US2642332A - Method of treating keratinous yarns and compositions therefor - Google Patents

Description

Patented June 16, 1953 METHOD or TREATING 'KER'ATINOUSQ mans AND COMPOSITIONS 'rnannroa .Qscar 13; Cohen, Watertown, Mass, assignor. to

Monsanto Chemical Co r A y, u l. Mon castr o P Delawar NoDrawing. Application October 1-, 1948,; SerialNo. 52,427"' w re 325 1 4 ihe present invention relates. to an improv I process of setting the twist of mechanically twisted keratinous. yarns. and particularly high y twisted keratinons yarns employed in the manfa tu o pile fabrics, frieze ug and th ke- The present invention also. relates to a method o mtroducing k ks in hi hly twisted .ke a n u yarns and. simultaneously therewith. setti g. .01 kinks.

n e ma u acture of twisted ke atin u yarns such as twisted ,woolyarns which are em.- p o ed. in the p oduct o of hi h u lity f ie s, e b s and. the: l ke. i has e n m r to. set t e w st o t r s b h sical and mechanical. methods. However, such methods have not been entirely. satisfactory both m the s n no n o cos an the permanen of the set which has been imparted to the twisted. yarn. For example, it is known that While I Pu s and pile fabrics fabricated from the. twist: ed yarns which have been set by the. aboveprocesses, are superior to rugs and pile. fabrics fabricated from twisted yarns. which have not. been set,. the yarns therein are not set with suflicient permanence to withstand :a' numberof. aqueous cleaning operations without losing a, con-9 siderable amount of their twist. The result is that the rugs or pile fabrics which are-cleaned h man er u r o mark han e 1 the appearance ofthe. pilel st ructure,

The present invention provides a processwhich not only obviates the abore described- ,disadr vantages, but also makes it. possible to set't'he twist of keratinous yarns, which'h'ave been given a high degree of twistgtol an extent which has not been possible by the prior. {art processes. I It is,.,a.ccording 1y, one ObjeIctof'th present invention to provide a simple. and. .efiicient process for setting the twist of mechanically twisted keratinous yarns .such as wool yarns whereby the twisted yarn possesses; after fabrication into a pile fabric, a high degree-of resistance to untwisting when such fabric-is-subjectedto aqueous cleaning operations. 7

A. further object of the present: invention is the processing of highly twisted keratinous, yarns such as wool yarns.- whereby thetwist of the yarns is, set and made-resistant to untwisting when subjected .tohot aqueous: solutions;

A further. object oftheapresent invention is the introduction of'kinks in highly. twisted he: ratinousv yarns and the: simultaneous setting thereof whereby the yarn; retains such kinks when fabricatedrinto rugs; and thencleaned-by aqueougcleaningmethods. V

A further object of the present. invention .is l

the preparation of novel twisted keratinous yarns which. are resistant after fabrication into pile fabrics to untwisting when such fabrics are subjected to aqueous cleaning methods or are treated with hot aqueous solutions.

.Still further objects and advantages. ,of the invention will appear from the. following. descrip tion and the appended claims... 1

The present inventionvis carried out in general by first. treating twisted keratinous yarns such as twisted wool yarns, twisted mohair yarns and the like at about 1.0 to 150? F. with an aqueous dispersion comprising a reducing agent capable of splitting the characteristic cystine linkage of keratin, preferably, reducing agent such. as mercapto compounds having. at least one hydroxyl group and containing from 2 to 6 carbon atoms, and a light stable thermoe plastic, resin which when dry is substantially nontacky. V r

As examples of suitable thermoplastic resins may be mentioned copolyrners of styrene: with ie e or isopre vinyl resins s he ystyrene polyvinyl. butyraln holyvinyl acetate; p ny ao ates. po vinyl ch or de and e k a d --v n d e es s: uc as no yv nylid ne chloride, polyvinyl methacrylatesand the like or o n l me o n l comp unds o v e e om ound .o in l and .v y d ne unds- .A e thea ee a in us arns h ve be re ed a es i ed for a e iod o t e i n t ceuseea onof abou to by wei t .Of re u i a nt w t t ke a n ba ed n t eo sh aoi t k ra .ou a n the a I x r ted t remo e ces 'liquidt e efr'om nd thendri d a t mne atu e b e n about -.35 .F1- heram mar hetu ther nshed i des ed by Washin h m w th an a ua so uti n omsris ne a emul i i age nd n .oiei iz ne. a ent] ca able o re d g with the r s dua un ee ted: redu n agent in the w est edh ndryin l Th venti n at. h prac ise on d ed P undyed at ous yarn H wever if the ais edra n ar to .be empl yed in .a loreo r o nileabr a; t e shon d b d ed n i r t reatme i b cau e-- th fin sh mpar ed to t e ra n e nts-seti a to r.dye nel ne twis a ifi k i he finis ed arn s set quite permanent y y. e'process. de r bed h e:

in;-v When 'suchyarn is fabricated into a pile fabric, it is resistant". to untwisting' ,when. the fab.- ric isnsubjectedto rug: shampooing and other aqueous cleaning operations or whensthe .pile

. 3 fabric is wet out with hot aqueous solutions. In addition, the tensile strength and abrasion resistance of the yarns is not appreciably affected by such processing.

In carrying out the present invention, best results have been obtained by employing mercapto compoimds having one or more hydroxyl groups and containing from 2 to 6 carbon atoms, since such compounds react with the keratin molecule more readily than other reducing compounds. These compounds are also used advantageously since they are compatible with most vinyl or vinylidene aqueous resin dispersions at the tem= peratures employed herein, that is such compounds do not ordinarily cause precipitation of the dispersed vinyl or vinylidene resin particles.-

Moreover, it has been found thatsuch mercaptans do not adversely affect the light stability of vinyl or vinylidene resins. However, it is possible in some instances to employ other organic and inorganic reducing agents which are capable of splitting the cystine linkages of keratin. As examples of such reducing agents may be mentioned inorganic agents such as alkali metal bisulfites, sulfites, sulfides, hydrosulfides and cyanides and the like and organic reducing agents such as the lower aliphatic mercaptans, water soluble derivatives of sulfinic acids and lower mercapto aliphatic carboxylic acids and water soluble salts thereof such as thioglycollic acid, sodium thioglycollate, ammonium thioglycollate and the like. It ispreferable, particularly when employing organic reducing agents of the type described to select compounds which have a solubility of at least 1 by weight in water since such compounds are employed in an aqueous dispersion and they do not react with the keratin to the extent desired if they are not sufficiently water soluble.

As examples of the preferred reducing agents employed in the present invention may be mentioned 2'-mercapto ethanol, l-mercapto sorbitol and l-mercapto glycerol.

The organic or inorganic reducing agents employed herein are most effective when supplied in an amount sufiicient to react with the wool or other keratin filler to the extent of about 1% to 6% by weight, based on the weight of the dry keratin yarn. This is readily accomplished when employing mercapto-alcohol compounds by treating about 1 part of the wool or keratin fiber with about 20 to 30 parts of an aqueous thermoplast dispersion containing about 1 to 4% by weight of mercapto-alcohol compound. The treatment is generally carried out at about 150 F. for 3 minutes or about 100 F. for 60 minutes or between such temperatures for proportionate periods of time depending on the temperature used. However, the same results may be accomplished at somewhat higher temperatures or for longer periods of time, and it is only necessary that the proper weight of mercapto alcohol or other reducing agent be reacted with the wool or keratin fiber and that the treatment be carried out at a temperature of at least 100 F.

' A suitable test for determining the amount of reducing agent reacted with the wool or keratin yarn is to titrate aliquot portions of the aqueous treating solution with iodine, using starch as an indicator, and then calculate the actual quantity of reducing agent removed from the entire treating solution by reaction with the wool or keratin. This value is then converted to a per cent value based on the weight of dry wool or keratin fiber being treated.

In practicing the present invention, either primary or secondary aqueous dispersions of thermoplastic resin are employed. The term primary aqueous resin dispersion as employed herein is intended to cover resin dispersions which have been prepared by the emulsion polymerization of polymerizable monomeric compounds or mixtures of polymerizable, or copolymerizable monomeric compounds. Secondary aqueous resin dispersions, on the other hand, is a term employed herein to designate resin dispersions which have been prepared by dispersing either partially or completely polymerized solid or liquid resin particles in an aqueous solution. This may be accomplished by the use of homogenizing apparatus such as colloid mills and the like or by dissolving or dispersing the resin particles in an organic solvent or plasticizer for the resin, forming a water-in-oil type of emulsion or dispersion and then inverting said emulsion dispersion so as to form an oil-in-water emulsion or dispersion.

The above described resin dispersions may comprise a small amount of plasticizer for the resin depending upon the characteristics of the particular resin being used. When the resin used drys to a flexible film no plasticizer need be employed therewith since the treated wool or keratin yarn comprising such resin will be sufficiently soft and flexible for its intended use. However, when resins such as polystyrene, polyvinyl acrylates and the like are employed in accordance with the present invention, it is desirable to employ a small amount of plasticizer therewith since the treated wool will have a softer feel and more flexibility in such instances.

Best results are obtained when from about 1% to 10% by weight of resin solids, based on the weight of dry wool or keratin yarns, are deposited on the wool or keratin yarn. The twisted yarn may be treated with the aqueous dispersion of reducing agent and resin in a variety of ways. A suitable method consists in immersing skeins of the twisted wool or keratin yarns in the dispersion until the desired reaction between the reducing agent and wool is efiected and then centrifuging or otherwise extracting the treated skeins until the desired amount of resin has been deposited on the wool yarn. Generally, aqueous dispersions comprising from about 2 to 16% by weight of resin solids are suitable for the treatment described above depending upon the method of extraction used.

A further understanding of the present invention will be obtained from the following examples which are intended to be illustrative, but not limitative of the scope of the present invention, parts and percentages being by weight unless otherwise specified.

, Example I A primary aqueous polystyrene dispersion was first prepared as follows:

Forty parts of monomeric styrene, 1.8 parts of sodium stearyl benzene sulfonate as emulsifying agent, 0.0? part of NaHzPOr, 0.28 part of NazHPOi, 0.10 5 part of KzSzOs (catalyst) and 53.55 parts of water were heated in an inert atmosphere of nitrogen at a temperature between about to C. for a period of several hours. The resulting dispersion contained about 40% polystyrene solids and it was diluted until it contained about 4% polystyrene solids.

About 2% of 2-mercapto ethanolwas added to the dilute dispersion ..of polystyrene (as preaccess:

pared above) land: the -dispersion-was:heated -to 130 A skein-of highly twisted-wool car-pet lgsln withzzbutyl ricinoleatev (plasticizc'ar) in a yarn was immersed in the heated dispersionfor about 5 minutes, after :whlch it was centrifuged and thoroughly dried. About parts-of dispersion were employedsfor 1 partof carpetyarn. The treated yarn was woven into a pile fabric which was then subjected to several .-aqueous cleaning operations. The twistrand kink-of the treated yarn was not substantially :afiected :by such cleaning'operations.

By preparing :an-aqueo'us dispersion contain ing about 25% dibutyl phthalat'e "(1313801012819 based on thestyrene monomer in the; preparation of the polystyrene dispersion by emulsion "polymerization and then treating a highly twisted wool carpet yarn as immediately describedabove,

:it is possible to produce 'a soiter, -a yet noneta'cky yarn.

'E'rample II A .primary aqueous polyvinyl acetate dispersion was preparedas follows:

Eight hundred parts of water, 10 partsof methyl cellulose v(emulsifying agent), lO parts of gum arabic (emulsifying agent), 12 a-parts of sodium salt of the sulphonic acid-of; dioctyl succinic ester (surface tension depressant), 93.0

parts of monomeric vinyl acetate and 1 partof contained about 100%,. based on the weight-of the yarn,of the dispersion andthe yarn was then dried. The treated yarn'was woven into a frieze rug whichwas thengiven severalaqueous cleanings. 'The kink and twist of the treated yarn was found to 'be'set' substantially" fast to such aqueous cleaning operations.

Earanrmle III One part of highly twisted wool carpet yarn in skeinform was immersed for-5 minutes 'in parts ofan aqueous dispersiongcontaining 5.% polyvinyl butyral (prepared as a secondary aqueous resin dispersion) and 1.5% ,of 2-mercapto ethanol. The dispersion was maintained at a temperature of approximately 150 F.during the immersion period. Thereafter the skein of yarn was centrifuged and dried. The treated yarn was woven into a frieze rug. The kink and twist of the treated yarn was found to be set substantially fast to aqueous rug cleaning operations.

The polyvinyl butyral employed in this example was prepared by condensing butyralde- Baker-Perkins mill and then slowlyadding water tolthe mix until first awater-rin-oiland then an .oilein-water dispersion..-is':-formed.

It isapparent, however, thatiother polyvinyl Jbutyrals differing inxhydroxy, acetate :andaeetal composition from the specific polyvinyl'butyral described above may also Joe-employed. .Moreever, the :aqueous polyvinyl butyral dispersion .mlayabe prepared in. other ways .as. 'for example, zby a homogenizing procedure using a colloid -mi11:.f.0. dispersionpf the r si a i e V V Various.amodifications may bemade in the 1 proc.ess -.d$cribe d herein and -it is intended that the invention beulimited only by the scope of he-ann n edw aims- What s-claimed s: H 1. process of setting .the twist of vtwisted keratinousyarns which consists in treatingsald yarns-with anaqueous dispersion omprising from 2 to 16% by weight o f dispersed particles of a thermoplastic resinselected ,fromthe group consisting of vinyl resins-and vinylidene resins, which resins; aresubstantially non-tacky when dry.xand from about -1 to 11% of an aliphatic memento alcohol .containing irom 2,1;0 6 carbon atoms which are,-,attached to each other in a carbo nto-carbon linka e, said compound consisting of.

a; mercapto group, at least one .hydroxyl, group, 163.1bilfl fifl0I-I1Sf3l'ld: hydrogen atoms-until from. about 1 to 6% by We ght. based on the weight. .of the, dry ,yarn, of saidmercapto.compound has:

reacted withsaid yarn, .the temperature ofsaid dispersion be ng above =about-100 F. during said. treatment; extractingsaid yarns to. remove excess-liquid therefrom andto deposit fromaboutl to 10% by weight-oi said resin particles based on the dry weight.-of;the-yarns;.and thendrying said yarns.

2. A process of setting'the twist .of twisted .leeratinousqyarns which consists in treating ,said

.yarnswith anaqueous dispersion comprising from 2.to 16% by weight of dispersed: polystyrene particles and from about .1 to 14%v by weight of an aliphatic meroaptoa lcohol containing. from 2 to 6. carbon. atomswhich ,are attached to I each other in =a....carbon-to-carbon linkage; said compound consisting :of a. mercapto ;group, at least one hydroxyl group.- carbon atoms and hydrogen hyde with a partially hydrolyzed polyvinyl acetate and contained on a weight basis 17 to 20% hydroxy groups calculated as polyvinyl alcohol, 7

less than 3% acetate groups calculated as polyvinyl acetate and the remainder substantially atoms, =until from about1= to 6% by Weight, based 011:0 1'l8 W6ifih b. of the dry yarns, of said mercapto compound has reacted with said yarns, thetem-- perature of .said dispersion being between about :and.150] F. during said treatment; extracting said yarns to remove excess liquid therefromandi to -deposit from about 1 to 10% by weightoff said polystyrene particles based on the dry weight. of the yarns; and then drying said yarns.

3. A process of setting the twist of twisted. keratinous yarns, which consists in treating said yarns with an aqueous dispersion comprising from about 2 to 16% by weight of dispersed polyvinyl acetate particles and an aliphatic mercapto alcohol containing from 2 to 6 carbon atoms which are attached to each other in a carbon-to-carbon linkage, said compound consisting of a mercapto group, at least one hydroxyl group, carbon atoms and hydrogen atoms, until from about 1 to 6% by weight of said mercapto compound, based on the weight of the dry yarns, has reacted with the V yarns, the temperature of said dispersion being between about 100 and F. during said treatment; extracting said'yams to remove excess liquidtherefrom and to deposit from about 1 to 10% by weight of polyvinyl acetate particles.

based on the dry weight of the yarns; and then drying said yarns. 11,.

4. A process of setting the twist of twisted keratinous yarns which consists in treating said yarns with an aqueous dispersion comprising from about 2to 16% by weight of dispersed polyvinyl I atoms, until from about 1 to-6% by weight of said mercapto compound, based on the Weight of the dry yarns, has reacted with said yarns, the temperature of said dispersion beingbetween about 100 and 150 F. during said'treatmen't; extracting said yarns to remove excess liquid therefrom and to deposit from about 1 to byweight of said polyvinyl butyral particles based on the weight of the dry yarns; and then drying said yarns.

5. A process of setting the twist of twisted keratinous yarns which consists in treating said yarns with an aqueous dispersion comprising from about 2 to 16% by weight of dispersed particles of a thermoplastic resin selected from the group consisting of vinyl resins and vinylidene resins, which resins are substantially non-tacky when dry, and

said yarns-to remove excessliquid therefrom and to deposit from aboutl to 10% by weight of said resin particles based on the weight of the dry yarns; and then drying said yarns;

6. A process of setting the twist of twisted keratinous yarns which consists in treating said yarns with an aqueous dispersion comprising from about 2 to 16% by weight of dispersed particles of a thermoplastic resin selected from the group consisting of vinyl resins and vinylidene resins, which'resins are substantially non-tacky when dry, and from about 1 to 4% by weight of l-mercapto glycerol until from about 1 to 6% by weight of l-mercapto glycerol, based on the weight of the dry yarns, has reacted with said yarns, the temperature of said dispersion being between about 100 and 150 F. during said treatment; extracting said yarns to remove excess solution therefrom and to deposit from about 1 to 10% by weight of said resin particles; and then drying said yarns.

7. A process of setting the twist of twisted keratinous. yarns which consists in treating said yarns with an aqueous dispersion comprising from about 2 to 16% by weight of dispersed particles of a thermosetting resin selected from the group consisting of vinyl resins and vinylidene resins,

.which resins are substantially non-tacky when dry, and from about 1 to 4% by weight of l-mercapto sorbitol until from about 1 to 6% by weight of said mercapto sorbitol, based on the weight of the dry yarns, has reactedwith said yarns, the temperature of said dispersion being between about and F. during saidtreatment; extracting said yarns to remove. excess liquid therefrom and to deposit from about 1 to 10% by weight of said resin particles based on the weight of the dry yarns; and then drying said yarns.

8. A composition for treating keratinous yarns consisting of an aqueous dispersion comprising from about 2 to 16% by weight of dispersed par-V ticles of a thermoplastic resin selected from the group consisting of vinyl resins and vinylidene resins, which resins are substantially non-tacky when dry, and from about 1 to 4% by weight of an aliphatic-mercapto alcohol containing from 2 to 6 carbon atoms which are attached to each other in a carbon-to-carbon linkage, said mercaptoalcohol consisting of amercapto group, at least 1 hydronyl group, carbon atoms and hydrogen atoms.

9. A composition for treating keratinous yarns consisting of an aqueous dispersion comprising from about 1 to 4% by weight of Z-mercapto ethanol and from about 2 to 16% by weight of dispersed particles of a thermosetting resin selected from the'group consisting of vinyl resins and vinylidene resins, which resins are substantially non-tacky when dry.

OSCAR P. COHEN.

References Cited in the file of this patent 'UNITED STATES PATENTS 7 Number Name Date 2,201,929 Speakman May 21, 1940 2,212,744 Masland Aug. 27, 1940 2,238,672 Arthur Apr. 15, 1941 2,261,094 Spe'akman Oct. 28, 1941 2,403,937 Lubs July 16, 1946 2,499,444 Allison Mar. 7, 1950 2,509,347 Jackson May 30, 1950 FOREIGN PATENTS Number Country Date 17,990/34 Australia June 13, 1934 117,071 Australia June 3, 1943

Claims (1)

1. A PROCESS OF SETTING THE TWIST OF TWISTED KERATINOUS YARNS WHICH CONSISTS IN TREATING SAID YARNS WITH AN AQUEOUS DISPERSION COMPRISING FROM 2 TO 16% BY WEIGHT OF DISPERSED PARTICLES OF A THERMOPLASTIC RESIN SELECTED FROM THE GROUP CONSISTING OF VINYL RESINS AND VINYLIDENE RESINS, WHICH RESINS ARE SUBSTANTIALLY NON-TACKY WHEN DRY, AND FROM ABOUT 1 TO 4% OF AN ALIPHATIC MERCAPTO ALCOHOL CONTAINING FROM 2 TO 6 CARBON ATOMS WHICH ARE ATTACHED TO EACH OTHER IN A CARBONTO CARBON LINKAGE, SAID COMPOUND CONSISTING OF A MERCAPTO GROUP, AT LEAST ONE HYDROXYL GROUP, CARBON ATOMS AND HYDROGEN ATOMS, UNTIL FROM ABOUT 1 TO 6% BY WEIGHT, BASED ON THE WEIGHT OF THE DRY YARN, OF SAID MERCAPTO COMPOUND HAS RECTED WITH SAID YARD, THE TEMPERATURE OF SAID DISPERSION BEING ABOVE ABOUT 100*F. DURING SAID TREATMENT EXTRACTING SAID YARNS TO REMOVE EXCESS LIQUID THEREFROM AND TO DEPOSIT FROM ABOUT 1 TO 10% BY WEIGHT OF SAID RESIN PARTICLES BASED ON THE DRY WEIGHT OF THE YARNS; AND THEN DRYING SAID YARNS.