then closed, allowed to come to room temperature and put in an agitator with a constant temperature bath at 45 C.

After 16 hours, the reaction was substantially complete as indicated by a very slight pressure within the reactor. The emulsion was then subjected to a vacuum of approximately 15 pounds per square inch to draw off the small amount of monomer gases that may be present. The polymer emulsion was then given an oxidation treatment as follows: added 1% of the sodium salt of sulfonated oleyl alcohol and 2% of a 30% hydrogen peroxide solution, then heated for one hour, the temperature rising gradually to 200 F. Since polymerization was almost complete, it was assumed that this dispersion contained 25% of polybutadiene.

This emulsion was diluted with water so that it contained 6% polybutadiene.

Four lengths of 8" each were marked on each sample, two in the direction of the warp and two in the direction of the fill. From these measurements the area in square inches was calculated. The wool samples were then washed for three hours in a mechanical washing machine, after which laundering they were rinsed, dried and remeasured.

The amount of resin and polybutadiene deposited on the fabric as well as the area shrinkage are shown below.

Percent Urea- The finished swatches had a dry, normal hand and the pieces which contained the urea-formaldehyde resin exhibited superior draping qualities.

Example 2.--A solution was made from equimolecular quantities of dimethylolurea and urea. The solution was diluted to a point where it contained 10% solids, to which was added 5% of ammonium sulfate, based on the weight of the solids. Four swatches of flannel were measured accurately and the area was calculated, after which they were thoroughly wet out with the urea-formaldehyde solution. The amount of liquid pick-up was determined by weighing the wool samples before wetting and after the excess pad liquor had been removed by passing the swatches through squeeze rollers. Of the samples, two were cured for 10 minutes at C. and two were cured for 12 hours at 60 C.

()ne piece-each, cured at a low and at a high temperature, as well as an untreated piece of flannel were then immersed in a polybutadiene dispersion, and after complete wetting out had taken place, the excess was removed by passing the goods through squeeze rollers, thereby removing the excess pad liquor. The polybutadiene solution was similar to the one used in the previous example, and the amount of solids deposited on the fabric was calculated as outlined above.

After drying, the samples were given a threehour laundering. The amount of shrinkage, as well as a resume of the treatment which was given to the fabric may be found in the table below.

Per Cent Per Cent Urea-formal- Polybuggg Sample No. dchyde Cure tadlene Shrink Resin on on Fabric Fabric age l7 12 hrs. 60 0--.- 6 4.2 l7 10 min. 125 6 4. 6 17 12 hrs. 60 C 23.1 I l7 10 min. 125' C-.. 29. 9 5 6 5. 2 6 Untreated. 24. 0

The flannel had retained its original desirable hand and the draping characteristics of the ureaformaldehyde containing fabrics was greatly enhanced.

Example 3.-A set of samples was prepared exactly as described in Example 2 except that 15% urea-formaldehyde condensation product Example 4.A set of samples was prepared exactly as described in Example 2 except that 12% urea-formaldehyde condensation product was applied to the fabric instead of 17%.

A firm hand was imparted to the fabric. The samples which were treated with the poly'butadiene emulsion showed superior resistance to felting and shrinkage on laundering.

The results of a three-hour wash best are given herewith.

Per Cent Per Cent Urea-formal- Polybuigs Sample No. dehyde Cure tadiene shrimp Resin on on 9 Fabric Fabric 88 1 12 12 hrs. 60 6 5. 4 2 12 10 min. 125 6 4. 9 3 12 12 hrs. 60 0.--- 27.4 4 12 10 min. 125 0. 29.1 6 6 6. 6 Untreated- 31. 0

Example 5.'A treating bath was prepared by dissolving 120 parts dimethylolurea and'30 parts of urea in 850 parts of water. To this solution was added ammonium sulfate, based on the weight of the urea-formaldehyde condensation product and 2% sodium lauryl sulfate based on the total weight of the pad liquor. Wool flannel squares 10" x 10" in size were weighted and immersed in the liquor. After thorough penetration had taken place the excess liquor was removed by passing the fabric through squeeze rollers. The goods were weighed again and from the weight increase as well as the strength of the solution the amount of urea-formaldehyde on the fabric was calculated. After drying, two swatches were cured at 125 C. for ten minutes while the other two were cured for twelve hours at 60 C.

One piece each cured at 60 C. and at 125 C. were treated with the polybutadiene emulsion of Example 1, as follows:

. 12 The samples were rinsed with warm water and dried.

A piece of wool to which no urea-formaldehyde had been applied was also treated with the polybutadiene emulsion according to the procedure as outlined above.

All samples, as well as an untreated swatch were washedfor three hours in a washing machine, containing 35 parts of powdered neutral treated.

soap in 18,500 parts of water at 65 C. After rinsing and drying the samples were remeasured. The results have been tabulated below. v

Per Cent Polybutadiene on Fabric Per Cent Area Shrinkage Sample N o. Cure The urea-formaldehyde treated fabrics had superior draping qualities.

Example 6.-A set of samples was prepared exactly as described in the previous example with the exception that only 14% of the urea-formaldehyde condensation product was applied instead of 20%. v

The fabrics had good draping qualities and. good shrink resistance, as well as superior 'resistance to felting. The degree of felting, etc. occurring after a three-hour laundering is tabulated below.

Percent Pol butad sue on Fabric Degree oi Sample No. Felting RODS.

s ht. considerable.

. o. 5 slight. U n considerable.

Example--7.A similar set of samples was prepared and tested but in this case only 10% ureaformaldeh'yde condensation product was applied to the fabric. In all otherrespects the procedure was identical to the one used in Example 5.

Excellent draping eifects were imparted to the I treated fabrics, as well as good shrink resistance The two pieces of wool weighing 24.2 parts were put into a bath consisting of 485 parts of water at -'70 C. and 4.8 parts of 50% acetic acid. After five minutes, 4.8 parts of the polybutadiene emulsion was added, this amount containing a weight of polymer corresponding to 6% of the weight of the samples. Five minutes later 2.4 parts of anhydrous sodium sulfate in the form of a 10% solution were added and these additions were repeated until the bath cleared completely, indicating complete exhaustion. The

samples had been agitated continuously throughout the application, and the temperature kept between and C.

to the samples to which polybutadiene had been applied.

Percent Urea-formaldehyde Resin on Fabric Percent Polybutadiene on Fabric Sample De of N o. Fst i g slight.

Do. considerable.

Do. none. considerable.

Example 8.-Three squares of wool flannel, measuring 10" x 10" were treated with 5% polybutadiene dispersion according to the procedure outlined in Example 5.

After rinsing and drying one sample was immersed in a 10% aqueous alkylated melamine formaldehyde solution. This solution was preaccuse sulfate was added to the urea-formaldehydesolution. Both percentages were based on the weight of the solids present in the solutions.

After complete penetration had taken place The area shrinkage was as follows:

Area t? Treated with Shrinkage Per cent 6% polybutadiene+l% Resloom" 0. 7 6% polybutadiene+10% urea-formaldehyde 1. 6% polybutadiene 6. 4 10% R 00111" 11.2 10% urea-formaldehyde- 30. 6 Con 31. 1

Example Ili -Samples of wool flannel were the excess liquor was removed by passing the treated with aqueous alkylated melamine form aldehyde solutions, prepared from a commercial Samples through squeeze i After drying product known to the trade as Resloom M75 iifis tfffiliifnfiffifi.iiiitdtiififuttstt This 55% was h t i th 1 n th diluted with water so as to form solutions which as mm t 6 q i 0 6 so u e contained 19, 14, 10 and 5% solids and to which amount of resin deposited on the fabric was 3% of diammomum phosphate based on the determmed; weight of the solids, had been added. The ex- Two additional pieces ofjlannel were treated v cess solution was removed by passing through m the Same manner wlth and squeeze rollers, the fabric retaining 100% of its formaldehyde solutions without having had the weight of solution After drying an samples polybutadiene treatment first. were cured for ten minutes at 125 C.

All pieces as well as an untreated piece were A similar Set f samples was prepared and washed for three hours in a mechanical washing ft curing these Swatches were immersed m machine- After drying they were remeasured a solution which'had been obtained by diluting and the ar a rin a was calculatedan aqueous polybutadiene dispersion with water A rsum of the vari tr m t as Well to such an extent, that the resulting solution as the area shrinkage is givenherewith. contained 6% of the polymer. The samples pPergertit P C R T PeiCent sampleNoeat: one "me astas that.

Fabric age 1 5 10m1n.125 9%Res1oom 0.9 g 5 10 min. 125 C 10.8% urea-formaldehyde g 411 163%15516651 1111: 2016 5. 11.0% ureaformaldehyde. 23. 3 fiUntreated 24.6

Example 9.Five solutions were made up as Alkylated Melamine formaldehyde (Resloom M75 solids) 18.2 18.2

Urea formaldehyde condensation product 15% solids 66.7 66.7 Diammonium phosphate .3 .3 Ammonium sulfate .5 .5 67.5 88 76 81.5 32.8

Watch--.

1 The urea formaldehyde condensation product-solution was prepared by dissolving equimolecular quantities of dlmethylol urea and urea in sufficient water to yield a solution containing a total of 15% solids.

Measured swatches of wool were thoroughly wet out, the excess liquor removed by passing the fabric through squeeze rollers, and the amount of liquid pick-up determined. From the pick-up, the amount of polymer and/or resin deposited on the wool was calculated. These amounts as well as the shrinkage may be found inthe table below. The pieces were dried, and those containing the urea-formaldehyde and the alkylated melamine formaldehyde condensation products were cured for ten minutes at 125 C. After curing, these pieces had a normal, full hand and pleasing draping characteristics.

All pieces, including an untreated piece, were washed for three hours and. remeasured.

were permitted to remain in contact with the bath until they were completely wetted out. The excess liquid was then removed by passing the swatches through squeeze rollers.

The samples were found to have doubled in weight, and since the pad liquor contained 6% of polymer, 6% polybutadiene was deposited on the fabric.

All samples were measured before and after laundering and the percent area shrinkage was determined. The results were as follows:

Area kjf" Treated with Shrinkage Per cent 19% alkylated melamine formaldehyde 10. 5 19% alkylated melamine formaldehyde+6% 4.5

polybutadiene. 14% alkylated melamine formaldehyde 17. 9 14% alkylated melamine formaldehyde+6% 4.2

polybutadiene. 10% alkylated melamine formaldehyde 2i. 0 3a 10% alkylated melamine'formaldehyde-Hi9, 4.2

polybutadiene. 4 5% alkylated melamine formaldehyde 23. 3 4a 5% alkylated melamine formaldehyde+6% 6.7

polybutadiene. 5 Untreated 80.1

Example 11.A solution of a melamine-formaldehyde condensation product was prepared by dissolving with heat melamine and formaldehyde in a molar ratio of 1 to 3 in sufficient water to above.

acemes give a product containing 10% solids. Qn cooling of ammonium sulfate based on the weight of the solids was added as a catalyst.

Two swatches of wool x 10" were weighed andimmersed in this solution. After the samples had wetted out thoroughly. the excess solution was removed by passing them through squeeac The samples were reweighed, dried and rollers. cured by allowing them to remain at room temperature for 24 hours.

The solution was then diluted with water soas to contain 5% melamine-formaldehyde condensation product and an additional two samples were heated according the procedure as outlined In each case the fabric increased 100% in weight.

After the curing one sample each containing 1.0% and 5% of melamine formaldehyde as well as an untreated swatch were treated with the 6% polybutadiene emulsion oi Example 1.

The emulsion .was applied by padding and in this manner 6% Dolybutadiene was deposited on the fabric. Thesamples. which included those which were treated with melamine-formaldehyde only, as well as a measured untreated swatch. were then dried and laundered for three hours.

After drying, the swatches were remeasured and;

the amount of area shrinkage was calculated in per cent;

control follows: y

Per Cent P Cent Per Cent Melamine- Po ybuta- Area Sample N o. ior mg l geggda (em on swab Fabric 5 2;. t Y 5 3 i o'fl'fiir' 2a shrink resistance were imparted to the fabric as tabulated below. 4

ufih th 1 S t. M

0 0 y ll rea dehydo Resin dlene on Shrinkon Fabric Fabric age 10 2a.: 10 e as a 2a: 6 a a1 c 6.2 6 Untreated- 24. 4

Example 13.A solution of a melamine-formaldehyde condensation product was prepared by dissolving with heat melamineand formaldehyde in a molarratlo of 1 to 4 in suflicient water to give -a product containing 10% solids. After the solusqueeze rollers, dried and cured for 24 hours at v A rsum of the treatment and the shrinkage room temperature.

One of these wool squares was then padded from a 6% polybutadiene emulsion and permitted to dry. Another two swatches were treated with a 10% solution of a melaminei'ormaldehyde condensation product prepared by dissolving melamine and formaldehyde condensation product preparedby dissolving melamine and formaldehyde'in' a molar ratio of 1 to 3. No catalyst was added to this solution. The treated wool pieces were cured for 24 hours at room temperature.

One of these pieces was also treated with 6% polybutadiene and dried. Finally all these swatches, as well as a swatch of wool treated with 6% polybutadiene and an untreated square were washed and measured for shrinkage control. A good full hand was imparted to the fabric which had excellent draping qualities.

. Per cent Polybutadiene on Fabric Per cent Catalyst Area I Shrinkage The samples which were treated with the melamine-formaldehyde resin had a desirable drape and a full-hand.

Example 12.A similar set of samples was preterlstics, and in some instances good felting and Having thus set forth my invention, I claim:

i l bath for shrinkproofing wool while retaining substantially normal hand which comprises an aqueoussubstantially stable emulsion containing a synthetic butadiene-1.3 polymer of polymerization and at least one of the ureaformaldehyde and melamine-formaldehyde resins, the ratio of resin to polymer being from 4:1 to 1:12 for the urea-formaldehyde resin and from 3.1:1'to 1:12 for the melamine-formaldehyde resin, the polymer and resin being present,

17 in amount to give 1 to 50% by weight of polymer and resin deposition on the wool, the amount of polymer being from 2 to 15% by weight on the wool, the bath also containing a non-cationic emulsifying agent and at least 25% by weight on the polymer of a water-soluble neutral salt of an alkali metal as conditioning electrolyte and having a pH below about 7. l

2. A bath as set forth in claim 1, in which the emulsifying agent is anionic.

3. A .bath as set forth in claim 1, which ineludes a curing catalyst for the resin.

4. A bath as set forth in claim 1, in which the resin is a urea-formaldehyde resin and the resin to polymer ratio is from 4:1 to 1:12.

5. A bath as set forth in claim 1, in which the resin is a melamine-formaldehyde resin and the resin to polymer ratio is from 3.1:1 to 1:12.

' JOHN B. .RUST.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,173,242 Young 1 Sept. 19, 1939 2,211,959 Maney Aug. 20, 1940 2,299,786 Battye et a1 Oct. 27, 1942 2,340,358 Young Feb. 1, 1944 2,384,880 Britton et a1. Sept. 18, 1945 2,405,038 Jennings July so, 1946 OTHER REFERENCES Rubber Age (N. Y.) V01. 48 of 1940, DD- 23-25.