Патент USA US2412125код для вставки
2,412,125 Patented Dec. 3, 1946 r l l UNITED STATES PATENT‘OFFICE 2,412,125 ARTICLE AND TREATMENT OF CASEIN ' FIBERS John E. Conrad. Baia-Cynwyd, Pa., assignor to Collins 8; Altman Corporation, Philadelphia, Pa., a corporation of Delaware No Drawing. Application October 18, 1,941, ~ Serial No. 415,631 11 Claims. (Cl. 8-21) 1 This invention relates to a process‘of preparing synthetic ?bers derived from casein or from other protein substances for dyeing in certain dyebaths so that these synthetic fibers may be blended or otherwise used together with wool and/or mohair ?bers in the manufacture of textile fabrics which are to be dyed in the piece to a substantially uniform shade without oblectionably noticeable striations appearing. My improvements are of ‘particular utility in the union dyeing of fabrics, both pile and ?at, containing cotton or other cellulose ?bers as well as‘ wool and/or mohair. By my improvements a novel ?ber and fabric are produced. 2 When untreated synthetic casein fibers are in cluded in the pile yarn blend together with wool and/or mohair, and the fabric union dyed in a ‘ pad dyeing operation, the synthetic casein ?bers ‘ will ordinarily dye much darker or deeper than the wool and mohair ?bers. As indicated here inbefore, if such a fabric be union kettle dyed, the difference will not be as great due to the often repeated immerslons. but there will never the less be a substantial contrast in shade. A difference in color or shade will also occur ‘ ii’ untreated synthetic casein ?bers be blended with wool and/or mohair ?bers in fabrics. such as worsted ?at fabrics. having no cotton and ' fabrics dye by pad dyeing methods with acid Throughout this speci?cation the term “casein 15 the dyestuiis in a substantially neutral bath. ?bers" will for brevity be used, but the term will According to my improvements I may produce be understood to include other synthetic protein 9. treated casein fiber which will dye to a shade ?bers such as those derived from the soy bean approximating that of wool or mohair when the 20 two types of ?bers are dyed together in a sub casein. stantially neutral aqueous union bath contain Synthetic casein ?bers are of protein material ing neutral dyeing acid dyestuffs and substan and accordingly have affinity for many of the tive dyestutfs using either short time immersion same dyes as have wool and mohair, but the ini methods. as in pad dyeing. or long time repeated tial a?lnity oi’ the synthetic casein ?bers for dye stuffs is much stronger than that of the wool 25 treated immersion casein methods. ?ber willasalso in dye kettle similarly dyeing. to wool My or from zein (corn), as well as those derived from and mchair ?bers. Consequently. if untreated casein ?bers be blended with wool and/or mohair or mohair when the two types are dyed together by either pad or kettle methods in a substantially ?bers in yarns which are then dyed by short time neutral aqueous bath containing only neutral immersion methods, as in pad dyeing, the casein dyeing acid dyestu?'s or when the two types are ?bers will dye so much darker than the wool and 30 pad dyed together with vat dyestu?s. My treated mohair as to constitute a difference in color. casein ?ber does not. however. dye like wool or Where the time of immersion is long, as in kettle mohair when the two are dyed together by either dyeing, the stronger initial a?inity of the syn pad or kettle methods in acid dye baths. thetic casein ?bers will be partially overtaken but The treatment given the casein ?ber to accom' there will nevertheless be a substantial differ ence in shade between the synthetic casein and the natural wool and/or mohair ?bers. In the manufacture in quantity of textile pile pllsh the foregoing e?ects does not weaken the or without other fibers, including casein ?bers, in the pile. it is very desirable for reasons of whereby a water insoluble metallic tannate is incorporated with the casein ?ber. The tannate ?ber nor does it make the fiber sti? or hard or harsh or gummy. In other words. the treated ?ber retains substantially its initial strength. fabrics having a. cotton backing or base por ?exibility. elasticity and feel. tion and wool. or mohair, or blends thereof. with 40 My method comprises a two bath treatment speed and economy oi.’ production to dye the fabric in the piece in a union dye bath in a continuous is preferably light colored so as to affect as lit tle as possible the color or shade to which the A union 45 fiber is dyed. This is important in connection dye bath which I contemplate is an aqueous bath with producing shades currently used for most containing (a) neutral dyeing acid dyestuffs for operation using pad dyeing methods. the wool. casein and mohair ?bers, and (bi sub stantlve dyestuffs intended primarily for the cot ton fibers. The wool. casein and mohair fibers also have affinity for the‘substantive dyestuffs so that the shade or color to which they dye is the combined effect of both components of the union dye bath. Application Serial No. 655,592 .Jh-ls-l Fnv.‘ ,. is a. uJvlbiGn c.I Lk ....2 press... ems. automobile upholstery pile fabrics. According to a preferred embodiment of‘ my improvements, the casein ?bers are first sublect ed to an aqueous solution of tennis acid. The ex cess solution may then be removed and the ?bers next immersed in an aqueous solution, preferably of stannous chloride, whereby tin tannaie is in corporated with the ?bers. The ?bers may then $319,126 be rinsed and dried. The second bath may if desired be an aqueous solution of any water solu ble aluminum salt such as aluminum sulphate or aluminum acetate, whereby aluminum tannate will be incorporated with the ?bers. Or the sec ond bath may be an aqueous solution of tartar emetic, whereby antimony tannate will be incor porated with the ?bers. A small amount of acetic acid may preferably be used in each bath, i 4 mately 120° F., cdhtaining stannous in an amount approximating three‘ percent. of the weight of the stock. A temperature substantially higher than 120° F. would damage the available casein ?bers, and a substantially lower tempera ture would give markedly inferior-"resist e?'ects for the contemplated dyebaths. Acetic‘acid in an amount approximating one percent. ‘of the weight of the stock may be contained in the sec the presence of acetic acid being more important 10 ond bath. As'a result of the reaction between , in the second bath than in the ?rst. The time the tannic acid and the stannous chloride, tin of immersion, the temperature of the baths and tannate is incorporated with the ?bers. the concentration of the solutions will be more The metallic salt of the second bath may. if fully described hereinafter. desired, be aluminum sulphate or aluminum ace It is an object of this invention to prepare syn 16 tate. in which case aluminum tannate is in0or_ thetic ?bers derived from casein or other protein porated with the ?bers. Or the second bath may substances for dyeing so that the said synthetic be an aqueous solution of tartar emetic, in which ?bers may be blended or otherwise used together case antimony tannate is incorporated with the with wool and/or mohair and cotton ?bers and ?bers. Tin tannate, aluminum tannate and an dyed in arunion bath without objectionably no 20 timony tannate' are all light in color-and accord ticeable striations appearing. ing’ly will not substantially darken the natural More speci?cally. it is an object of this inven color of the casein ?ber so as to interfere with or tion to prepare arti?cial ?bers derived from ca limit the color or shade which it is desired to ap. sein for dyeing in a union bath containing neutral ply in the subsequent dyeing operation. ' dyeing acid dyestuffs and substantive dyestuds, 25 In each bath the volume otaqueous solvent or for dyeing with neutral acid dyestu?s, or with should be su?lcient to work the ?ber stock there vat dyestuffs using short time immersion methods in. The weight of the aqueous solution‘ may as in pad dyeing. conveniently be aboutr?i'teen times the weight of Another object is to produce a synthetic casein the ‘?ber stock. ?ber having a water insoluble metallic tannate 80 Attention is directed to the (act ‘that in the incorporated therewith. which when subjected to preferred treatment described‘ above the tem neutral dyeing acid dyestuffs, or to substantive perature of the tannlc acid bath is approximate— dyestu?s; or to both as in union dyeing, or .to vat ly 160° F. This temperature is Just above the dyestu?'s in a short time immersion operation will point where the casein ?bers swell markedly and dye to a shade approximating the shade of wool 35 at this temperature the ?bers will absorb the ?bers subjected to the same dye bath for the tannic acid solution more readily than at sub same length 0! time under the same conditions. stantially lower temperatures. Temperatures Another object is to provide a method of in - below 160° F‘. may be employed if desired, but the corporating a water insoluble tannate with the time oi‘ immersion should be increased accord casein ?ber. 40 Another obiect is to produce a unlormly dyed ' Higher temperatures than 160' I". may also be inely. textile fabric including casein, cotton and other cellulose ?bers, and wool ?bers; said casein ?bers having a water insoluble metallic tannate incor Dorated therewith. ‘ Another object is to incorporate tin tannate, ' . . employed, but temperatures lubstantially in ex cess oi 180° F. should not be used. as thestrength' oi the casein ?l'irs will be impaired. I have 45 obtained satisfactory resist eflects using as a ?rst bath a one-half of one percent. aqueous or aluminum tannate, or antimony tannate, with solution of tannicacid at a_.temperature of. 180,’ the casein ?ber, whereby the ?ber will have an F., the time of ‘llnmerslom‘bein-g- two‘ minutes; a?inity approximating that or wool ?bers for indicated, this is a-maxlmum temperature and neutral dyeing acid dyestuffs. or substantive dye 50 aAstwo minute immersion-period is minimum, as stu?‘s, or both as in union dyeing. . shorter periods o-i' immersion do not give sum Another object is to treat casein ?bers so that ciently strong resist e?ects. . they may be blended together with wool and/or The time of immersion in the second bath mohair ?bers in the pile of pile fabrics having a as indicated above, be ?ve minutes or 3 cotton backing, and dyed together therewith in a 55 should, more and the amount 01' stannous chloride in union bath using short time immersion methods solution should neither greatly exceed nor be as in continuous pad dyeing, all of the blended greatly less than three percent. of the weight ?bers in the pile being dyed to nearly the same of the ?bers being treated, as in either case the shade. shade of the dye would be adversely ailected, These and other objects of invention will be 60 and if more is used the ?bers may be weakened. manifest from a consideration of the speci?cation My improvements are particularly applicable for and ot the claims. '~ pad type union dyeing where the time of immer— According to a preferred embodiment of my invention, the synthetic casein ?bers are im mersed in one quarter of one percent. aqueous solution of tannic acid at'l??i' F‘. It is deslrab‘e but not essential that the solution contain a small quantity of acetic acid. After about ?ve or more minutes of being worked in the solution as by gentle agitation, the stock may be rinsed or nipped or the solution may be merely permitted to drain oil’. The casein ?ber stock is then immersed for five or more minutes in the second bath, which is preferably an aqueous solution, at approxl— sion is very short. that is, a matter of seconds. This type of dyeing is widely used in the produc tion of pile fabrics, as is set forth in United States Patent to Drobile et al. No, 2,071,922. A‘ satisfactory dyebath immersion time in process lllg according to the prior patent is ten seconds. I have found that after a ten second immersion my treated casein ?bers will approximate the shade of wool and/or mohair blended therewith. It is to be understood that wool and mohair do not dye identically, but that they dye sufliciently close in shade to permit blending without ob jectionably noticeable striations in the ?nished 5 2,412,125 6__. piece. My treated casein ?bers may be brought within a shade range which permits blending with with wool ?bers. and- ‘pad dyeing the blerided ?bers to approximately the same shade with a wool or mohair to give a like uniiorm appearance substantially neutral dyebath’ containing neutral to the cloth utter a ten second immersion as set dyeing acid colors.‘ forth. This result is accomplished by the treat ment illustrated by this preferred embodiment. A typical treatment -01' a commercial quantity of casein‘?bers according to my method is as fol 120° F. 500 lbs, of synthetic casein ?bers is placed in a 10 suitable container or kettle. The aqueous solu tion of tannic acid at about 135° F. is drawn from a reservoir, placed in the kettle and then brought to a temperature of 160° F. and held there for ap proximately ten minutes, during which the ?ber 15 stock may be gently agitated. The tannic acid solution is then drained out and pumped back water or solution may be removed. The ?bers are now ready for the second bath. Water and half of the required acetic acid is poured into the kettle, then the solution of stanncus chloride and the remainder of the acetic acid is added and the entire solution brought to 120'’ I". and held there. The ?bers are kept in this solution for approxi mately five minutes, after which the kettle is - drained. the ?bers rinsed and then dried. In this condition the ?bers are ready for blending . 6. A process of making blended fabrics con taining casein ?bers and natural animal ?bers of approximately the same shade, which includes treating the casein ?bers so as to form a metallic tannate on the ?bers, blending the treated casein ?bers with natural animal ?bers and then pad dyeing the blended fabric to an approximately uniform shade with a substantially neutral dye bath containing neutral dyeing acid ‘colors. 7. An undyed synthetic ?ber derived from 1 casein and having a water insoluble/metallic tan nate incorporated therewith in an amount which will provide a partial resist for neutral dyeing acid colors to an extent that it will cause said ?ber when immersed for a period of ten seconds 25 in a substantially neutral aqueous medium con so . taining neutral dyeing acid colors and then nipped as in pad dyeing to dye to approximately the shade of wool ?bers immersed in the same dye bath for the same period of time under the with wool or other ?bers or for use alone in the 80 same practical dyeing conditions. formation of yarns. . perature of the tin salt solution approximates lows: into the reservoir. A light rinse may then be given the casein ?bers, after which any excess , 5. A process as set forth in claim 4 further characterized in that the temperature of the tan- . nic acid solution is less than 180° F. and the tem- % ' 8. In a process of 'preparing synthetic‘?bers As indicated hereinbei'ore, casein ?bers treated derived from casein so that they will be partially , according to my methods will dye approximately resisted and, will dye approximately like wool in like wool when the two types 0! ?bers are dyed a substantially neutral aqueous medium contain together, by either pad or kettle methods, in a ing neutral dyeing acid colors in ill-second im substantially neutral aqueous medium containing mersion pad dyeing operations, the steps which neutral dyeing acid dyestu?s or substantive dye consist in treating the ?ber with each of two stuffs, or both as in union dyeing, or pad dyed separate aqueous solutions, one solution contain with vat dyestu?’s. .Casein ?bers treated accord ing tannic acid and the other being an aqueous ing to my method will not, however, dye like wool (0 solution of stannous chloride, said stannous chlo where the two are immersed together in an acid ride being present in an amount approximating bath containing acid dyeing acid dyestuffs, 3% by weight of the ?bers being treated and the Having descrlbedmy invention, I claim: temperature of said stannous chloride solution 1. A process of making blended fabrics con being approximately 120° F. during processing. taining casein ?bers and natural animal ?bers 45 9. An undyed textile fabric including cotton, of approximately the same shade which includes wool, and casein?bers, said casein ?bers con-L, treating the casein ?bers so as to form a tin taming a metallic tannate in an amount that tannate on the ?bers, blending the treated casein the casein ?bers are partially resisted to neu ?bers with natural animal ?bers'and then pad tral dyeing acid colors in a manner which dyeing the blended fabric to an approximately 50 causes them to dye to approximately the same uniform shade with a substantially neutral dye shade as the natural wool ?bers when the fabric bath containing neutral dyeing acid colors. is immersed for ten seconds in a substantially 2. A process as set forth‘in claim 1 further neutral dye bath containing neutral dyeing acid characterized in that the tin tannate is formed dyestuffs and substantive dyestuffs and then by treating the casein fibers with each of two 55 nipped as in pad dyeing. separate solutions, one of which contains tannic 10. An undyed textile fabric including wool and acid and the other of which contains a tin salt. casein ?bers, said casein ?bers containing a light 3. A process of treating‘ textiles which includes colored metallic tannate in such percentage that the steps of treating synthetic ?bers derived from the casein ?bers are partially resisted to neutral casein with each of two separate aqueous solu 60 dyeing acid colors in a manner which will cause tions, one of which contains tannic acid and the the fabric, when immersed for ten seconds in a other of which contains a tin salt, then drying substantially neutral dye bath containing neu the treated ?bers, blending the treated synthetic tral dyeing acid dyestu?‘s and then nipped as in ?bers with wool and dyeing the blended fibers pad dyeing, to dye to an approximately uniform to approximately the same shade with a sub shade. stantially neutral dyebath containing neutral 11. A synthetic ?ber derived from casein, said dyeing acid colors. ?ber having a water insoluble metallic tannate 4. A process oi’ treating~ textiles which includes incorporated therein in such an amount that the the steps of treating synthetic ?bers derived from ?ber will be partially resisted for neutral dyeing 70 casein with each of two separate aqueous solu acid colors but will dye to a uniform shade in a tions, one of which contains tannic acid and the substantially neutral aqueous dyebath containing other 01’ which contains a tin salt, then drying neutral dyeing acid colors. the ?bers, blending the treated synthetic ?bers JOHN’ E. CONRAD.