US1914059A - Textile material and method of dyeing the same - Google Patents

Description

Patented June 13, 1933 UNITED STATES PATENT OFFICE cmnmrcn 28. WHITE,

or MON'I'CLAIR, NEW JERSEY, ASSIGNOR T vIvATnx PROOESSES, II IG., LOIDI, NEW JERSEY, A CORZPORAIION OF NEW JERSEY TEXTILE Merriam AND mnTHoD or DYEIN'G THE sum 't. v No Drawing. Driginal application filed April 16, 1924, Serial No. 706,884. Divided and this application filed November 7, 1927. Serial No. 231,7?2."

. The invention which forms the subject of the present application. (a division of my copending application Serial No. 706,884, filed April 16, 1924, now Patent No.- 1,648,433,

issued November 8, 1927) relates to waterduce a dyed textile material which will be highly resistant or repellent to fungus growth and bacterial attack, and which will be more repellent to water and less subject to shrinkage than materials dyed by the commonly used processes.

- Another important obj ect of the invention is to produce or deposit within or upon the fibres of the textile material, prior to. or simultaneously with the d eing operation, insoluble compounds or substances of a basic character which shall be capable of absorbing or neutralizing acidic substances or acid radicals which may develop from the molecular dissociation (under the influence of light, heat, moisture, or radiant energy) of the color compounds or the color lakes. with which the textile material is dyed; to produce or deposit upon or within the fibresof the textile material, compounds or substances which have strong alfinity for the acidic ions that may be liberated through the action of the agencies noted above and which, once united with these acidic ions, hold them tightly and are not readily dissociated therefrom, thereby preserving the fibres from the tendering which inevitably results when such ions are free to unite with or attack the cellulose of the fibre.

A still further important object of the in:

vention is to provide a method of produc- One obupon or within the ing or depositing compound, within or upon the fibres, prior to or simultaneously with the dyeing opera-' 1 Another important object of the invention" is to incorporate organic dyestufi's or dyeing media within the bodyof mineral dye or water or fungus-repellent compounds or substances referred to above, to the end that such dyestuffs, coloring media or color lakes thus enclosed shall be more or less protected from the influence of atmospheric agencies,

heat, light, and moisture, and will thereby be rendered faster to light and also more resistant to fading in washing.

The objects above mentioned are achieved in the present invention by the use, in. or upon the fibres of the suitable metal compounds, preferably .of metals of the rare earth group and, in some cases, by the use of chromium, aluminum,

magnesium, and titanium. Among the rare textile material, of

the protecting compound I or substance, or the fungus or water repellent earth metals usable are cerium, neodymium,

praseodymium, lanthanum, yttrium and erbium. Thorium may be used also, and in using the term rare earth metals hereinafter I mean to include thorium therein. These metals possess the important property of being precipitated as hydroxids when their compounds are acted upon by alkaline sulfids. these hydroxidswhen formed or precipitated fibres of textile material impart marked water-', mildew-, and bac teria repellent properties, and, in addition,

many of the hydroxids have strong and defi-Y chromium hynite colors. For example, droxid 1s graylsh green, cerium h droxid is Many ofyellowish white, neodymium hy roxid has a reddish tone, pras'eodymium hydroxid has een and erbium hydroxid a purple-red color. Thehydroxids of these elements are. i

all strongly basic, as are also their carbonates,

and are in a high degreecapahle of neutraliz ing acids. While alkaline sulfids precipitate hydroxids of the above mentioned metals, on

, preclpitated as sulfids, some and chromium.

' upon the fibre,

rately or combined'together.

the other hand copper, nickel, cobalt, antimony, iron, cadmium, and manganese are of which have high tinctorial value. Thus antimony sulfid is orange in color, cadmium sulfid is yellow, and copper sulfid blackish brown. Such colors are, in general, more decided than those of the corresponding hydroxids, and when mixed in varying proportions are capable of producing varied tones and shades of a wholly mineral character. But nearly all the sulfids are capable of more or less easy oxidation to sulfates, which latter, because of their solubility, may be readily washed out, or because of their tendency to dissociate may libcrate acidic ions which react upon and hy-' drolyze the cellulose of the fibres u on which they may have been precipitate thereby tendering the fibres and eventuall rendering the -fabr1c1 useless. It is there ore of the highest importance to have present, in or basic elements or compounds, as forexample an insoluble hydroxid, which will neutralize or destroy acidic ions as rapidly as'the latter may be formed and set free.

The presence of the insoluble rare earth compound (usually an hydroxid) renders the textile material repellent to water and to fungus and bacterial growth, as explained in my copending application Serial No. 639,219 filedMay 15, 1923.

Some of the sulfids referred to above (for example antimony, fids) are when dry considerably resistant to oxidation, and especially so when they are occluded or embedded in a mass of basic ma terial, or are protected from atmospheric agencies by water repellent coatings or nonabsorbent and repellent compounds such as copper, antimony, nickel, cobalt, and iron, chemical reaction or-p'rocess that produces hydroxidsfof the rare earth metals and hydroxids of aluminum, titanium, magnesium sulting color is a blend of wholly mineral origin, possessing the intrinsic 'fastness of mineral colors to light. Many of the shades thus produced are unique, and the colors may "be further. varied b various admixtures of tin, antimony, or ca ium sulfids, usedsepa- The destructive eifect of sulfuric acid ions can also be avoided, or measurably and substantially diminished,.by the use of insoluble diflicultlysolublecompounds of the alkali earth metals, as calcium, strontium and barium, or the related magnesium, among which compounds may be mentioned hydroxids, carbonates, tannates, and insolubleorganic compounds in general. Such compounds have a very strong afinity for the sulfuric acid ion,

cadmium and co per sulas sulfids in the same treatment to effect such after-treatments almost invariably have an In many such cases the red and once united therewith release are very diflicult of dissociation therefrom. With the exception of magnesium, they have the advantage that the compounds formed with sulfuric acid are very insoluble, barium sulfate being one of the most insoluble com pounds known.

n The scope and utility of the'invention are not limited to the production and application of the so-called mineral dyes, but on the contrary the invention admits of a wide extension and application to the field of sub stantive and adjective dyeing in which organic coloring media are also used. This is strikingly illustrated in the field of direct dyes, and especially the so-called sulfur dyes,

where the coloring medium is dissolved in and applied with a strong sodium sulfid solution or other alkaline sulfid solution. If the sulfur dye be applied in an alkaline sulfid bath to a fabric already impregnated with a and substances already noted, the sodium sulfid or other alkaline sulfid will decompose the impregnating salt, forming an insoluble hydroxid, which hydroxid will, as it is formed, be thoroughly permeated by the color medium, occluding it in a colloidal or gelatinous mass which when dry strongly protects it from light. or radiant energy in general and from atmospheric agencies. The action is not essentially different when used with certain mordant dyes, such as for to; pro uce or deposit; upon or withinthe the metalllc soaps and hydroxlds of the class fi alluded to, and I have found it practicable to precipitate cadmium,

bres, compounds which render the textile material strongly repellent to water and milunnecessary, in most cases, any drastic afterpurposes. Such appreciable, and in some cases a ver.

am'aging effect upon the colors and of the dyed material.

great shaded duction dation or breakin down of thecolor molecule (as in sulfid-dyed material, for example) it is not always necessary,.in my invention, that tain or carryncompounds of a strongly basic character. other cases the" requ rements of fast color non-tendering of the fibres, etc.,

are met by the presence of aninsoluble compound which occludes or envelops the dolor dew and to bacterial attack, thereby making Except where there is danger of the proof acid radicals or ionsthrough oxi-' soluble salt of one or more of the elements the fibres of the textile material also conrial advantageous wate'r-, bacteria-' and fungus-repellent properties but also furnish the necessary mordant for mordant dyes. These insoluble compounds are formed and precipitated by the action of alkaline fluorids, phosphates, borates, etc., and in many cases the precipitating solutions can be added directly to the dye bath, so that when textile material previously impregnated with soluble rare earth metal compounds is passed through the,

baththe latter compounds will be converted into insoluble compounds simultaneously with, and as a part of, the actual dyeing opmy process as ble salt of a metal or element capable of being insolubilized as hydroxid by reaction withalkaline hydroxide, carbonate or sulfide. For the purpose of coloring the textile material the impregnating solution also contains a salt of a metal capable of being precipitate as a metallic sulfide of suitable color or tint by reaction with an alkaline sulfide. Among the salts capable of being converted into insoluble hydroxides I may mention chloride, acetates, and nitrates of the rare earth elements; and as examples of salts capable of being converted into insolublesulfides which.

also are capablev of dyeing the textile material, I may mention any salt (preferably sulfur-free) of iron, copper, nickel, cobalt, cadmium, antimony, and bismuth. The following are excellent formulas-for impregnating baths: w

' Percent Water- 50 @opper acetate; .25. liars-earth metal acetate or acetates 25 (b) 1.

Waten 50 Copper acetate 16 Chromium acetate 18 Rare earth acetate or acetates 16 Both the above solutions when treated with sodium sulfide or other alkaline sulfide as a precipitant .yield a mineral dye of an olive drab color, the shade being darker with a greater amount of copper and lighter with a greater amount of chromium or rare earth,

rial passes into the dye bath the alkaline sulbonate as the precipitating I precipitants,

bath I sometimes rial) and hence a large variety of shades can be obtained by proper proportibnin of these two ingredients. he alkalinesul de treatment also precipitatesupon or in'the fibres of the textile material the rare earth metal in the form of insoluble hydroxide, which, being strongly basic, serves to neutralize any acid ions that may be set free by subsequent dissociation of the copper or chromium sulfide in the manner previously-alluded to, thereby protectin the fibres from injury by the ten-. dering 'e ect which such ions or radicals would otherwise have. The impregnation can be effected at ordinary temperatures, by immersing the textile material in the selected solution, Ion enough (usually-momentarily) for thoroug impregnation. The material can then be dried, with or without the use of heat, and treated with the selected precipitating bath, which may be a solution of sodium sulfide of, say, from Sto 20 per cent strength, at practically any temperature up to boiling, according to the nature of the fibre; cotton, for exam le, permitting a high temperature, while sil requires a relatively low temperature. 7

Many dyestuffs are, or can be, applied in a strongly alkaline bath. Notable among these are the direct dyes known as sulfur dyes, which are soluble only in'a strong solution 0 an alkaline sulfide; and dyes of the mordant I type, and their prototypes,

the madder dyes.

In using a dye of these classes, I first impregd nate the textile material with any soluble salt (preferably an acetate) of a metal which can be recipitated in insoluble form by alkaline sul des, hydrates or carbonates. For this purpose I pre though I can use salts of other metals,-as aluminum,'magnesium, chromium and titanium, After impregnation the. textile material is dried, and is then ready for the alkaline dyebath. In the case of sulfur dyes, as the matefide therein, usually sodium sulfide, reacts with the soluble salt with which the material has been impregnated andconverts it into the insoluble hydroxid pre'ci itates, and at the same time carries into t e ap arently colloidal precipitate on the fibre t e color base of the dye-bath. In the case of alizarin, madder and other dyes requiring alkaline baths, I prefer to use caustic soda or sodium carhowever, should not be used for textile material impregnated with an aluminum com und.

f as

fer salts of the rare earths medium. These After yeing cotton with an alkaline dye treat it with a soap solution, for the urpose of brightening andfurther fastenmg the color. In such case the soap reacts (afterwashing the mate- Y with the metallic compound on the fibre, forming an insoluble soap which rendersthe fabric repellent to water.

Preferably the 130 gus growth; as for example the rare earth dyeing, and in the subsequent dyeing of the metals, especially thorium, cerium, didymium and lanthanum.

In the case of dyes which cannot be applied from an alkaline but require a neutral or an acid bath, I first impregnate the textile material with'a rare earth element, notably thorium, cerium, lanthanum or didymium, in the form of a compound (as for example an acetate) from which a compound can be precipitated which is insoluble or but slightly soluble in dilute acids such as are used in acid impregnated material I include as a precipitant in the acid dye-bath a fluorid, phosphate,

benzoate, salicylate, or other suitable salt pf an alkali metal or alkaline earth metal Their as a result of the reaction betwcenthe salt or salts just named and the rare earth salt the latter is converted into an insoluble compound-a fluorid, phosphate, etc, as the case may be, with the same effect'as is produced in the case of dyes requiring alkaline baths as described above.

Cotton exhibits no basic properties, and hence cannot be dyed by means of certain acid colors which are available for animal fibres, and the choice of dyestuffs for use with cotton is therefore much more limited than in the case of animal fibres, for example wool and silk, which latter occupies an intermediate position between cotton and wool. In general, cotton dyeing is confined to the following classes of dyestuffs:

1. Basic colors. (salts of organic bases). the dyeing power of which lies wholly in the basic portion of the salt and requires an acid or an acid salt to develop the color. These dyes require a mordant.

2. Direct colors, the characteristic feature of which is that they dye cotton directly, without mordanting. These colors fall into two distinct groups, which are known as direct cotton colors and sulfid colors. They are mostly alkali salts of sulfonated tetrazo bases, formed by diazotizing benzidine or diamido-stilbene, and then uniting the products with amines or phenols. Such dyes are thus already alkalin or at least are of the nature of alkaline salts and are not incompatible with other alkaline bases.

As an application of my invention to the dyeing of cotton with direct dyes the following example may be given:

The cotton is first impregnated with a rare earth salt or salts, as for example cerium acetate. The impregnating solution may also contain, for example, a soluble chromium salt,

' say chromium acetate, for the purpose of increasing fastness to light and washing. The impregnated cotton is preferably dried, after iterates may be of the composition:

l/vater 1 gallon Dye (direct color or colors) 5 oz. Sodium fiuorid 6 oz. Sodium carbonate oz.

The amount of dyestufi is variable, especially since the absorption by the fabric is in inverse proportion to the amount of dye liquor in the dye bath. The sodium carbonate can be replaced by the same amount of soap. When the impregnated material is passed into the dyeing and precipitating bath the sodium fluoride converts the rare earth metal salt on the fibres into an insoluble fiuoride; and carries into the fibre, and into the fluoride precipitated thereon, a certain portion of the dyestuif. The sodium fluoride may be replaced by any other salt capable of producing a like effect, as for example sodium, potassium or ammonium phosphate, benzoate, salicylate, silicate, hydroxide when not incompatible withthe dyest uif), carbonate, cyanid, etc.

The sulfur colors canb'e applied only in a strongly alkaline bath, a circumstance that limits them, practically, to cotton, linen, jute, and other vegetable fibres. The usual sol-= vent for the dye is a strong solution of sodium sulfide. In applying my inventionwith this class the textile material is first impregnated with soluble salt of one or more of the metals heretofore mentioned fora like purpose. Preferably, but not necessarily, the salt'(is one of an acid which has no tendering effect when dried, as for example an organic acid, say acetic or lactic. The impregnated fabric, preferably dried, is passed into the sulfur dye bath, thereby converting the soluble metallic salts of the impregnated fibre into insoluble compounds, as for example hydroxides. At the same time the color medium dissolved in the bath is released by the decomposition of the sulfide and appears intimately incorporated with the amorphous colloidal or quasi-colloidal hydroxide precipitated on and within the fibre. If desired, the conver sion of the soluble salt into an insoluble compound can be effected before dyeing, in which case the yeing operation may proceed exactly as with an unimpregnated fabric, but the ancorporation of the dye is not likely to be 45 to water or mildew or both.

' cent.

' the textile material is,-as

' at the same time,

- der consideration have the power of comb usable for the purpose,

Mordantcolors possess the property of combining with metallic oxides and other I compounds, the combination, in general producing the tint, which varies with the particular oxide or compound employed. Others of this class possess, within themselves, the property of dyeing, irrespective of their ability to formcolor lakes with metallic oxides. The chemical explanation of this class characteristic is found in the fact that the members of the class all contain hydroxyl groups while others contain both hydroxyl and car boxyl groups. It is not, however, necessary that the metallic base exist in the textile material in the form of oxide or hydroxide, inasmuch as the color media of the class un- 1ning with oleates, tannates, silicates, etc., to form the lake on or within the fibre. In applying my invention with mordant colors in the case of the dyes already described, first impregnated with the desired metallic salt, preferably an acetate, and is then dried or tightly squeezed between rollers to eliminate at least the major portion of the moisture. The dried or squeezed fabric is next passed through the dye bath, which latter contains in addition to the color medium or media a chemical agent capable of precipitating and rendering insoluble the metallic salt or salts with which the material. was impregnated. Among the precipitating or insolubilizing agents I may mention hydrates and carbonates of the alkali metals, alkaline-silicates, oleates, tannates, borates, oxalates, fluorids, phosphates, etc. In this way the necessary mordanting, that is, the formation of the color lake, is efiecte'd, and

as in the other cases hereinbefore described, a substance is introduced into the textile material, in or upon the fibres thereof, which renders the latter repellent Developed colors include a group of colors which are developed upon the fibres by the successive ap lication of their constituent parts, one 0 which is usually of an acid Y character. In applying my invention with a dye of this class the metallic compound which is'precipitated upon or'in the fibre must be of such nature that it will not readily dissolve in dilute acids. Such compounds are well illustrated by the phosphates of the rare earth metals (includinghypophosand the fluorids of the same group, as well assilicates and, to a lesser extent, the dried hydroxides. The latter are, as arule, very soluble in the freshly precipitated wet state, but many, as for instance thorium and cerium hydroxides, are rendered relatively insoluble'by drying. Zirconium hydroxide precipitated from a hot with neutral or alkaline dye-baths.

solution is almost insoluble 'in dilute acid I solutions, although the hydroxide formed by cold precipitation is easily soluble in such solutions. The acids used to develop the colors in the dyeing operation are'quite dilute and hence there is little or no danger of dissolving the metallic compound with which the textile material'has been im regnated;

The most striking example o'fthis sub-group .is the well known paranitranilin red.

(b) Developed direct aol'ora-These "are developed from primuline or from direct colors containing free amido compounds by passing the dyed material into a solution of an amine or a henol. (0) Benzo-mtrol colora-With these the material is dyed by means of certain direct colors which are developed by assing the textile material into a solution 0 diazo compounds, as for instance .diazotized paranitranilin. The process is similar tothe development of the insoluble azocolors. I

In dyeing operations in which the. actual dyeing'is conducted in an alkaline bath, the

fixing or precipitating agent'required for insolubilizing the water-repellent or mildewrepellent compound or compounds may be in general directly incorporated with the dyebath and the insolubilizing operation is then carried on simultaneously with the dyeing of the textile material. When the dye-bath is of a neutral character the insolubilizing can also be effected simultaneously with the dyeing, but for this purpose a neutral precipitant fluoride, phosphate, oleate, silicate, etc. With the exception of the developed dyes, such as the insoluble azo 'dyes and their" related groups, nearly all cotton dyeing is efiected With silk and wool the case is different, these materials being usually dyed in an acid bath, and in this case the fixing or precipitating agent for insolubilizing the water-repellent or mildew-repellent compound must be such that the compound so produced shall be relatively insoluble acid dye bath. the rare earth in general confer mildew-repellency as ,well as affording a basis for building up water- These conditions are met by repellency. Typical examples of precipitated compounds (of rare earth elements) which are relatively insoluble in-dilute acids oleates, stannates and tannates,

in the dilute acidity of the Y and in somev element compounds, which is not limited to the (deposited upon thorough, approximating in fact the thorough penetration so characteristic of yarn or stock dyeing, and the result is therefore relatively faster to light and washing. Nevertheless, where the simultaneous method is not practicable on account of the incompatibility of the insolubilizing media and the.

dye-bath, the fabric or other textile material can be made water-repellent or mildewor bacteria-resistant before dyeing and may then be dyed by any of the well known methods. It is important, however,-where the dyeing is to be carried out with an acid bath, to take precautions that the compound or within the fibres) by which the resistant or repellent properties are imparted to the material, shall be of such nature that it is relatively insoluble indilute acids. Although the simultaneous method is to be preferred, the subsequent dyeing method is equally efiicacious in preventing the staggering of .colors which is almost inevitable in former processes in which an already dyed material or fabric is subjected to treatment for the purpose of rendering it repellent to water or resistant to bacterial attack.

I do not claim herein I ble salts or other componds as media for pro tecting textile material from tenderingproducts resulting from the action of atmospheric or other agencies on the coloring agent; 'nor do I claim for such pounds of elements (as for example calcium, strontium, barium, and zinc) which are capable of forming sulfids in the wet way. Such compounds in solution react to form sulfids when the textile material is treated with alkaline sulfid, and the sulfide so produced in the textile material not only have no protective effect but may even in some cases be themselves a source of damage to the material. In the term compound of an alkali metal, and the like, in the appended claims, I include ammonium compounds as equivalents.

It is to be understood that the invention specific details herein described but can be de ned by the following claims.

I claim- 1. The method of coloring textile mate-' the use of Water-solu;

purposes the use of com-" carried out in other wags without departure from its spirit as to those imparted terial attack, or tending products, comprising impregnating the textile material with a soluble compound of a metal selected from the class consisting of thorium and the cerite and ytterite earth metals, capable of conversion into a compound having the said repellent property and treating the impregnated textile material with a solution of a compound of an alkali metal adapted to effect such conversion and containing a dyestufi", whereby the compound of the selected metal is converted intoan insoluble compound having the said repellent property and the dyestuff is deposited in or upon the textile material. i

2. The method of coloring textile material with organic dyestufl's and renderingv the same repellent to fungus growths, bace terial attack, or tendering products, comprising impregnating the textile material with a soluble compound of a-metal selected from the class consisting of thorium and the cerite and ytterite earth metals, capable of conversion into a compound having the saidrepellent property, and treating the impregnated textile material with a solution containing a dyestufi' compound which will react with the said metal compound to precipitate an insoluble compound of the metal, whereby the dyestufi and a soluble alkali metal is deposited in or upon thetextile material I and the converted into a condition of insolubility in water, in the said solution, and in subsequent solutionsused for treating the said dyestuff.

The-.method of coloring textile material and rendering the same repellent to fungus growths, bacterial attack or tendering' products, comprlsingimpregnating the textile material with a soluble salt of a metal selected from the class consisting of the rare earth metals, capable of conversion into a compound having the said repellent property, and treating the impregnated textile material with a solution of a compound of an alkali metal capable of efiecting said conversion, said solution containing an organic dyestufi', whereby the selected metal is converted into a compound insoluble in the said solution or in subsequent solutions which could be used to treat the said dyestufi and the dyestuff is deposited in or upon the said textile material.

4. The method of rial and rendering the same repellent to fungus growths, bacterial attack, or tendering products, comprising impregnating the textile material pound of a metal selected from the class consisting of the rare earth metals and a commg of chromium, aluminum, magnesium and titanium, capable of conversion into a compound having protective properties similar by compounds of thGc'fiI'SfG compound of the selected metal is 4 with a solution of a cominto a condition of insolubility in water and v in the second solution and the dyestufi'is deposited in or upon 'the textile material.

5. The method of coloring textile material and rendering the same repellent to fungus growths, bacterial attack and tendering products, comprising impregnating the textile material with a soluble salt of thorium, and by treating the impregnated material with a solution containing an'organic dyestufi" and a suitable compound of an al-' kali metal converting the thorium salt into a compound insoluble in the treating solutior. or in subsequent solutions which could be used to the dyestufi in or upon the textile material.

6. A. method as described in claim 5, in which the thorium salt is acetate.

7. A method as described in claim 5, in which the thorium salt is acetate and the alkali solution is a solution of sodiumsulfid,

whereby the thorium acetate is converted into thorium hydroxid.

8. The method of coloring textile material and rendering the same repellent to subsecomprising colorquent tendering products, ing the textile material with a dyestufl in a suitable vehicle and depositing in the textile material a substance serving to protect the textile material fromsaid tendering products, said substance consisting of a compound of an element selected from the class consisting of chromium, aluminum, magnesium, ti-

tanium, and the rare earth metals, incapable of forming a sulfid in the wet way, said compound being insoluble in water and in the vehicle by which the said dyestuif is applied.

9. The method of coloring textile material and rendering the same repellent to subsequent tendering products, comprising simultaneously coloring the textile material with a dyestufi in a suitable vehicle and depositing in the textile material a substance serving to.

protect the textile material from said tendermg products, said substanceconsisting of a compound of an element selected from the class consisting of chromium, aluminum,

-. magnesium,

' ing hydroxide of a metal titanium, and the rare earth metals, incapable of forming a sulfid in the wet way, said compound being insoluble in water and in the vehicle by which the said dyestuii is applied. i

1'0. Textile material organic dyestufi and containing a neutralizselected from the class consisting of thorium and the cerite and ytterite earth metals, m at least organic dyestufi' organic dyestufi treat the dyestuti and depositing.

.- pound ofan element selecte colored withan insoluble in water'and one solution by which the dyestufi could be applied to textile material.

11. Textile material-colored with a sulfur dyestufi and containing a protective neutralizing compound of an element incapable of forming a sulfid in the wet way, said compound being insoluble in water and in at least one solution by which the dyestufi could be applied to textile material.

12. Textile material colored with a sulfur dyestuii and containing a neutralizing hydroxid of a rare earth metal, insoluble in at least one solution by which the dyestufi could be applied to textile material.

13. Textile material colored with an and containing thorium hydroxid. v

14. Textile material colored with an and containing a protective compound of a rare earth metal, said compound being insoluble in water and in at least one solution by which the dyestufl could be applied to textile material.

15. Textile material colored with a sulfur.

rotective comfrom-the class consisting of chromium, aluminum, magnesium, titanium, and the rare earth metals, said compound being insoluble in water and in at least one solution by which thedyestufi could be applied to textile'material.

In testimony whereof I hereto afiix my signature.

CLARENCE B.

dyestufi and containing a