Патент USA US2406408код для вставки
. Patented Aug._ 27, 1946 2,406,408 ' UNITED STATES PATENT OFFICE TREATMENT OF TEXTILE MATERIALS George W. Seymour and Walter Brooks, Cumber land, Md., assignors to Celanese Corporation of America, a corporation of Delaware . - No Drawing. Application December 30, 1942, Serial N0. 470,662 8 Claims. (01. 252-835)‘ 1 2 , This invention relates to the treatment of tex- ' tile materials and relates more particularly to the conditioning of ?bers and ?laments‘ made of organic derivatives of cellulose whereby the upon the ?bers or ?laments treated or presented other difficulties of applications. Particularly in the case of conditioning of rela tively short length or staple ?bers formed of or same are rendered more amenable to textile op 5 ganic derivatives of cellulose do the prior lubri erations such as carding, drafting,- spinning and, cating compositions fall short of what‘ was de-, - also weaving or knitting, and to the formed yarns sired. While some such compositions were ca and fabrics made from or containing said or ganic derivatives of cellulose ?bers or ?laments. pable of conditioning the ?bers to withstand the numerous bendings and twistings imparted there An object of the present invention is thepro 10' to during processing, they did not impart the vision of an improved method of preparing a sta- . desired degree vof friction between the fibers to I ' ble liquid for conditioning ?bers‘ and ?laments comprising organic derivatives of cellulose to im enable them to be drawn or drafted to ?ne yarns. On the other hand, some compositions are satis prove their amenability to textile operations such ~> factory with respect to their friction character as carding, drafting, spinning, twisting, coning, 15 istic but do not properly condition the ?bers for pirning, hanking, weaving, knitting and the like. weaving, knitting or other textile operations. ‘ A further object of our invention is to provide a treatment for textile ?bers or ?laments con We have found that these and other disad vantages arising' out of the use of known condi-r taining organic derivatives of cellulose with a tioning ?uids can be avoided by the use of the novel conditioning ?uid whereby they are ren 20 conditioning ?uid of the present invention com dered more anti-static and have the proper amount of friction between the ?bers to give a control to carding and drafting. prising a mixture of several ingredients, some of which react with each other. Fibers treated with our novel composition behave much more. A further object of the present invention isvto satisfactorily in carding and drafting operations provide a process for the treatment of organic 25 and in subsequent winding, twisting, warping, derivatives of cellulose textile materials with a weaving, knitting and like operations than do conditioning ?uid containing different types of untreated ?bers and ?laments, or ?bers and ?la lubricants, softeners and other ingredients where by fabrics made from such materials have a softer hand and present a uniform appearance. 7 Another object of the invention is the provision ments treated with known conditioning ?uids. Moreover, we have found that ?bers treated with 30 our conditioning ?uids are not deleteriously af fected upon storage and in some case may even of an improved textile material made of or con be improved after being stored for a time. Fur taining organic derivative of cellulose ?bers or thermore, the conditioning ?uid of our inven ?laments having applied thereto a conditioning tion does not alter its effects on the fibers stored ?uid of the present invention. ' . 35 for long periods of time but retains the same Other objects of our invention will appear from balance of friction for carding and drafting op the following detailed description and the ap pended claims. _ . erations, lubricative properties for other textile operations and conditioning properties to with stand the rigors of processing. Other advan Many substances such as vegetable, animal and mineral oils, both normal and specially treated, 40 tages are also imparted to the yarn by our con have been employed for lubricating or condition ditioning ?uid as will appear hereinafter. _ ing textile materials in order to render them In accordance with our invention we treat ?bers more suitable for processing a fabric. While or ?laments containing organic derivative of cel these substances have resulted in some improve - lulose with a conditioning agent formed by re ments in processing, they‘ still left much to be 45 acting a mineral oil, a fatty acid and sulphuric desired and in addition presented problems of . acid and to this reaction product adding a vege-> their own. Thus, the oils tend to gum or poly *tabl'e ‘oil, an alkali, an alkyloiamine and water. merize with time so that lubricated ?bers and This conditioning agent‘ is stabilized, preserved ?laments cannot be processed uniformly due’to ., against oxidation and given an enhanced cover the hardening of the oil. ‘Moreover, such gum 50 ing power by the addition of an alkylated phenol ming or polymerization makes it diiiicult for the or other spreading and penetrating agent. conditioning agent to beremoved from the fabrics The ?bers or ?laments to be treated in ac made with such textile materials. Also lubri .. cordance 'withv this invention may have as a basis cating or conditioning compositions heretofore any suitable organic derivative of cellulose such used did not penetrate or spreadevenly into or as organic esters of cellulose and cellulose ethers. 2,406,408 4 . ' lose acetate, cellulose propionate and cellulose acid, palmitic acid, etc. The preferred fatty acid, butyrate or mixed esters such as cellulose acetate butyrate or cellulose acetate-propionate, while I 1 , 1 . step of ourinvention may be any suitable fatty acid, examples of which are oleic acid, recinoleic . ‘ Examples of organic esters of cellulose are. cellu-' ‘however, is oleic acid of at least 'technical grade examplesof cellulose 'ethers are ethyl cellulose 5 or better. The sulphuric acid employed is fuming sulphuric acid containing about 20% SO: and is and‘benzyl cellulose.- However, the conditioning commonly termed “Oleum 20%”. " ' agent of the instant-ginventionis particularly ad ; - A preferredimethod of preparing the condition; vantageous in connection with the 'usefof cellulose‘ ; acetate as the basis for the ?bers or ?laments, . - ing ?uid of our invention is as follows: , especially acetone-soluble cellulose acetate hav 10 ._ About 29 parts of a white mineral oil of 50 vis 1, cosity, 21.5 parts of oleic acid or its equivalent of other fatty acids and 10.5 parts of raw vegetable oil such as olive oil, rice oil or peanut oil are f ing an acetyl value of 521/2% to 56%, preferably ._ Silt/2%, calculated as acetic acid. However,'par- ' ‘ tially saponi?ed organic estersof cellulose-may be mixed and "cooled to about 10° C. in a; jacketed ‘ also employed as the basis of the ?bers or ?la , ; , ‘ 1 l5 mixer through the jacket of which circulates a cooling medium having a temperature of --10° to This invention is applicable to the treatment of ?ne ?laments,,or a plurality of such ?ne ?la-h v —20° C. With constant stirring about 6.5 parts of fumingsulphuric acid are slowly added, say in ments associated together in the form of yarn, or ‘ a 30 minute period. The temperature rises to larger ?laments such as arti?cial bristles, horse- ' hair, straw and the like; and also to fabrics or 20 about 20° C. du'ring'the reaction time of about 75 other articles formed therefrom. It, is, particu ments. , minutes. h .. - To the above reaction product is-adde'd about : larly applicable to the treatment of relatively .parts. of diamyl phenol and then "a mixture of short lengths of ?bers, say from 1/4 inch to 6 or about 11.6 parts of triethanolamine or its equiv 1 more inches in length that are known in the trade ‘ as staple ?bers. The conditioning liquid may be 25 alent of other alkylolamine, 1.6 parts of: sodium ‘ , applied to the staple ?bers or to the continuous ’ hydroxide or its equivalent of potassium hydroxide ‘ , ?laments from which the staple ?bers are cut or and 14 parts of water. The whole batch is stirredv j to the ?laments as they are-being cut. The ?bers j' or'?laments need not consist wholly of ?bers or " ‘until all reaction ceasesand a clear oil'is formed. ~ Some of the raw vegetable oil may be added with ‘ ?laments of organic derivative of ‘cellulose but '30~ the alkali, if so desired. This conditioning liquid may contain ?bers of other materials such as - may be‘ mixed with water and applied as an emul sion to the ?bers, filaments, yarns. etc. , = natural silk; arti?cial ?bers of. reconstituted In the resulting product substantially 40% of the original oleic or equivalent fatty acid is sul j on arti?cial ?bers that contain ?nely divided pig 35 fated and/or sulfonated; substantially 9% of the original raw vegetable oil is sulfated and/or sul ‘ ment-like materials that alter the lustre and/or fonated; the mineral oil remains substantially un ‘ color of the ?ber without deleterious effect. ' affected chemically; none of the vegetable oil is As stated above, our novel- conditioning ?uid saponi?ed- ‘by the alkali and triethanolamine 1 comprises the reaction product of mineral oil, cellulose, wool, cotton, etc. The conditioning ' . liquid of the present invention may be employed ‘ fatty acid and sulphuric acid, which reaction 40 which has been added in amounts to neutralize all the sulfuric acid present and most but not all of the oleic or other fatty acid used. The product is slightly acid due to the‘ presence of about 10% 1 resulting compound stabilized and otherwise’ im of umieutralized oleic acid. ‘ proved by the addition of an alkylated phenol, 1 or where the ?bers to be treated contain an ester ‘45. a; The product is an oily compound which readily of cellulose with an alkylated phenol and/or’ . forms a stable, white emulsion in water, 2% emul ‘ product is reacted with a raw ‘vegetable oil, an‘ _j alkali, an alkylolamine and water and the whole' sian'thereof having a pH of 6.8. esteri?ed vegetable oil. In a preferred form of’ ' . " . In place of all or a part of the diamyl pheno our invention all or a part of the raw vegetable; employed in the above formula there may be sub oil is added with the fatty acid and takes part in‘ the ?rst reaction. Other materials may also be 50' stituted other alkyl derivatives of phenols; The alkylated phenol not only acts as an anti-oxident added, such as, for example, softeners for particu but also enhances the penetrative and spreading lar ?bers being treated; substances which aid in .e?ects of the. conditioning liquid in and on the emulsifying the com-position and also facilitate ‘?bers and yarns and stabilizes the conditioning ‘ the removal of the same by scouring; preserva ‘ tives'lsuch as Dowicide A (sodium ortho phenyl 55 ‘liquid whereby it does not separate into its com- _ ponents upon standing. Examples of other alkyl ‘ phenate), etc. Fugitive dyes or tints may also be derivatives of. phenols or alkylated phenols are added to identify the materials in processing also ‘ dibutyl and 'diamyl derivatives of\cresols and permanent dyes, etc. may be added. , xylenols, the dibutyl and diamyl derivatives of The mineral oil employed in forming the con ditioning liquid of our invention may be, one hav- ~ 60 any of thei‘mono-chlorophenols, etc. The diamyl phenol may also be‘replacedain whole. or in part by ' . ing a. para?inic or naphthenic base and a viscosity tricresyl phosphate or- triphenyl ' phosphate or of ‘ 50 to 75 seconds. The viscosity referred, to I‘ similar compounds. ‘ When the ?ber or yarn being herein is Saybolt Universal at 100° F. However, ' the viscosity of the mineral oilemployed is deter; " Y, treated, contains organic esters ,of cellulose, the ' mined by the over-all viscosity desired in the ‘65' addition ‘of an acetylated vegetable oil, such as acetylated castoror oilve oil, ‘may be employed ad conditioningvliquid or, in other words, the limit of viscosity of the mineral oil is set by the~over-. all viscosity of the conditioning liquid which dried ‘ on the ?bers gives desirable textile character-_ vantageously. . These-agents although having sev eral functions are‘ called, for the purpose of sim- _ ' plifying’the description of the ‘invention, spread " istics thereto. ' This over-all viscosity may be‘ on _70 ing and penetrating agents. _ ,_ , " the order of 80 to 200 seconds and preferably 4 about 150 seconds. ‘Optimum results are obtained , '“theremay be substituted otherjhydroxylated using a white mineral oil having a paraiilnic base amines such as_'monoethanolamine, diethanol i . and a viscosity of 50seconds. ' ‘In. place of all or a partof the'triethanolamine - ,llamine, viliethylamino ethanol,‘ .ethyl ldiethanol- ‘ The ‘fatty acid employed in'the ‘?rst reaction '75 amine, amethyl-zv-amino'propanol, etc. " 5 The proportions of the several ingredients may reacting a mixture comprising a mineral oil, a . be varied to some degree, depending somewhat on the use to which the treated ?bers are to be put‘ and the properties which it is desired to em- . phas'ize. Thus; where it is desired to increase the spreading, and wetting properties the amount of vegetable oil, ahigher fatty acid and fuming sul phuric acidat a temperature no greater than about 20° C. whereby sulphonation of at least part of the fatty acid and vegetable oil occurs and then adding diamyl phenol and an amount of alkali-metal hydroxide and an alkylolamine diamyl phenol may be increased from 5 parts to to‘ neutralize all of the sulfuric acid and the 10 or more parts. Also the amount of mineral oil may be varied from 20 parts to 35 parts depending a major portion of the higher fatty acid. on the lubricity desired. Also the amount of 10 _4. Process for the preparation of a conditioning ’ alkali and alkylolamines may be varied. In this liquid for textile materials whicncomprises re acting a mixture comprising, a mineral oil, a, respect we have found that the preferred condi vegetable oil, a higher-fatty acid and fuming sul tioning liquid should be one that a 2% emulsion phuric acid at a temperature no greater than of same in water has ‘a pH of from 6.6 to '7. The conditioning liquid obtained in accordance 15 about 20° C. whereby sulphonation of at least with our invention may be applied to ?bers and ?laments in the concentrated form or it may be applied as an emulsion, or dissolved or suspended in a carrier. The amount of conditioning liquid part of the fatty acid and vegetable oil occurs and then adding an acetylated castor oil and an amount applied may vary from 1 to 10 or more per cent 20 based on the weight of the untreated ?bers. The ' ning yarns and ?laments by wicks, rollers or other furnishing devices. However, it may also be ap plied to ?bers by dipping bales ‘thereof in a bath C. whereby sulphonation of at least part of ‘the fatty acid and vegetable oil occurs and then adding a spreading and penetrating agent and . -'I'he term “sulfonation" as used in the appended claims designates not only the phenomenon of sulfonation proper (that is the formation of prod ucts wherein sulfur atoms are linked directly to carbon atoms) but also sulfati'on (thatis the for an amount of alkali-metal hydroxide and an‘ so 6. Process for the preparation of a condition- ‘ linked to oxygen atoms that are in turn linked to It is to be understood that the foregoing de tailed description is given merely by way-of illus alkylolamine to neutralize all of the sulfuric acid and the major portion of the higher fatty acid. ing liquid for textile materials which comprises mation of products wherein the sulfur atoms are ' ' carbon atoms). hydroxide‘ and , an ‘acid at a temperature no greater than about 20° of the conditioning liquid or by. spraying the same _ alkali-metal ,5. Process for the preparation of a condition ing liquid for textile materials which comprises reacting a mixture comprising a mineral oil, a vegetable .oil, oleic acid and fuming sulphuric conditioning liquid is preferably applied to run-4 with a mistof some. of alkylolamine to neutralize all of thesulfuric acid and the major portion of the higher fatty acid. reacting a mixture comprising a mineral oil, a 35 vegetable oil, oleic acid and fuming sulphuric acid ‘ at a temperature no greater than about 20° C. whereby sulphonation of- at least'part of the fatty tration and that many variations maybe made acid and vegetable oil occurs and then adding therein without departing from the spirit of our diamyl phenol and an amount of alkali-metal invention. 40 hydroxide and an alkylolamine to neutralize all Having described our invention, what we desire of the sulfuric acid and the major portion of the higher fatty acid. " ’ ' to secure by Letters Patent is: 7. Process for the preparation of a condition .1.,Process for the preparation of a‘ condition ing liquid for textile materials which comprises ing liquid for textile materials which comprises reacting a mixture comprising a mineral oil, a‘ 45. reacting a mixture comprising a mineral oil, a vegetable oil, ‘a higher fatty-acid and fuming vegetable oil, oleic acid and fuming sulphuric acid sulphuric acid at a temperature no greater than at a temperature no greater than about 20° 0. about ‘20° C. whereby sulphonation of at least whereby sulphonation of at least part of the fatty part of the fatty acid and vegetable oil occurs acid and vegetable oil occurs and then adding and then adding a spreading and penetrating 60 an acetylated castor oil and an amount of alkali metal hydroxide and an alkylolamine to neu agent and an amount of alkali-metal hydroxide and an alkylolamine to neutralize all of the sul tralize all of the sulphuric acid and the major furic acid and the major portion of the higher fatty acid. ' portion'of the higher fatty'acid. . ', 8. Process for the preparation of a condition . 2._Process for the preparation of a condition 6,5 ing liquid for, textile materials which comprises ing liquid for textile materials which comprises ' reacting a mixture comprising a mineral oil. raw reacting a mixture comprising a mineral \oil, a peanut oil, oleic acid and fuming sulphuric acid vegetable oil, a higher fatty acid and fuming sul at a temperature no greater than about 20° C. phuric acid at‘ a temperature no greater than whereby sulphonation of at least part of the about 20° 0. whereby sulphonation of at least part 60 fatty acid and vegetable oil occurs- and then adding a spreading and penetrating agent and _ of the fatty acid and vegetable oil occurs and then adding an alkylated phenoland an amount an amount of alkali-metal hydroxide and an of alkali-metal hydroxide and an alkylolamine alkylolamine to neutralize all of the sulphuric acid and the maior portion'of the higher fatty ' to neutralize all of the sulfuric acid and the major portion of the higher fatty acid. a ‘ 8. Process for the preparation of a condition ing liquid for textile materials which comprises 65 acid. * ~ GEORGE W. SEYMOUR.