USRE17894E - of wattwil - Google Patents

Description

. N Drawing. Original No; 1,694,526, dated December 11, 1928, Serial No. 121,736, filed July 10, 1926, and in Reissued Dec. 2, 1930 UNITED STATES IPATENT OFFICE ALBERTBODMER, or WA'ITWIL, SWITZERLAND, nssIeNon To HEBERLEIN' & 00., A. (3., or WATTWIL, SWITZERLAND, AcoRPoRA'rIoN or SWITZERLAND DYEING Germany Ju1y 14, 1925] Application for reissue filed September 14,1929. Serial No. 392,749.

My invention relates to improvements in dyeing and more particularly the main object of the invention is to provide an improved method for. treating cellulosic fibers or fabrics to render the same relatively immune to substantive dyestuifs and also certain novel products which may be produced with the aid thereof. Further and more specific objects, features and advantages will more clearly appear from the detailed. description given below in which referred forms of the invention are fully set orth.

Heretofore certain methods have been proposed for changing the dyeing vegetable or cellulosic fibers by way of acetyla-ting, benzoating or the like, but these meth ods have certain disadvantages. According to the present invention in its preferred form the vegetables or cellulosic fibers or fabric are treated with a phosphorous halogencompound whereby novel and valuable products areobtained. If the material is treated withalcoholic caustic alkali in connection with the treatment with the phosphorous halogen compound the material becomes immune to substantive dyes and has as well an affinity for basic dyestufis. If the caustic is employed in water solution, for example as a water paste in printing, the immunity to substantivedyestuifs is not satisfactory although an increase in the afiinity for basic dyestuffs does occur. In addition topurely inorganic phosphorous halogen compounds such as phos phorous trichloride, phosphorous oxychloride, etc. organically substituted phosphorous halogen compounds such as ethyl-phosphooxy-chloride and other phosphorous compounds such as triphenyl-phosphate may be used with more or less success.

For the purpose of rendering the cellulose fibers immune to substantive dyestufis and increasing their alfinity for basic dyes, cotton yarn is immersed in a solution ofcaustic soda in alcohol, containing 10% of caustic soda by weight, to alkalize the cellulosic fibers thereof in a-manner well understood by those skilled in the art, and after removing the yarn from the solution the excess of solution is squeezed out ofthe same. The yarnthus prepared is then brought into a solution of phosphor properties of ous trichloride in xylol containing 200 grams of phosphorous trichloride per liter of- XyloL. Thus the cotton fibers of the yarn are treated with the phosphorous halogen compound in the presence ofsome. alkali which remains on the yarn from the alk'alizing treatment. When the yarn is thustreated with the phosphorous trichloride solution the reaction takes place after a short time,

with development of heat. The yarn is then thoroughly washed, soaped and dried and it is found that the fibers have lost their aflinity for and are substantially immune to substantive dyestufls while they have acquired a pronounced-capacity for dyeing with basic dyestuffs without previous mordanting.

' The yarn so treated may be woven with ordinary cotton yarn or untreated celtogether i lulosic threads to form a fabric and remains losic threads, and the fabric treated with asubstantive dyestufl' of a different color,

whereupon the threads which have been treat- .ed with the phosphorous compound will remain of a cliiferent color; from those which were untreated with the phosphorous colnpound. The reaction of the phosphorous alogen compound on the cellulose appears to set free halogen acid and the presence of alkali 'on the goods will serve to remove such acid-by neutralizing the same thus preventing its injuring the goods. The'phosphorous I believe combines with the cellulosic material to form a phosphorous cellulose-compound which is relatively resistant and immune to 1 substantive dyestuffs and relatively attractive to basic dyestufis, generally speaking. I

' Instead of treating --the yarn before itis woven into fabric, a woven fabric made of cotton orcellulosic fibres may be first treated with an aqueous caustic alkali solution in the well known way to alkalize the cellulose thereof. and then the excess alkali solution squeezed out and the fabric passed through a solution by weight of phosphorous oxychloride in benzol. Various other hydrocarbon solvents may be used-for producing the solution of the phosphorous compound or compounds. After completion of the reaction the material may be washed and may then be dyed with basic dyestuifs without previous mordanting.

The invention may be applied not only to ordinary cotton fibers and-fabrics but also to artificial silk fibers and fabrics, such as artificial silk made from regenerated cellu-' lose, e. g. hydracellulose such as viscose, cupra ammonia cellulose andcollqdion'silk. Such artificial silk may be treated with the phos phorous halogen compounds or the like and alcoholicv caustic alkali, and it will. then be found to have become substantially immune to substantive dyestuffs and to have acquired an afiinity and attractionfor basicdyestuifs.

. If these silks are treated with water solutions of caustic alkali or with water paste containing caustic alkali, they acquire an a ffinity for basic dyes, but they donot acquire a satisfactory immunity to substantive dyes. Therefore, by cellulosic fibers, and fabrics or material Iintend to include all such artificial silk as Well as other cellulosic material. With artificial silks which consist of cellulose esters-or cellulose ethers, e..g. acetate silk, and which -repel most, of the common dyestuffs, theiraflinity for basic dyestuffs becomes marked vwhen treated in -the manner described.

' The treatment with alkali may be applied after instead of before the treatment with the phosphorous compound. Thus it is not necessary that the cellulosic material be treat-' ed with the phosphorous compound in the presenceof the alkali and the cellulosic ma:

. terial may be washed With Water or with an inertsolvent and dried, if desired, between the two treatments. .Also in many cases the I alkali treatment'may be omitted-altogether 'and'substantially the same results obtained,

.as obtained by theuse xof water solution of bodied in the fiber or added to the solution to neutralize the acid liberated in the reaccaustic alkali. v v

, The cellulosic material may be directly treated withthe phosphorous compound, and without any treatment with alkali, and there may, according to the concentration, be emtion, acid'bi'nding'or removing bodies such as sodlum bicarbonate, 'calcium'carbonate and the like. This method is also not'only applicable-to the natural cellulose fibers but also to the'artificial silks and the like, and

ItIGSUItS in increasingtheir afiinity for basic White and colored or two colored efi'ect's j may also be produced'in avfabric by the local application or treatment to render certain 'by Lett'ers Patent, is:

pound solution either with previous alkaliza tion or subsequent alkalization or without the same. If the alkali treatment is a treatfmenfl with alcoholic caustic alkali immunity to substantive dyes and increased affinity for basic dyes result.-" If awat-er solution of caustic alkali is employed or if the caustic alkali is omitted, a satisfactory immunity to "substantive dyes is not obtained, but an increased. affinity for *basic dyestufis occurs.

'If desired 'thealkalization of the fiber may beaccomplished by printing a. thickened alkali directly on the fabric in accordance with a predetermined design and then the local chemical changes brought about by immersion of'th'e fabric in the solution of phosphorous compound and if desired a 'dyestuff may be'printed on the fabric at the same time with the thickened alkali, or a thickenedsolution of "the phosphorous compound may be printed on the fabric according to a predetermined design. v

Thus the process may be used for the pro.- duction of new materials of natural vegetable or artificial fibers, withpatternefiects by the local application of the phosphorous compound by printing or applying the same in accordance with any predetermined design, whereupon the portions s0 acted upon by'the phosphorous compound will be particularly resistant to substantive dyestuffs and relatively attractive to basic dyestuffs or simply have increased aifinit for basic dyes alone, and upon subsequent dyeing, clouded or other variegatedefiects may be produced. While a phosphorous chlorine compound is preferred, nevertheless other halogens and other, compounds of phos phorus may be used with more or less success.

While I have described my'improvements in-great d'et'ail and with respect to preferred forms thereof, I do not desire to' be limited to such details or forms since many modifications and changes may be made and the invention embodied. in widely different forms without departing from the spirit and scope ,thereof in its broader aspects. Hence I desire to cover all modifications'and forms coming within the language or scope of-any one or more of the appended claims.

' What I claim as new and desire to secure 1. Method of modifying the dying properties of cellulosic fibers whichrco nsists intreating the fibe'rs'with alcoholic caustic alkali and acting'on' the same with; a com' pound of'the class consisting of phosphorous halogen compound and triphenyl-phosphate relatively attractive to basic dyestuffs.

2. Method of modifying the dying proper-- ties of. cellulosic fibers which consistsin treating the fibers with alcoholic caustic alkali and acting on the same with a phosphorous halogen compound capable of making the cellulosic fibers relatively immune to substantive dyestuffs and relatively at tractive to basic dyestuffs without previous mordanting.

3. Method of modifying the 'dyingproperties of cellulosic fibers which consists in treating the fibers with alcoholic caustic alkali and treating the fibers with a phosphorous halogen compound sufficiently to make ,the fibers relatively immune to substantive dyestuffs and relatively attractive to basic dyestufis and removing the halogen acid formed. 4. A cellulosic fiber containing phosphorus capable of substantially resisting substantive dyestuftsfand attracting basic dyestuffs, so that when the fiber is treated with substantive dyestuffs, it remains substantially uncolored thereby.

5. Method of modifying the dyeing prop erties of cellulosic fibers which consists in treating the same with a phosphorous halo-' gencompound in the presence of an alcoholic solution of a caustic alkali material.

6. Method of making fabrics with variegated colored eifects which. consists in forming the fabric with cellulosic threads, some only of which have been treated with a compound of the class consisting of phosphorous halogen compounds and ,triphenyl-phosphate to render them relatively immune to substantive dyestuffs whereby when the fabric is treated with substantive dyestuffs the so treated threads remain substantially unaffected. v

7. Method of making fabrics with variegated colored effects which consists in formmg the fabric with cellulosic threads, some only of'which have been first colored and then treated with a compound of the class consisting of phosphorous halogen compounds and triphenyl-phosphate to render them relatively immune to substantive dyestuffs whereby when the fabric is treated with substantive dyestuffs theso treated threads remain substantially unaffected.

8. In the method of producing colored de signs on fabrics which step consists in .tak-

- ing a fabric of cellulosic threads and treating the same according to a predetermined desig with a compound of the class consisting or phosphorous halogen compounds and triphenyl-phosph'ate, and an alcoholic caustic alkali solution, whereb the cellulosic fiber at the places so treated is rendered relatively immune to substantive dyestuffs and relatively attractive to basic dyestuffs.

9. A fabric of cellulosic threads having certain portions thereof treated according to a predetermined design with a phosphorous use of a mordant whereby when the fabric is treated with substantive dyestuffs the so treated threads remain substantially unaffected.

10. Threads of cellulosic material containing phosphorous whereby the threads are rendered substantially immune-to substantive dyestuffs, so that when the threads are treated with substantive dyestuffs they remain substantially uncolored thereby.

11. Method of producing variegated designs on fabrics of cellulosic material which consists in printinga paste reverse, material on the fabric according to a predetermined design and exposing the fabric to the action of a phosphorous halogen compound locally according to said design.

12. Method of modifying the dyeing properties of cellulosic fibers which consists in treating the fibers with a compound of the class consisting of phosphorous halogen compounds and triphenyl-phosphate capableof making the cellulosic fibers substantially immune to substantive dyestuffs and.

relatively attractive to basic dyestuffs and. also treating withan acid binding material,

so that when the fibers are treated with sub-,

stantive dyestuifsthey remain substantially uncolored thereby. v

13. Method of modifyingthe dyeing properties of cellulosic fibers which comprises treating the cellulosic fibers with alcoholic car sti'c alkali, introducing the material thus treated into a solution of a compound of the class consisting of phosphorous halogen compounds and triphenyl-phosphate and allowing reaction between said compound and the material to occur whereby the material to occurwhereby the material is rendered practically immune to substantive dyestuffs and has an increased affinity for basic dye-.

stuffs.

14. A method of producing variegated designs on a fabric of cellulosic material which comprises printing a .reserve on the fabric according to a predetermined design, treating the fabric with alcoholic caustic alkali solution, treating the fabric with a solution of a compound of the class consisting of phosphoroushalogen compounds and triphenyl-phosphate whereby the unprinted portions of the fabric are rendered immune to substantive dyestuffs and have an increased affinity for basic dyestuffs, removing the reserve and dyeing the fabric to reproduce the design printed thereon.

15. A cellulosic fiber in which at least some of the cellulose has been subjected to caustic alkali deposited thereonfrom-an alcoholic solution and'to a phosphorous halogen compoundiand which is relatively more resistant to substantive dyestuffs, and more attractive to basic' dyestuffs.

16. A fabric of-cellulosi'c' threads having certain portions thereof treated according to a predetermined design with a ph0sph0r-.. ous halogen compound in the presence of a caustic alkali deposited thereon from an alcoholic solution of said alkali rendering the fiber of such treated portions relatively resistant to substantive dyestuffs and relativelyattractive to basic dyestuffs.

15 17. Artificial silk fiber of regenerated cellulose in which at least some of the fiber has been subjected to a caustic alkali material deposited thereon from an alcoholic solution and treated with a phosphoroushalogen compound, the fiber being relatively immune to substantive dyestuffs and relatively attractive to basic dyestuffs.

In testimony whereof, I have signed 'my name to'this specification; v

a ALBERT BODMER.