US1845569A - Fibrous material and process of treating same - Google Patents

Description

Patented F eb.16, 1932 UNITED STATES PATENT OFFICE MERWYN o. TEA'GUE, or .mcxsoN nnxerrTs; AND NEIEMIAH n. BRE STER, or BROOKLYN, NEW YORK, ASSIGNORS To THE NAIJ'GATUCK onnmonx. COMPANY, or

AueATucx, oONNncTIouT, A CORPORATION or coNNncTIcuT No Drawing.

- FIBBOUS MATERIAL AND rnoonss or TREATING sans It is well known that fabric materials composed of various types of associations of yarns may be treated with rubber'in order to improve their physical properties. rubber" treatment, however, has heretofore been carried out in such a manner that the rubber component of the rubber-fabric as sociation has been readily apparent to the eye and to the touch. For this reason it has been impracticable to use a large number of rubber treated fabric materials for the purposes for which these fabric materials are normally utilized when not rubber treated.

Consequently it has heretofore beenim-.

possible to fully utilize the advantageous characteristics in physical properties imparted to various types of fabric material by the For instance'silk materials product has possessed a distinct rubber appearance and feel and has thus been rendered unsuitable for wearing apparel.

Probably the reason for the very apparent rubbery appearance and feel of rubber treated textile fabrics as .at present manufactured is because ofthe quite appreciable amounts .of rubber which have been incorporatedtherewith to form an impervious, waterproof structure, either distrlbutedthroughout the fabric structure, or localized at the surface inthe form of a coherent coating.

'Even when fabrics are impregnated .or coated with what are considered very small amounts of rubber in any of the various ways heretofore known we have found that there is between -50 per cent of rubber associated with the fabric, this ercentage being based upon the dry weiglit of the fabric- 7 treated.

This invention invblves the use of rubber with various types of fabric material, particularly, fine. abrics adapted for use in wearing apparel, draperies, upholstery," etc. By this invention the hysical pro rties of suchfabrics are great y improved y meth ods involving a particular manner of apply-' in rubber in relatively small'amounts, con- 7 .si erably less than thoseabove indicated,

yet no atent rubbery'appearanceand feel 1s mani est, in fact the treated fabric ma- This Application filed January 7, 1932. Serial No. 585,834.

rics of various types, but is particularly applicableto natural or artificial silks wherein it is desired to soften or reduce the lustre or natural shine of this type of material and to resist its tendency to run whenincorporated into knitted structures. The invention is also a plicable to woven and knitted fabric .materia s of coarser nature, such for instance as wool, cotton or woolen and cotton material constructed for use as upholstery or jersey cloth for garments. other a plications will more clearly appear from the following specification and claims. 7

The advantages to be derived by the use of the invention are various and vary in accordance with the specific application thereof. In all cases, however, fabric materials composed of yarn associations are increased in strength and wear resistance and the appearance of the fabric. which has been treated in accordance with the principle of the invention is advantageously affected in that the yarns appear to than do the yarns 'of untreated material and on close inspection give the effect'of a quality fabric constructed of finer yarns more thoroughly twisted. The normal appearance and feel of the fabric, however, is not deleteriously affected and it is impossible for anyone but an expert to perceive any evidence in rubber in the finished product. With silk and rayon there are additional advantages in the application of the invention in certain embodiments as the extreme -l'ustre of this type of material may besoftened and reduced without the application thereto of heavy metal'salts as is the common practice, and without increasing the twist in the single and plied c more firmly knit or woven advantageous over rubber treating processes heretofore known in that it provides for reducing the tack of the rubber treated material prior to the time it is taken from the rubber treating apparatus and led into or through subsequent processing apparatus.

This results in great facility in handling.

The invention consists essentially in treating fabric material with dilute aqueous dispersions of rubber having compounding and modifying ingredients incorporated therein if desired, in a manner so that the rubber particles are uniformly distributed throughout the fabric and in and upon thecomponent yarns. When the rubber particles have been completely distributed they are coagulated in situ, after which the excess aqueous bath, carrying rubber particles which have not become attached to the yarns and carrying other liquid and solid particles which have not become attached to the yarns or entrapped in. the rubber coagula which have become attached thereto, is expressed from the fabric and thereafter the fabric is dried in the desired form. Coagulation of the rubber may be brought about by the utilization of heat or by chemical coagulents, theaqueous rubber dispersion may be modified by various modifying agents and the fabric material may be simultaneously treatedwith scouring and dyeing agents, all of which will be hereinafter particularly described. The invention also consists in the novel product of the above described process. l

In its preferred form the invention is carried out by the utilization of heat for the purpose of coagulating the rubber. As a .specific example of the manner in which the invention may be accomplished by the use of .heatas the coagulant, the following is exem- .plary. In this example, directed specifically vto the manufacture of silk hosiery, the process is carried out as a complete fabric finishing operation, including scouring and dyeing the material as well as treating it with rub- Silk. stockings in desired quantity are shakenloosely into mesh bags which are placed into. the compartments of the suit- ,able washing machine, for instance an Amer- -:ican laundryxmachine or a Smith & Davis drum' dyer. "The-machine is filled with cold water in an amount sufiicient to give approxilings are removed and placed in a centrifug mately two gallons of water for every pound of silk. A good grade of soap in the proportion of about one pound of soap on five dozen pairs of stockings (or about one pound of soap with every four lbs. of silk) is added and the water is heated to boiling temperature, for instance by the use of-steam. The machine is put into-operation and the stock ings agitated in the soap solution for a suitable time, say 15 to 25 minutes in order to scour the material and remove the natural gums from the silk fibers. If desired the scouring liquor may at this time be drained from the machine which may then be refilled with a dilute soap solution and heated. At this time there is added an aqueous disper sion of rubber in amount sufiicient to give 18% rubber dispersion solids on the dry I weight of the silk charged into the machine (but yielding a very dilute dispersion when intermixed with the treating bath), said dispersion being mixed, if desired, with about 5% (based on the dry Weight of the silk) of soluble pine oil prepared by dissolving the pine oil in a small amount of boiling water, together with 5% glycerine on the same basis. A dye solution in the proportion of .01 lb. of dye to 1 lb. of silk is then added and the whole solution allowed to come to approximately 180 F. The dye maybe any water soluble organic dye and is preferably composed of 75% acid dye and 25% direct dye. For instance the above proportions of Gyanone R Bluefrom National Aniline & Dye Co. and 'Pontamine B from Du Pont Co. may be used in order to give the stockings a blue color. Heating is continued for a suitable interval, say 35 min. or for sufiicient time to dye the stockings the required color several times. After the last rinse the stoc d or vacuum extractor and the residual liquor" largely extracted, for instance to a pointwhere no liquor can be wrungf from thetstockings by hand. They are then remov'ed from the machine and placed on steam heated metal forms where they are left until dry, and, if suitable vulcanizing ingredients have been incorporated in the rubber dispersion, at least partially vulcanized' When dry they may be removed and stored until the vulcanization of the rubber is complete. 7

It should be noted that while aqueous dis- (.115 oif and the stockings rinsed w1th cold water" persions of rubber having variable solids content are used, they in all cases are diluted with tions may be used and the result, namely,-of-

having a small amount of rubber in the finished material, obtained by utilizing moreefficient extracting or wringing apparatus for expressing excess aqueous materials as well as solid particles which have not adhered to or, between the fibrous elements of the yarns or which have notbeen entrapped in the rubber coagula which have been distributed throughout the yarns. It is obvious alsothat if a large Volume of water, is used to treat a very small amount of material, the weight of the rubber on the material may be large, yet the actual percentage concentration of the solution will likewise be small.

When vulcanization is carried out, it is probably commenced during or immediately after coagulation of the rubber in the bath and is given impetus on the heated form, yet

is not complete untilseveral days, perhaps as much as several weeks after the stockings are dried and removed. The time for complete vulcanization of course may vary depending; upon the amount and kindof owerful accelerators of vulcanization use the time for which and the temperature at which they are stored.

The following is exemplaryof the aqueous rubber dispersion which may be used in the preceding example:

This mixture is prepared in a state of aqueous dispersion by first adding the stabilizer to the latex, then solubilizing the casein with borax .and adding1 the same to the mix' and next preparing t e vulcanizing ingredients in the form of a paste and addin them to the mix. The dispersion is prefera ly one hav ing a total solids content .of about 30%, but may be of any desired concentration. A suitable stabilizerisa'product sold under the. trade nameof Nekal which is a condensation roduct of an aromatic hydrocarbon and an a iphatic alcohol in the presence of sulphuricacid. The accelerator may be any suitable organic accelerator or mixtures thereof. The other ingredients may of course be varied 'in'aeoordance with the reuirements of particular cases. For instance t e borax may be replaced b ammonia or some fixed alkali; the sodium il u replaced by some other germicidal agent. The casein may be omitted or replaced by other compounding ingredients. The glue used to stabilize the paste may be replaced by oride. may be' other colloidal material and the amount may a be varied. The pine oil indicated as being mixed with the dispersion may be omitted. The glycerine may, if desired, be omitted. Other variations may be made without-dearting from the principles of the invention,

or instance after dye has been added and the solution boiled, about 10% Glaubers salt may be added (based on the dry weight of silk),

to fix the dye more permanently. A suitable wetting agent such as sulphonated mineral oil,

may be added at any time prior to coagulating the rubber.

Stockings treated as above described are easily boarded and stripped from the forms and manifest increased resistance to wear and increased bursting strength when tested on an apparatus similar to a Mullen tester. The resistance of the material to runs is greatly increased. In addition the solids deposited add to some extent to the weight of the masultsin respect to rayon fabric prepared in.

knitted state and-in'tubular form:

A suitable type of washin machine is charged with water into whic is mixed '2].

the machine operated to scour the fabric. There should beeenough water to cover the rayon and allow it to be agitated in the bath with facility, the proportionof water being approximately two gallons for every poundv of rayon to be treated. The washing step may be accomplished with. the application of heat at say 180 F. and will require anywhere from one-half hourltoan hour. After the scouring is complete the liquor is drained from t e container andthe fabric rinsed in fresh water, if desired, to'remove the scouring ingredients, after which. the machine is again filled with water in the same amount and heated .as before. The drawing off of the scouring liquor may be omitted if desired.

The next step is the addition of the rubber the material. With the rubber may be added a. wettin agent such as sulphonated mineral oil or ekal in the proportion of 1 to 2% added in weak solution of soap, the fabric added and Y pending upon the type of dye used) dissolved in water. It should be understood that by reason of the presence of a relatively large amount of water the effective concentration of the rubber dispersion is small despite the fact that rubber has been added in the proportion of based on the dry Icoa weight of the material.

The solution is kept agitated and heated for approximately one-half hour at a temperature near boiling, by which time the dye is set and the rubber particles of the dispersion are coagulated and set in the fabric.

After the rubber and dye have been coagulated and set, the fabric may be removed, rinsed in cold water and the liquid extracted to a condition near dryness, after which the fabric may be dried in a. hot air heater at approximately 190 F. for at least one-half hour, preferably longer, in order to speed up the vulcanization of the rubber.

Material which hasalready been dyed or material which is desired in its natural color or in its bleached or unbleached state may be treated in accordance with the principles of the invention as above set out, the steps relating to scouring and dyeing being omitted. For instance a mixture of cotton and wool material, woven into a fabric in the-form used as automobile upholstery, may be immersed in an amount of water suflicient to immerse the same with facility, or in an apparatus known as a dyeing jig, an aqueous dispersion of rubber added, and the water heated to near boiling. The aqueous rubber dispersion is preferably compounded as in the preceding examples, and added in amount sufficient to give 15% dispersion solids based on the weight of the dry fabric treated, but of course the elfective concentration of the solution is small on account of the relatively large amount of water with which the rubber dispersion is intermixed. The fabric may be agitated or continuously passed through the jig or other apparatus to effect uniform and thorough saturation, during which the boiling is continued for a desired period, at least of sufficient duration to cause the rubber to coagulate on and between the fibers, after which rinsing, extracting and drying may be accomplished as hereinbefore set out.

The invention may be also practiced by the utilization of a chemical to bring about ation. The following is an example .of t e process wherein this type of coagula- ,tion is effected. Although heat is used in this embodiment, its utilization is largely for the purpose of fixing the dye and has no function as far as coagulation is concerned. This above indicated up to the step where the heating is continued for the purpose of coagulating and fixing the rubber on the fibres. In the present embodiment at this point the heatlng need not be continued longer than is necessary to set the dye and the temperature need not go higher than 110 F. which is usually suflicient for this purpose. At this time and after the desired color has been obtained, the rubber and associated solids are coagulated by the addition of a chemical coagulant which this case may be a 5% solution of ammonium or potassium alum. This c0- agulant can best be added in two or three portions with an interval of several minutes between each addition in order to get thorough distribution of the coagulant throughout the bath. The precise amount of alum solution can best be predicted by experiments since diflerent latex compositions will contain varying amounts of ammonia or otheralkali. The amount of a particular case,

however, may be determined by adding the, alum solution slowly until such time as. the" entire bath becomes and remains for a few minutes neutral or slightly acid since under these conditions the aqueous dispersion of rubber is precipitated to most efi'ectively lock the rubber within the individual yarns or fibrous associations.

Whenspecific delustering effects on silken fabrics are desired there may be variations in the embodiment of the process above described. For example if it be desired to obtain a final product of very dull appearance an adjustment should be made in the amount and type of soap in the bath and the amount of alum or other coagulant finally used so as to precipitate in situ, simultaneously with the rubber, the desired amount of insoluble soap. The combined precipitation of such soaps and coagulation of rubber produces a more permanent delustering effect than many delustering processes now used and involving the use of heavy metal salts. On the other hand if it be desired to get the maximum advantage of the rubber present but without so vmuch delustering efi'ect, then just before the coagulant is added the dye and rubber dispersion bath may be drained from the container (having first made sure that a suflicipitated in the yarn without the formation of a large amount of insoluble s'oa After the coagulation of the ru bar in the fabric the stockings are removed from the bath and wrung, as by a centrifugal extractor,

to the desired extent and then dried on forms in the usual way.

lar knit rayon fabric like that indicated .in the example involving the treatment of this type of material by the utilization of heat as a means of coagulation. i

The fabric is placed in a textile dyeingmachine commonly known as a jig or open dye kettle and the ends knotted together at the corners so that the fabric may be circulated in and out of the bath of the machine in the form of an endless belt. The container is charged with soap as indicated in the preceding example and the steps preceding coagulation, namely those of scouring,a'dding rubber dispersion, wetting agents, dyes and other ingredients carried out i-n the manner hereinbefore described in connection with rayon fabric.

.of dye to 1,000 of water.

continued in operation fora further period In this example a dye known as Sky Blue 63, obtained from the National Aniline and Dye Corporation or the General Dyestuffs Corporation is added to the aqueous bath in quantity 'suflicient so that for each pound of fabric there is added one pound dye solution made up in the proportion of 1 lb. The machine is and at a temperature sufficient to fix the dye. It should be understood that the quantity of material andvother factors as hereinbefore referred to require a variation in the temperature of the dye bath and the times of agitation therein, although for rayon fabrics treated as above described the temperature range may be fixed between 110 F. and 200 F. and the times of agitation fixed accordingly.

i The material may now be treated with a chemical coagulant which may be in the form of a 5% solution of alum.- This is most co nveniently added in two or three portions with continued agitation. The amount of coa lant in this case may be ascertained as t at sufficient to make and hold the bath slightly acid in reaction for a few minutes. The agitation of the fabric in the bath is preferably continued after the, addition of the coagulant.

In case it is desired to destroy or decrease the normal lustre to theirayon, this may be 0 some soluble barium'salt such as some barium chloride just before the addition of the alum.

In this way there is formed in situ an insoluble, precipltate'such as barium sulphate simultaneously with the rubber in and through the rayon yarns. r

The aqueous bath may now be removed and the fabric thoroughly rinsed, the excess water then removed by wringing or extracting and this followed by drying, say in a whirlwind dryer at 190 F. .Other methods can of course be used for drying as will be apparent to one skilled in the art.

Still another example of the commercial use of the invention embodying the step of coagulating by chemical means, is given in the following procedure used for the treatment/of flat woven silk, such as satin fabric which has been previously scoured and dried in the usual manner. In. this example of course the incorporation of a scouring agent in the treating bath is unnecessary and the process is' illustrated as proceeding from the point where the clean satin is taken from a supply and charged into the treating apparatus: Into the usual jig type of machine such as usually contains say 300-400 gallons of water during operation is introduced the desired amount of cold water, the silk fabric placed in the machine in the form of an endlessbelt, and the machine started-to operate. An aqueous dispersion of rubber with or Without awetting agent is then added slowly into the bath during agitation.' In this case the aqueous dispersion solids are added in the proportion of about 25-30% of the weight of the silk fabric but forming a dilute dispersion when intermixed with the water. Attimes it is desirable although unnecessary except for the purpose of removing the odor of rubber from the finished article,.to add soluble pine oil, and glycerine, for the purpose of retaining moisture in .the fabric pending drying, each in the proportion of 1% based on the weight of the dry fabric and added as described under the treatment of stockings, noted above.- The machine is operated for a. time sufficient tothoroughly distribute the aqueous dispersion solids throughout the fabric and bath after which the temperature of the bath is'increased over a eriod of a prox'mately 10 minutes to about 180 Duri g the heating is added the usual quantity' o dye solution together with a small minutes at this temperature, at the endof which time the dye becomes more firmly fixed. The dispersed rubber solidsare then precipitated or fixed in the fabric by the ad- 7 i dition of logwood extract br other forms of fixing agents such as tannic acid. It has been found advisable, to use more than the amount of logwood extract normally used in dyeing operations so as to make sure of sufliciently setting the rubber solids. An alternative procedure of coagulation may be followed by using the normal amount of logwood extract to set the dye but to supplement its action of coagulating the rubber solids by the subsequent addition of another chemical coagulant such as an alum solution, a heavy metal salt, etc. 'The machine is, continued running for say to minutes after the addition oft-he coagulant, after which the fabric is rinsed, extracted and dried.

Still another commercial use of this new process, as embodying the principles of-chem- 1cal coagulation, is that of treating heavier fabrics such as woolor wool and cotton fabrics. The procedure noted with respect to treating this type of material by utilizing the heat coagulation embodiment of the invention .may be followed, except the temperature need. not be raised.- That is to say the fabric isplaced in a jig type of equipment andcirculated in and out of cold or warm water. In this case the fabric has been previously scoured and dyed and woven so as to produce a fi rain the fabric. Instead of coagulating t e rubber from aqueous dispersion by heating the bath, a coagulant such as alum is slowly added to the bath as described in the above examples until such time as the. solution becomes and remains for afew minutes neutral or slightly acid in reaction. Thefabric is agitated in the solution containin the coagulant for about 10 01-15 minutes or a period suflicient to insure coagulation of the rubber particles in the position in which they have lodged, after which time-the fabric is thoroughly rinsed, the exces s water squeezed or extracted and the fab-- ric dried.

It is of course understood that the process may be carried, out by successively immersing the fabric'to be'treated in various baths. As a matter of practicability the embodiments hereinbefore exemplified I have been described ass involving a treatment of the material in o e container, the various ingredients being :added successivel or concurrently depending upon the con itidns inythe particular case. As an example of the manner inwhich the process may be carried out by utilizing successive treatments, silkstockings which have been previously washed and dyed-may be immersed in a water bath con a wetting agent of the nature descri inthe preceding examples. After this the stockings may be taken out and immersed in a water bath containing a suitable latex composition, for instance one prepared as previously described. The bath may be heated to a temperature near boiling to co- Elatethe rubber, or thestockings may be en from the bath and immersed in a third bath'containing dilute acid to coagulate the rubber. After coagulation the excess liquor is extracted and the stocking is washed in the manner previously described.

.5 We have found that in practically all cases the amount of dispersed rubber solids added to the treating bath and based on the dry weight of the fabric or fabric stocks will range from 3 to 30% but it should be understood that due to the large amount of liquid present in the treating bath the dispersion is actually of a very dilute nature-that is the total percent rubber solids in the aqueous bath is small. Consequently the principle of the invention may be observed to involve a treatment with a dilute agueous dispersion of di erent from present rubber which is quite known treatments with rubber dispersions involving the application of the relatively thick and concentrated aqueous dispersion of rubber and resultin in rubber films or impregnations which 'stinctly alter the normal appearance and feel of the fabric treated. Materials treated in accordance with this in-' vention possess no rubbery feel or undesirable stiffness or hardness. They do, however, posmss improved physical characteristics which vary in a manner commenurate with the different physical characteristics of the fabrics themselves. The normal appearance and feel are not materially altered, in fact it is diflicult for anyone except an expert to note a diflerence between similar pieces of treated and untreated material. With silk and rayon, depending on theamount of rubber and associated insoluble precipitates, the

changed 'nature of the material is most apparent as in these cases the normal lustre'of the material is usually reduced. In all cases, however, close in tion reveals a I yarn structure more close y associated than in untreated goods, and a firmer and smoother feel and more closely knit or woven construction is readily apparent toan expert. The strength and wearing qualities of the material is in all cases materialy increased. With knitted fabrics-the knit loops tend to hold themselves in (position thus appreciably decreasing the ten ency'of this type of material to run where a loop in one course is broken. In general fabric materials treated in accordance with the invention manifest a natural appearing yarn structure in whichupon close inspection with-the aid. of a microscope the'structural elements. (filaments,

fibres, etc.) are more closely associated than in untreated material, the rubber particles being indiscriminately distributed between them, binding them together-"into a substan-' tially unitary yarn structure'and tending to invention enables the use of as much stabiliz-v ing colloidal material as is. desired to prevent prematurew coagulation of the rubber bymechanical" agitation, and that such materials are largelyremoved' by reason of the selective coagulating)step and the succeeding ex-- tracting step. nly the rubber and someof the associated materials are coagulated, or

entrapped in the coagula, leaving a considerable amount of water soluble constituents of the rubber dispersion freely suspended therein and subject to being washed out or wrung from the fabric by subsequent operations. The resulting coagulated rubber may be seen therefore to contain a less amount of water solubles than does the rubber in aqueous dispersion with which the fabric has been treated. It is apparent therefore that the advantages of using stabilizing colloids in the preparation and processing of the rubber dispersion used may be utilized, yet the disadvantages of having these colloids present 1n the deposited rubber binder obviated.

Due to the more compact relation assumed by fibers or elements making up the individual yarns of which a knitted silk fabric is constructed, such as silk stockings, it is more difficult for a splinter, fingernail or other sharp projection to catch .on thesefibers or elements thus reducing liability to rung Moreover, if a fiber or element does become caught and broken, the parts thereof will not easily become disassociated from the adjacent fibers or elements and this also tends toward the prevention or continuation of runs and the occurrence of pull threads.

3 ,This same structural characteristic, namely the more 'firm and compact yet flexible relationship of the fibers or elements going into the individual yarns, greatly increases the resistance of a fabric to wear, probably because it reduces or eliminates friction between the component parts of the yarn. Whatever the. reason, however, this characteristic has been definitely established, and with coarsewoven cotton and wool uphol- 40 stery fabric treated in accordance with the invention, wear tests have indicated an increased resistance to wear of several hundred per cent.

While in the foregoing the invention has been disclosed with respect to the utilization of natural or reclaimed rubber dispersed in an aqueous medium, either as found naturally or compounded, or as manufactured artificially according to known processes, at least some of the advantages of the invention may be obtained by using synthetic rubber and dispersing it either at the time of'its production or after its production by methods similar to that utilized in dispersing natural or reclaimed rubber. Accordingly, in the claims the term rubber is used broadly and is to be understood'as comprehending synthetic as well as natural rubbers.

This application is acontinuation of our prior co-pending applications, Serial Nos. 491,071, filed October 24, 1930; 544,030, filed J une 12, 1931; 569,262, filed October 16, 1931;

and577,702, filed November 2'17, 1931. Having thus described our invention,

what we claim and desire to protectby Lettors-Patent is:

1.. The process of treating fabrications of yarn which comprises impregnating the same with an aqueous dispersion of rubber in dilute form containing not' more than approximately 10% concentration of rubber solids precipitating rubber from such dilute dispersion throughout the fabrications in discontinuous small particles by a slow coagulation and then drying.

2. The process of treating fabrications of yarn which comprises immersing the same in an aqueous dispersion of rubber in dilute form containing not more than approximately 10% of rubber solids, coagulating rubber in and on .the constituent yarns while so immersed, removing the treated fabrications from the bath and mechanically wringing them largely free of the medium in which they have been immersed, and finally drying the same in the form desired.

3. The process of treating fabrications of yarn which comprises immersing the same in a water bath containing dyeing agents and not more than approximately 10% dispersed rubber solids, heating the bath at an elevated temperature not in excess of the boiling point of water for a length of time sufficient to at least fix'the'dye, coagulating rubber in and on the yarns of the fabrications, removing the. treated fabrications of yarn from the bath, and finally drying the same in the desired form.

4. The process of treating fabrications of yarn which comprises immersing the same in a .water bath containing scouring and dyeing agents and not more than approximately 10% .of dispersed rubber solids, heating the bath at an elevated'temperature not in excess of the boiling point of water for a length of time sufiicient at least to fix the dye, coagulating rubber in and on the yarns of the fabrications, removing the treated fabrications of yarn from the bath and finally drying same in the desired form.

5. The process of treating fabrications of yarn which-comprises immersing the same in a water bath containing-scouring agents, heating the bath for a short interval at an elevated temperature not exceeding 212 F., I

subsequently adding to the bath coloring agents and a dilute aqueous dispersion of rubber, further heating the bath to fix the dye and coagulate rubber from the dispersion in heating the bath for a short interval at an elevated temperature not exceeding 212 F., sub sequently adding to the bath coloring a cuts and a dilute aqueous dispersion of ru ber, further heating the bath to fix the dye and coagulate rubber from the dispersion in and on the yarns and also to at least partially vulcanize the rubber particles associated therewith, removing the treated fabrications of yarn and mechanically freeing them largely of such liquid and solid materials as have not become associated with the coagula or the yarns and finally drying the fabrications of yarns in the desired form.

7. Process of treating fabrications of yarn which comprises immersing the same in a water bath containing not more than approximately 10% rubber solids and the desired coloring dye, heating the bath for a sufiicient length of time to fix the dye, adding a coagulating agent to the bath, removing the fabrications of yarn and ridding them of the bath liquor, and finally drying the fabrications in the desired form.

8. The process for strengthening fibrous associations comprising depositing in situ therein and indiscriminately throughout the same separate rubber coagula from a dilute aqueous dispersion of rubber of less than approximately 10% concentration, the resultmg rubber being distributed throughout the fibrous association in such manner as to be indiscernible to the the touch. a I 9. The rocess of treating fabrications of yarn whic comprises immersing the same m an aqueous dispersion of rubber in dilute form containin not more than approximately 10% of rub fiisolids, slowly coagulating rubber in and on the constituent yarns in discontinuous form by immersing in a weak coagulatin bath, removing the treated fab- ,ricationsmm the bath and mechanically them largely free of the medium in whic t ey have been immersed, and'finally d 'ng the same in the form desired.

iged at New York, county and State of New ork, this 4th da of J anuar 1932.

MERWYN TEAGUfi,

NEHEMIAH H BREWSTER.

eye and imperceptible to