US2733975A

US2733975A - Process of coating and dyeing textile

Info

Publication number: US2733975A
Authority: US
Publication date: 1956-02-07
Anticipated expiration: 1973-02-07

Description

United States Patent p 7 2,733,975 PROCESS OF COATING AND DYEING TEXTILE FIBERS AND RESULTANT ARTICLE Thomas C. Whither, Elizabeth, N. J.

No Drawing. Application July 19, 1950,

Serial No. 174,777 7 17 Claims. (Cl. 818) This invention relates to the treatment of textile fibers impregnated with an alkali-copper complex, sericeous material and (in some instances) an alkaline agent. It involves particularly the treatment of such impregnated fibers whereby removal of the alkali-copper complex and of the alkaline agent (if present) is effected and textile,

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centration of acidic agent should be the same or substan- No. 2,565,832, is disclosed a procedure whereby an disclosed a process whereby an aqueous solution of an alkylolamine-copper complex and sericeous material can be prepared (for impregnation of textile fibers) in which the proportion of alkaline agent (e. g., sodium or potassium hydroxide) is very-small. In my copending application, Ser. No. 162,385, now U. S. Pat. No. 2,675,326, is disclosed employment of aqueous solutions in which an alkali metal hydroxide or a tetra-alkyl ammonium hydroxide serves as both the copper complex-forming agent and as the alkaline agent.

In all of the above disclosed methods, the fibers after impregnation with the aqueous solution of copper complex and sericeous material (and while they are still wet or damp and in some instances after the impregnated fibers have been dried) are washed with an aqueous solution of an acidic agent which forms water-soluble salts with the alkali-copper complex and with the alkaline agent (if present). Afterwards, the fibers are washed with water to eliminate substantially all of the salts and acidic agent and to leave them impregnated with substantially only sericeous material.

I have observed that substitution of the aqueous solution of an acidic agent by an aqueous alcoholic solution of an acidic agent, in the above-mentioned procedures, furnishes fibers which contain an increased proportion of sericeous material. Also, I prefer that the aqueous alcoholic solvent for the acidic agent contain a major proportion by volume of the alcohol. To illustrate, two samples of the same cotton cloth are impregnated in the same manner and with substantially the same proportion of the same aqueous solution of alkylolamine-copper complex, sodium hydroxide and sericeous materiahand one impregnated sample is washed with an aqueous solution of hydrogen chloride and the other with an aqueous alcoholic (say, 85 per cent isopropyl alcohol) solution of tially so in each solution. Afterwards, each sample is washed well with water and dried. Then it will be found that the cloth washed with aqueous alcoholic acid has gained more proportionally in weight due to treatment than the other cloth, generally will possess a smoother fuller feel, and usually will be dyed to a deeper or darker color wheneach fabric is dyed in the same manner.

In the above-indicated procedure, treatment of the impregnated fibers with aqueous alcoholic acid leads to the formation of alkylolamine hydrochloride, copper (cupric) chloride and sodium chloride. Of these salts, the alkylolamiue hydrochloride and copper chloride are soluble in the aqueous alcohol and for the most part will be removed from the fibers during washing with the aqueous alcoholic solution of acid. Sodium chloride,

however, hasa limited solubility in the alcoholic liquid and it is necessary that the fibers be washed with water sothat this salt as well as the acid and any residua of copper and alkylolamine salts be eliminated from the fibers. In other words, I seek to prepare fibers which are impregnated with substantially only sericeous material and are substantially devoid of any salts or acidic agent. I do not mean to limit my invention to the use ofinorganic or mineral acids as the above-indicated method can be modified so that organic acids may be employed. Forexample, cotton cloth impregnated with an aqueous solution of an alkylolamine-copper complex, sericeous material and potassium hydroxide can be washed with an aqueous alcoholic (say, per cent isopropyl) solution of benzoic acid. Afterwards, the cloth is washed with some of the aqueous alcohol to eliminate copper benzoate (which is substantially insoluble in water) as well as unreacted benzoic acid and alkylolamine benzoate. The benzoates of copper and alkylolamine are formed as the result of interaction between benzoic acid and the copper complex. Next, the cloth is washed with water to'remove potassium salt. If desired, warm water, e. g., water at a temperature of 50 to 60 C., may be used in this instance in place of water at room temperature as benzoic acid is somewhat more soluble in the warm aqueous liquid and employment of the latter may remove traces of the acid from the treated fibers.

Still another modification of my invention involves treatment of fibers impregnated with an aqueous solution of an alkylolamine-copper complex, a tetra-alkylol ammonium hydroxide and sericeous material. In such cases, the impregnated fibers may be washed, for example, with 90 per cent aqueous isopropyl alcohol in which hydrogen chloride is dissolved. Afterwards, the fibers are washed with aqueous alcohol only, since the alkylolamine, tetraalkylol ammonium and copper salts are soluble in the aqueous alcohol. 7

The following examples'will furnish additional illustrations of my invention but it will be understood that my invention is not to be limited to them.

Example 1.--To an aqueous solution consisting of 3 g. of copper chloride (CuCl2-2H2O) disso1ved in about 20 cc. of water was added triethanolamine in smal portions until a dark blue aqueous liquid was obtained in which all the copper compound was dissolved. The liquid then was diluted with water to a volume of 50 cc. In the diluted solution was dissolved sufiicient solid sodium hydroxide to react with theamine salt (from interaction of triethanolamine with copper chloride) and to give substantially 1 per cent of the free or uncombined alkali metal hydroxide. During dissolution of the latter compound, the aqueous liquid was cooled externally with Water to prevent any appreciable increase in its temperature.

The solution of alkylolamine-eopper complex and alkali metal hydroxide was admixed with 7 g. of silk fibers the mixture allowed to stand overnight at room temperature. Afterwards, water equal to onefifth the volume of liquid was added to the mixture and the latter thenfiltered to remove any undissolved material.

A sample of bleached cotton cloth was impregnated with this filtered solution of sericeous material by im mersion in a portion of it for minutes at room temperature. Afterwards, the cloth was allowed to drain at room temperature, washed with aqueous acid (prepared by admixing 1 volume of concentrated aqueous hydrochloric acid with 3 volumes of water), then washed well with water, and dried. Increase in weight of the cloth indicated it contained 1.29 per cent of sericeous material.

Simultaneously, another sample of the same bleached cotton cloth was treated in like manner with this modification: the acidic solution for washing the impregnated cloth was prepared by admixing 1 volume of concentrated aqueous hydrochloric acid with 3 volumes of substantially anhydrous isopropyl alcohol. In this instance, increase in weight of the cellulose material indicated it contained 2.65 per cent of sericeous material.

Example 2.Two grams of copper chloride (CuClz-ZHzO) were dissolved in 20 cc. of water and to this solution diethanolamine was added slowly and with stirring until a clear blue solution of the copper complex was obtained. Then the aqueous liquid was diluted with water to a volume of 50 cc. Next, sufiicient solid potassium iydroxide was dissolved in the solution to react with the amine salt (formed by interaction of diethanolamine with the copper salt) and to furnish substantially 4 per cent of the free or uncombined alkali metal hydroxide. This solution of alkylolamine-copper complex and alkali metal hydroxide was admixed with 6 grams of silk fibers and allowed to stand at room temperature for 1 hour. During this time the mixture was shaken occasionally. Afterwards, water equal to approximately one-fifth the volume of liquid was added to the mixture and the latter then filtered to eliminate undissolved material.

A sample of unbleached cotton cloth was impregnated with some of this filtered solution by immersion therein for 30 minutes at room temperature. The sample then was allowed to drain at room temperature and afterwards was washed twice with aqueous acid prepared by admixing 2 volumes of glacial acetic acid with 38 volumes of water. Next, the fabric was washed with water and dried. Increase in weight indicated it contained 1.68 per cent of sericeous material.

Simultaneously, another sample of the same unbleached cotton cloth was treated in like manner with this modification: the acidic solution for washing the impregnated textile material was prepared by admixing 2 volumes of glacial acetic acid, 2 volumes of water and 36 volumes of substantially anhydrous n-propyl alcohol. in this instance, increase in weight of the sample indicated it contained 4.23 per cent of impregnating material.

Example 3.-Copper hydroxide was admixed with water and to the mixture was added slowly diethanolamine until the copper compound dissolved and a bluecolored solution was obtained. The latter then was diluted with water to give an aqueous solution in which the concentration of copper Was equivalent to 2.66 g. of copper hydroxide per 100 cc. of liquid. In this solution was dissolved sufiic'ient potassium hydroxide to furnish substantially 4 per cent of the alkali metal hydroxide. Silk fibers were admixed with this solution of copper complex and alkali metal hydroxide (maintained at room temperature) over a period of 1 hour until an excess of the fibers had been added. The liquid then was separated from undissolved fibers by filtration.

Two samples of unbleached cotton cloth were impregnated separately with some of the filtered solution. in each instance, the fabric was worked in the liquid at room temperature for 15 minutes, then removed and allowed to drain at room temperature. One of the impregnated fabrics was washed twice with an acid solution prepared by admixing 5 volumes of per cent aqueous lactic acid with 35 volumes of water. Afterwards, the fabric was washed well with water and dried. increase in weight of this sample indicated it contained 0.75 per cent of impregnating material.

The other impregnated fabric was washed with an acidic solution prepared by admixing 5 volumes of 85 per cent aqueous lactic acid, 4 volumes of water and 3l volumes of glycerine. In this instance, the acidic solution was rather viscous and consequently it was taken up very slowly by the impregnated cloth. Also, the alkaline bodies and copper complex (present in the impregnated cloth) reacted slowly with the acid. It was necessary in this case that the fabric remain immersed in the aqueous alcoholic acid. for approximately 16 hours at room temperature. And during that time the acidic solution was stirred occasionally to insure, as far as possible, that the aqueous glycerine solution in contact with the cloth was always acidic in character. Afterwards, the treated cloth was Washed well with water and dried. Increase in weight of this sample indicated that it contained 7.79 per cent of impregnating material.

The two treated samples and also one of the original unbleached cotton material were dyed separately and in each instance the dye bath consisted of 100 partsof water per 1 part of cloth and 5 per cent (on weight of sample) of a basic dye (Malachite Green). The samples were immersed in their respective baths at room temperature, and after 15 minutes the temperature of the baths was increased to 65 C. over a period of 30 minutes, then kept at 65 to 70 C. for 30 minutes, and afterwards the baths were allowed to cool to room temperature. Then the fabrics were removed, rinsed well with cold water, and dried. The untreated cloth was CuClz- 21-120 dissolved in 50 cc. of water was added triethanolamine slowly and in small amounts until a deep blue aqueous solution of the copper complex was obtained. The

liquid then was diluted with water to a volume of 100' cc. In this solution was dissolved sufiicient sodiumhydroxide to react with the alkylolamine salt (from interaction of alkylolamine and copper salt) and to give substantially 3 per cent of the alkali metal hydroxide. Sill; fibers were admixed with the liquid (keeping the quantity of fibers in excess of that which dissolved) and the mixture allowed to stand with occasional stirring for 2 hours at room. temperature.v Afterwards, the liquid was filtered from undissolved fibers.

Two samples of unbleached cotton cloth were impregnated separately at room temperature withthe filtered solution. One of the impregnated samples then was washed with 8 per cent aqueous sulfuric acid in which was dissolved 2 per cent of sodium sulfate, afterwards washed with water, and dried. Increase in weight of this" fabric indicated it contained 3.36 per cent of sericeous material.

The other sample of impregnated cloth was washed with an 8 per cent solution of benzoic acid in a solvent consisting'of volumes of n-propyl alchol and 5 volumes of water. In this instance, three successive portions of indicated it contained 5.16 per cent of sericeous material. 7

As the function of the acid is to react with the copper complex and with the alkaline agent and thereby precipi tate sericeous material in or on thefibers, the quantity of acid in solution as well as its concentration should such that more than sufficient acid fo'r such -reactions is present and the liquid in direct contact with the fibers should be appreciably acidic at all times. Because of the small solubility of benzoic acid .inwater, it seemed in+ advisable in thisinstance tocornpare the effect of this acid in aqueous solution with that of the acid in aqueous alcohol. If aqueous benzoic a'cidhad been employed, then a large proportion ofalkylolamine-copper complex and alkali metal hydroxide (and consequently of sericeous material) would have been washedout of the impregnated fibers prior to reactingfwith the acid due to thelarge volume of water needed to'dissolve the required quantity of acid. For these reasons,an acid more soluble in water, namely, sulfuric acid, was used when water only was the solvent. Also, a'small proportion of alkali metal salt was dissolved in the aqueous acid to aid in precipitation of sericeous material. Employment of an.

aqueous acid containing a small proportion of a dissolved alkali metal salt in the treatment of textile'fibers iinpregnatedwith an alkylolamine-copper' complex and sericeous material has been described in my copending application Ser. No. 101,499. 7 a

Example 5.-To g. of copper chloride (CuCl2 2H20.)

dissolved in a small quantity of water'was added Z-amino- 2-methyl-propanediol-L3' in small portions and with stirring until all of the copper compound was changed into the alkylolamine-copper-complex and a deep blue colored solution was obtained. The latter thenwas diluted with water to a volume of 100 cc. Next, sufficient potassium hydroxide was dissolved in the aqueous solution to react with the alkylolamine salt (resulting from interaction of alkylolamine with copper compound) and to give sub stantially 3 per cent of the u'ncombined alkali metal hydroxide. Silk fibers, in an amount greater than that which would dissolve, were admixed with the aqueous solution and the mixture allowedto'stand for 2 hours at room temperature. Afterwards, undissolved fibers-were separated by filtration.

Two samples of unbleached cotton cloth were impregnated with some of the filtered solution by immersion therein at room temperature. The two samples were al' lowed'to drain and to remainexposed to the atmosphere overnight. One of these samples was washed with 10 per cent aqueous hydrochloric aeidfthen with water, and dried. Increase in weight of this sample' indicated it contained 4.43 per cent of sericeous material."

The other fabric was immersed in alO per cent solution of salicylic acid in a solvent consisting of 95 volumes of propylene glycol and 5 volumes of Water; The cloth was permitted to remain immersed'in' this acidic liquid at room tmperature for about 18 hours" (overnight). Afterwards, the sample was removed," washed wellwith cold 1 water, then washed with warm" water (temperature, 50 to 55 C.), and dried. Increase in weight'of this fabric indicated it contained 9.02 per cent sericeous material. I

The reasons for comparing washing of one sample with aqueous hydrochloric acid with washing of the other sample with salicylic acid in an aqueous alcholic solution are similar to those 'given under Example 4 forcomparing the effect of aqueous sulfuric acid with that of 'benzo-ic acid in an aqueous alcholic solution.

Example 6.-To a mixture of 2.5 g. of copper hydroxide and 100 cc. of 70 per cent aqueous ter.-butyl alchol was added 2-amino-2-methyl-propanediol-1,3 in small portions substantially anhydrous isopropyl, alcohol. NEXLfthiS until allot the copper compound dissolved and. a deep blue colored solution was obtained. In this'solution dissolved sutficientjsolid' sodium hydroxide to give sub-' stantially 2.5 per cent of the alkali metal hydroxide.

This solution was admixed with a relatively large quantity of silk fibers and the mixture allowed to stand at room temperature, with occasional stirring, until the supernatant liquid possessed only a very light blue color.

The alcoholic liquid then 'was separated from the treated tained by them. vThe treatedand washed fibers were.

admixed with 100 cc. of water and the mixture allowed to stand overnight. Filtration of the liquid then removed undissolved fibers. This method of preparing aqueous solutions of'sericeous material is described in my copcnding application Ser No.y101,499.

Two bleached cotton cloth samples were impregnated with some of the 'filtered aqueous solution of sericeous material, andthen allowedjto drain and to dry at room temperature. One sample was washed with aqueous 10 per cent sulfuric acid, then with water, and dried. Increase in Weight of thissample indicated it contained 552 per cent of'sericeous material.

The other sample was washed with 'per cent aqueous isopropyl alcohol in which was dissolved substantially 10 per cent by weight of concentrated sulfuric acid; Afterwards, the sample of cloth was washed with water and dried. Increase in weight of thisfabric indicated it contained 8.48 per cent of sericeous material.

Example 7.An aqueous solution of sericeous material was prepared in the following'manner: 14 volumes of water were mixed with 6' volumes of glycerine and then lithium hydroxidewas dissolved in the aqueous alcoholic liquid in theproportion of 1.2 g. to 20 'cc. of liquid.-

Afterwards, thealkaline solution was saturated with copper hydroxide (Cu(OH)2) lay-admixing the latter with" the alkaline solution'in small portions and stirring the mixture. When an excess of the copper hydroxide had been added, the mixture of liquid and solid was allowed to stand overnight atroom temperature. Then theresulting blue solution Was'separated from undissolved copper compound by filtration.

Silk fibers were admixed with the solution of copper compound in the proportion of 5 g. of fibers to 20 cc. of liquid. 'Afterthe mixture had stood, with occasional stirring, at room temperature for 1- hour, the resulting pound. The diluted mixture was permitted to stand for a few' minutes at room temperature and then was filtered.

Substantially all of the silk fibers had dissolved.

Two samples of the same bleached linen cloth were impregnated with some' of the filtered solution. "After: the samples had drained, one of them was washed with dilute aqueoushydroch'loricacid, then with water, and dried. Increase in weight of this sample indicated it contained 0.67 per cent of impregnating material.

The other impregnated sample, after draining, was washed with three separate portions of aqueous alcoholic acid made by admixing 15 volumes of concentrated hydrochloric acid, 15 volumes of Water and 70 volumes of fabric was washed well with water, and dried. Increase in its weight indicated it contained 1.53 percent of impregnating materialf j I i 1 Example 8.-An aqueous'solution containing substantially 20 per cent of tetraethanol ammonium hydroxide was admixed with copper hydroxide (Cu(OH)2) and the admixture allowed to stand at room temperature, with oc-' casional stirring, until no more of the coppercompound 7 appeared todissolve. The blue colored solution then was separated from undissol'ved coppel' hydroxide.

I Silkfibers were admixed with the a ueous solution of copper complex and allowed to stand", with occasional stirring, for 18" hours at room temperature. Afterwards, undissol'ved fibers were eliminated by filtration of the mixture.

Two samples of unbleached cotton cloth were saturated with some of the filtered aqueous sericeous solution by working therein at room temperature. Then both samples were permitted to drain and to dry by exposure to the atmosphere. One sample was washed with dilute aqueous sulfuric acid, then water, and dried. Increase in weight or" thiscloth indicated it contained 1.4 per cent or impregnating. material. This procedure, includes the prep aration of aqueous solutions containing, substantially only a tetra-alkylol ammonium hydroxidecopper complex and silk and the application of such solutions to the treatment of cellulose fibers, is described in my copending applica' tion Serial. No. 221, 323.

The other sample was washed three successive times with portions of an acidic solution prepared by admixing volumes of concentrated sulfuric acid, volumes of water, and 80 volumes of substantially anhydrous isopropyl. alcohol. Next, it was washed with water, and dried. Increase in weight of this fabric indicated it contained 8.03 per cent of impregnatingmaterial;

As perviously mentioned in thisspecificat-ion, the alcohols which I prefer are water-soluble, acyclic, saturated, normally-liquid compounds. I They may be either monohyd roxy or polyhydroxy. The alcohols should be sulficiently soluble in water. or should be capable of dissolving sufficient Water so that the resulting aqueous alcoholic liquid will not contain less than about 60 per cent by Q volume of the alcohol. Aqueous alcoholic liquids containing a greater proportion by volume of the alcohol, say, 86 or 90 per cent, also are suitable. It necessary or desirable, the alcoholic liquid may have only a. very small proportion of water, say, 0.5 to 1 per centby volume, and may even be substantially anhydrous. Mixtures of alcohols are permissible, provided the total alcoholic content of the aqueous liquid is not less than about 60 per cent.

By the term saturated I- mean that the alcohols do not contain. any unsaturated (e.g., olefinic or acetylenic) linkages in their molecular structures. By the term normally liquid Imean that the alcohols are liquids at roomtemperture or thereabouts. Examples of such. alcohols are ethyl, isopropyl or ter.-butylalcohol, propylene or trimethylenc glycol, and glycerine. Alcohols which are solids at temperatures appreciably higher than room or atmospheric temperature, e.g., mannitol, are not included in this invention.

I- have illustrated my procedure with fibers which. have been impregnated with aqueous solutions containing, in addition todissolved silk fibers, a complexcompound of copper. kylolamine-copper complex, an alkali metal hydroxidecopper complex, a tetra-alkylol ammoniumhydroxidecopper complex and a tetra-alkyl ammonium hydroxidecopper complex. The alkylolamines-suitable for my purpose can be either a primary, secondary or teritary amine or they can be either morl'ohydroxy or polyhydroxy compounds. The tetra-alkylol ammonium hydroxides and the tetra-alkyl ammonium hydroxides may be compounds in which all four groups (alkylol' or alkyl) are the same or in which two or more of these groups differ from the others. My invention is applicable also to the treatment of cellulose fibers impregnated with aqueous solutions containing, in addition to dissolved silk fibers, other alkali copper complexes, e.g;, thoscformed by'interaction of ammonia or of primary, secondary or tertiary amines with copper hydroxide; Since all these complexes either contain. copper and an. alkaline compound or are the resultof interaction of. a copper compound with an: alkaline com pound to furnish a water-soluble substance, I include all Examples of such copper complexes are an" al-' 8 such: complexes under the general term of alkali-copper complex. It shouldb'e noted that the alkaline com ounds may be inorganic (egg ammonia or sodium hydroxide) or organic (e.g;, ethyl'ar'nine or diethanolamine) in char acter;

The impregnated cellulose fibers may be treated according to this invention while they are still wet with the aque'ous solution containing" the copper-complex and dissolved silk" fibers; Or; the ii'nprcg'nate'dfibers may be partially or substantially'dry prior to treatment. Preferabl'ythe drying operation is effected at room oratmosphe'ric temper'ature' or thereabouts' and thereby avoid anyhamiful' action on: the cellulose fibers or on the' s'er'iceous material impregnated therein.

The acidic agents suitable forr'ny purpose can be either inorganic or organic (carboxylic) com ounds; Illustrations of inorganic acids are hydrochloric, hydrobromic or sulfuric acid. Examples of carboxylic acids are acetic or benzoic acid. Substituted carboxylic acids such as lactic acid, salicylic acid; chlbracen'c acid and bromobenzo'ic acid may be employed also. In some instances the hydr'ox'y-subsfit'ut'ed acids, v such as lactic or salicylic acid, are particularly applicable since they furnish copper salts which exhibit appr'eciable's'olubilities in water and in alcohol'. Whatever acidic agents are employed, they should meet the following conditions: 1') should not react in an undesirable manner with the aqueous alcoholic liquid, (2') should not be present in sufficient concentration in the acqueous alcoholic solution so as to exert any deleterious action of the cellulose fibers or on the sericeous material impregnated therein, and (3) should furnish salts, on reaction with the alkaline agent and copper complex, which are appreciably soluble in water or in the aqueous alcoholic liquid or in both.

When cellulose fibers impregnated with an alkali-copper complex and sericeous material are washed with the aqueous alcoholic solutionof acidic agent, the latter should be present in sufficient quantity to react with all the alkaline agent (if present) and all of the copper complex. This step of washing the impregnated fibers requires somewhat more time than if an aqueous solution of the acidic agent is employed. In the case of polyhydroxy alcohols, such as propylene glycol or glycerine,.which. furnish (when employed in accordance with the method of this invention) rather viscous solutionsof acidic agent, immersion of the impregnated fibers for several hours in the acidic liquid is often required to elfect substantially complete conversion of the copper somplex-into the corresponding copper salt. Moreover I do not Wish tobe limited to one washing of the fibers with the aqueous alcoholic solution of acidic agent. If necessary,-fibers impregnated with alkali copper complex and sericeous material may be washed two or more successive times and each operation involves employment of an unused portion of the acidic solution.

After the fibres are treated with the acidic solution, they are washed with the aqueous alcoholic solvent, or with water, or successively with the aqueous alcoholic solvent and with water. The solvent or solvents used in this operation will depend upon such factors as the alkali-copper complex and the aqueous alcohol and the acidic agent dissolved therein. For example, if cellulose fibers are impregnated with an aqueous solution containing alkylolam-ine-copper complex, alkali metal hydroxid'e and dissolvedsilk fibers and are washed with an acidic solution consisting of sulfuric acid dissolved in aqueous isopropyl alcohol, then the acid wash should be followed by one with water so as to eliminate any alkali metal sulfate and copper sulfate which may not be removed by the aqueous alcoholic liquid. Or, if. the same impregnated fibers be-wa'shed with an acidic solution of benzoic acid in aqueous isopropyl alcohol, then it is essential that the fibers be washed: aitclwards with. aqueous alcohol, to eliminate copper benzoate, prior to the water wash. In any event, the liquids employedsubsequent to treatment of the fibers with the solution of acidic agent should remove substantially all salts, acidic agent and alcohol (if not readily evaporated at room tem perature or thereabout) from the fibers and leave them impregnated with substantially only sericeous material.

Although I have illustrated the process of this invention by its application to the treatment of cellulose fibers, I do not wish to be limited to the treatment of such fibers. Some of the aqueous solutions containing dissolved sericeous material (as a copper-containing complex) and a small proportion of alkaline bodies, as for example those solutions described in my copending application Ser. No. 101,499, can be employed for impregnation of animal fibers (such as wool or silk) with sericeous material. Animal fibers impregnated with such aqueous solutions or copper-silk complexes and alkaline bodies may be treated according to the method of this invention.

What I claim is:

1. The process for treating textile fibers impregnated with a water-soluble alkali-copper complex selected from the group consisting of alkylamine containing no alkylol groups-, alkylolamin'e-, tetra-alkylol ammonium hydroxide-, and alkali-metal hydroxide-copper complexes, and sericeous material which comprises washing said fibers with aqueous alcohol containing a dissolved acidic agent, and then washing the fibers with aqueous alcohol, said aqueous alcohol consisting of an admixture of a saturated acyclic normally-liquid water-soluble alcohol and water and containing at least about 60 per cent by volume of said alcohol, and said acidic agent forming salts with said copper complex which are soluble in said aqueous alcohol which acidic agent does not interfere in any undesirable way with the aqueous alcohol and is present in amount insuflicient to exert any deleterious action on the fibers and sericeous material.

2. The process according to claim 1 in which the water-soluble alcohol is a monohydroxy alcohol.

3. The process according to claim 1 in which the watersoluble alcohol is a dihydroxy alcohol.

4. The process according to claim 1 in which the watersoluble alcohol is a trihydroxy alcohol.

5. The process for treating textile fibers impregnated with a water-soluble alkali-copper complex selected from the group consisting of alkylarnine containing no alkylol groups-, alkylolamine-, tetra-alkylol ammonium hydroxide-, and alkali-metal hydroxide-copper complexes, and sericeous material which comprises washing said fibers with aqueous alcohol containing a dissolved acidic agent, then washing the fibers with aqueous alcohol, and afterwards washing the fibers with water, said aqueous alcohol consisting of an admixture of a saturated acyclic normally-liquid water-soluble alcohol and water and containing at least about 60 per cent by volume of said alcohol, and said acidic agent forming salts with said copper complex which are soluble in a solvent selected from the group consisting of water and said aqueous alcohol which acidic agent does not interfere in any undesirable way with the aqueous alcohol and is present in amount insufficient to exert any deleterious action on the fibers and sericeous material.

6. The process according to claim 5 in which the acidic agent is a mineral acid.

7. The process according to claim 5 in which the acidic agent is a monocarboxylic acid.

8. The process according to claim 5 in which the acidic agent is a monohydroxy monocarboxylic acid.

9. In a process of treating textile fibers impregnated with a water-soluble alkali-copper complex selected from the group consisting of alkylamine containing no alkylol groups-, alkylolamine-, tetra-alkylol ammonium hydroxide-, and alkali metal hydroxide-copper complexes, and sericeous material, which comprises washing said fibers with aqueous alcohol containing a dissolved acidic agent, said aqueous alcohol consisting of an admixture of a saturated acylic normally-liquid-water-soluble alcohol and water and containing at least about by volume of said alcohol, and said acidic agent forming salts with said copper complex which are soluble in said aqueous alcohol which acidic agent does not interfere in any undesirable way with the aqueous alcohol and is present in amount insutficient to exert any deleterious action on the fibers and sericeous material.

10. The process according to claim 9 in which the water soluble alcohol is a monohydroxy alcohol.

11. The process according to claim 9 in which the water soluble alcohol is a dihydroxy alcohol.

12. The process according to claim 9 in which the water soluble alcohol is a trihydroxy alcohol.

13. The process according to claim 1 which includes the further step of dyeing the washed textile fibers.

14. The process according to claim 5 which includes the further step of dyeing the washed textile fibers.

15. The process according to claim 9 which includes the further step of dyeing the impregnated textile fibers.

16. Textile fibers impregnated with substantially only sericeous material, resulting from the method of claim 1.

17. Dyed textile fibers, the fibers being impregnated with substantially only sericeous material, resulting from the method of claim 1.

References Cited in the file of this patent UNITED STATES PATENTS 1,936,753 Dreyfus Nov. 28, 1933 1,955,221 Borner Apr. 17, 1934 2,417,388 Whitner Mar. 11, 1947 2,417,389 Whitner Mar. 11, 1947 2,446,682 Whitner Aug. 10, 1948 2,565,832 Whitner Aug. 28, 1951

Claims

1. THE PROCESS FOR TREATING TEXTILE FIBERS IMPREGNATED WITH A WATER-SOLUBLE ALKALI-COPPER COMPLEX SELECTED FROM THE GROUP CONSISTING OF ALKYLAMINE CONTAINING NO ALKYLOL GROUPS-, ALKYLOLAMINE-, TETRA-ALKYLOL AMMONIUM HYDROXIDE-, ALKALI-METAL HYDROXIDE-COPPER COMPLEXES, AND SERICEOUS MATERIAL WHICH COMPRISES WASHING SAID FIBERS WITH AQUEOUS ALCOHOL CONTAINING A DISSOLVED ACIDIC AGENT, AND THEN WASHING THE FIBERS WITH AQUEOUS ALCOHOL, SAID AQUEOUS ALCOHOL CONSISTING OF AN ADMIXTURE OF A SATURATED ACYCLIC NORMALLY-LIQUID WATER-SOLUBLE ALCOHOL AND WATER AND CONTAINING AT LEAST ABOUT 60 PER CENT BY VOLUME OF SAID ALCOHOL, AND SAID ACIDIC AGENT FORMING SALTS WITH SAID COPPER COMPLEX WHICH ARE SOLUBLE IN SAID AQUEOUS ALCOHOL WHICH ACIDIC AGENT DOES NOT INTERFERE IN ANY UNDESIRABLE WAY WITH THE AQUEOUS ALCOHOL AND IS PRESENT IN AMOUNT INSUFFICIENT TO EXERT ANY DELETERIOUS ACTION ON THE FIBERS AND SERICEOUS MATERIAL.