Патент USA US2122100код для вставки
gram" Patented June 28, 11938 strap stares @KQQEQE ' > 2.12am PRQCESS FOR GOILGRHNG AND WATER ?RQQlE-‘ENG TEXTILE MAUI-‘HERBAL Rudolf Kern, Qschatz, Germany, assignor to ‘the - ?rm Chemische Fabrih lit. Baumheier Korn manditgesellschaft Oschata-Zschollau No Drawing. Application December 13, 1933, Se rial No. 702,259. In Germany December .15, 1932 2 Claims. This invention relates to a process for simul taneously coloring and water-proo?ng textile materials in one bath. It has been found that the application of the dispersed water-proo?ng - substances can be effected simultaneously‘ with the coloring matter. The surprising discovery has been made that coloring matter or dyestufi‘ and dispersed water-repelling particles do not ’ impair each other’s action in any operative M phase, and that therefore, in spite of the pres _ ence of an emulsion, the coloring or dyeing takes ~ place uniformly and. not, as might be expected, irregularly, whereas for example uncleaned or unscoured cotton ?bre containing a small quane 15 ‘city of wax, and readily repelling water, ‘colors . very irregularly, and in addition it is known that the parts of ?bres coated with paraiiin are not colored at all. _ ' The surprising technical effect is that in spite ‘go of this a uniform coloring takes place. The process represents a very economical simpli? cation of textile ?nishing since the operative‘ time is considerably shortened, one operation be ing avoided._ Thus the cost in manufacture is 25 reduced considerably. After the dyeing it is not necessary to dry, before impregnating and then to dry again. The water-proo?ng emulsions are , simply added to the coloring bath and the dye ing is e?ected in the usual way. The resulting 3o wares are uniformly dyed and rep'el water to remarkable extent. The impregnation produced (oi. 91-68) sions of these'emulsions, which relate to the pro duction; ‘they are subdivided into , v (0.) those homogenizedunde'r pressure. lb) those emulsi?ed in .‘ ‘stirring machines, emulsifying machines or colloid mills. 14 parts of oil soap are stirred up with 15 parts of swollen bone glue and then diluted with wa ter. This solution is stirred into 500 parts of a solution of formate of alumina having a spe ci?c gravity of 1.095. Thereupon 1-2% of hexa- 10 line, butanol, acetic ester, acetone and the like are added. This emulsion is homogenized by , forcing through ducts by means of suitable ma chines at a pressure of 60 atmospheres pressure. ‘(2) Emulsions according to (1 ) both as regards 15 composition and production, but characterized by the addition of water-proo?ng substances Water-proo?ng substances like paraf?ns, waxes, resins, fats, fatty oils or mineral oils may 2@ be ,used. Here also a distinction is to be drawn between emulsions which are ' (a) homogenized under pressure and (1)) stated briefly, “emulsi?ed”. - By saponifying a mixture of 3.10 kg. of fatty HO 5 acid with 4 kg. of mineral oil and 7.4 kg. of para?ln an emulsion is produced to which are added 1.29 kg. of high class glue dissolved in water. This substance is mixed with‘ anialu minium formate solution which. has been pre pared by dlssolving 1.55 kg. of 50% hydroxide of alumina in 1.75 kg. of 90% formic acid. The in this way will stand rinsing even in the case of moist articles, so that the auxiliary chemi whole is then homogenized at 100 atmospheres~ ' cals can be removed and in this manner subse-~ of a' white paste are then obtained after cooling, a 2.5% solution of which is sufficient for impreg nation purposes. ga quent damage to the fibre is avoided. _ g All emulsions used for water-proo?ng pur~ poses may be employed, consisting of aqueous emulsions of water-proofing substances like para?in, aluminium soaps, and so forth, or mixas tures of such substances. ' The following special emulsions also belong to emulsions of this type: ' ' (1) Aqueous emulsions of soaps of 'polyvalent . 45 metals > The chief polyvalent metals are zinc, lead, magnesium, aluminium and copper. The acids which form soaps with these metals are fatty 5o acids of the oleic and stearic acid type, or natu= rally occurring acid mixtures, such as, for ex ample, acids of tallow, of palm oil, or of cocoa» nut oil, or acids of the resin acid type such as abietic acid. ‘ v ‘ Distinction is made ostween ' further subdivi; 0 pressure. At the concentration employed 50 kg. (3) Emulsions of water-moo?ng' substances which contain water-soluble salts of poly talent metals, chie?y‘wcter-soluble aluminium 40 salts, with a positive disperse phase All the above mentioned three groups of emul sions are acidic, and their disperse'phase is posi ti‘velyycharged. They all stabilize by means of ‘ colloids which swell in- waterfmost advanta- 5% .ge‘ously however by means'of glue and gelatin. Allthree groups of the said emulsions may contain wetting agents. ' l 30 parts of good gelatin are swollen in 550 parts of water, the glue is meltedby heating 543* and, with the aid of stirring mechanism, a mix ture of 110 parts of paramn (:iiow point 54°), 20 '\ parts of bleached Montan wax and 80 parts of paramn oil are stirred in. Whilst further stir ring in the hot, 80 parts of aluminium formate 55 . , 2 2,122,100 dissolved in 400 parts of water are slowly added, and' the mixture thereupon homogenized under pressure and then cooled down. The emulsions according to (1) and (2) form the subject matter of U. S. Patent application No. 555,148 ofApril 8, 1931, (Fabric impregnated with dispersed substances, etc.). > and 40 parts of para?in oil are emulsi?ed therein. This emulsion is treated with formate of alumina of 7° Bé. I The diluted emulsion solution is poured into a bath of the following composition: ' Parts 5 Water__..._‘__~_ 1 ' _ 500 ~ Diamine black‘ BH, (Schultz Farbsto?’ta bellen 7th edition, volume 1, No. 393) _____ (4) Emulsions having a negative dispersed part 10 , 2 consisting of soap,‘ glue, gelatin, starch, dex Glauber’s salt trin, aliphatic or aromatic sulphonic acids as Calcined soda_, _________________________ __ emulsifying agent The cotton fabric is introduced in this solution at 60° C. and, whilst thoroughly stirring, the whole ___ g ' _ 15 15 10 The disperse phase consists of the water brought to boiling, maintained at the boiling proo?ng substances already mentioned above. point for 20 minutes after which the fabric‘ is 5 parts of glue are dissolved in 100 parts of, 15 rinsed, squeezed out and dried. The waterproof 15 " water and to this solution are added 4 parts of the sodium salt of amylnaphthalene sulphonic qualities are determined according to U. S. speci acid. Into this emulsifying solution is stirred a ?cation Serial No. 684,074, of July 8, 1933, (Meth "mixture of 22 parts of paraffin, 4 parts of cetyl od of and system for testing the imperviousness to 20 alcohol and 6 parts of olive oil. The whole is water of impregnated textiles). The following constants are used in the present 20 worked up in a colloid mill to a ?ne emulsion. ' The process may be carried out by adding the determination: waterproofing substance as such to the dye bath, _Reduction in height in the examination of for example in the case of substantive dyes or 25 acid .wool dyes. The‘water-proo?ng substance, however,-may also be added to the individual treatment baths in the dyeing, for example to the copper bath, to the after-chroming bath, to the generating bath of naphtol dyes, to “the vat or to 30 the aluminous mordant. In the latter case those emulsions are advantageously preferred which already contain aluminium salts. Such emul sions occur in commerce in gelatinous form and consist of aqueous aluminium formate solution 35 as continuous phase, paramn or paraf?n-like sub ~ stance as the disperse phase, and glue as stabiliz the cotton ________ ___ ______ __- ____ __cms". 30 Drop sequence________ __drops in 7 seconds_. 10 Drop weight ________ __l _____________ __mg__ 125 25 The following drop values are obtained: I Drops Cotton dyed without water-proo?ng agent in ~ the dye bath __________________________ __ 2 30 Material impregnated in the usual way with the Waterproofing substance as previously described diluted 1:100, i. e. as 10 g./litre, impregnated 10 min. at 60° C __________ -_ 1d Dyed and impregnated as described above in Example 1 ing and gelatinizing agent. The following manu facturing receipt will illustrate the composition of, ___ ' 35 ~31 It follows from this that the water-proof qual ity when waterproo?ng in the dye bath is con . siderably higher than is produced by- impreg 30 parts of good quality gelatin are swollen in 40 ‘ 40 550 parts of water; the glue is melted by. heating nating in the usual way. In order to examine the fastness to rinsing and and, by means of a stirring mechanism, a mix ture of 110 parts of paraffin (?ow point 54°), 20 to prove that the impregnating substance adheresv parts of ~bleached Montanlwax and 80 parts of very ?rmly, the piece impregnated in the dye paraffin oil are stirred in. Whilst continuously Y bath is to be, boiled in pure water for 3 minutes 45 stirring in the hot, 80 parts of aluminium for and then dried. The imperviousness to water vmate dissolved in 400 parts of water are slowly still amounted to 10 drops after this treatment. added after which homogenization is effected Example 2.--Chroming dyestu? under pressure and the whole then cooled down. Cotton fabric is dyed in the following bath: When using such emulsions in alkaline baths Grams 50 the aluminium formate for the purpose ‘of avoid ' Water ____ __'_a ________________________ __ 1200 ing precipitation of aluminium hydroxide, is con Dianil chrome brown R (Schultz Farbsto? verted into an alkali-stable complex form by ad tabellen 7th edition, volume 1, No. 682) ___ 2 dition of tartrates or other polyoxy-compounds. Calcined soda _______ _; ________________ __ 10 the emulsion. - . ‘To the above emulsion. for example 3 kg. of Glauber’s salt ______________________ _-___ ‘15 55 sodium tartrate are added and the emulsion then Tartaric acid __________________ ___ ______ ___ 4 neutralized or rendered alkaline with caustic soda. The statements made in respect of the The imperviousness to water amounts under the above emulsions illustrate the composition only same conditions as in Example 1 to 3 drops, after-chromed at 60° C. for half an hour,~—Drop 61% of one group of emulsions. which can contain the value: 2 drops. _ . various substances compounded together in vary- . A parallel experiment has been then carried out ing amounts. The use as well of the oils which 55 are usual in dyeing operations, which consist of in which 10 parts of ‘the same gelatinous emulsion . as in Example 1 were added to 1000, parts of sulphonated fatty acids or aromatic substances, bath, after‘ which dyeing was effected at 60° C. and which are used for wetting or equalizingpur 65 for half an hour, and "the material rinsed, poses, does not impair the action of the impregna squeezed out and ironed-Drop value: 19 drops. tion. ' ~ ' Example 1.—Substantive dyeing After-chroming was then carried out in the fol lowing bath: “Makko” fabric is treated with the following bath: Ten grams of a-gelatinized emulsion are dispersed in 500 grams of a 1% tartaric acid solu tion. The emulsion used has the following com Potassium dichromate_'_ ______________ __ position: Glacial acetic acid ___________________ __ 5 80 parts of gelatin are dissolved in 1000 parts of '_An emulsion as in Example 1 _______._'__-_ 75 water and a. mixture of 40 parts of cake paramn Drop value: 25 drops. 10 _ ‘ '. 7 Parts Water _______ __'_~___\ _______________ ___..- 1150 Copper sulphate- ___' _______ __,_________ __ .70 2. 5 r i 2.5‘ 3 2,122,160 . minium formate solution which has been pre ~ A piece of fabric treated in this way is boiled for 10 minutes. The imperviousness to water pared by dissolving 1.55 leg. of 50% hydroxide of alumina in 1.75 kg. of 90% formic acld. Homo- , still amounted to" Mumps after this treatment ,genlzation is then carried out at a pressure of 100 atmospheres. With the concentration em ployed 50 kg. of a white paste are obtained after cooling.’ Generation of the dye is carried'out for 30 - delay ?xed during half an hour at 50° C. with a minutes at 31° 0.; the material is then twice 10 solution of‘ aluminium salt-containing emulsion rinsed, dried and ironed. of 15 g. per litre. This emulsion has the follow- ‘ Drop value: 26 drops. Example 3.--;Basic dyestu?s , Artificial silk is preliminarily mordanted with a 2% tannin solution, and after a considerable ing composition: _ - \ . _ Example _6.-Indigo vat 30 parts of good quality gelatin are swollen in 550 parts of water and the glue is caused to White raw wool fabric is boiled out and intro duced into a ‘oath of the. following composition: 15 melt by application of heat; by means of a stir ring mechanism a mixture of 110 parts of paraf?n , (flow point 5t°), 20 parts of bleached Montan ' Parts Water; _____________________ -l ________ __ 4500 Sodium hyposulphite ____ __-_ __________ __ 2.25 wax and 80 parts of para?in oil are stirred in. Whilst further stirringin the hot‘la solution of Indigo (Schultz, Farbstofftabellen, 7th 80 parts of aluminium‘ formate dissolved in 400 edition, volume 1, No. 1301) ________ __ parts of water arevslowly added, and thereupon ‘Water-proo?ng emulsion made as in Ex the whole is homogenized under pressure and ample 5 _______________ __~ _________ __ then cooled down. 1 ' _ v . "I'artaric The ‘material is then rinsed in ‘the cold and acid _______________________ __ 1.13 20 45 - 15 The impregnating substance, together with the 25 quarters of an hour at 60°? C. in a bath of 1000 tartaric acid, isv neutralized by means of am ' parts of water, 2 parts vof rhodamine B (Schultz, ‘ monia. ‘The fabric is dyed in the usual way and Farbstoiftabellen, volume 1, 7th edition, No. 864) after hanging awhile is dried. The value for and 5 parts of glacial acetic acid, after which it the imperviousness to water for a falling height is rinsed. hot and cold. in the usual manner, of 20 cms. amounted to 12 drops. Operations 30 squeezed out and after drying dyed ,for three so squeezed out, dried and ironed. The water re polling e?ect is very marked. Example 4 are carried out in a similar manner with hydro'ne , blue B (Schultz, Farbsto?tabellen, 7th edition, ‘volume 1, No. i113); ' Example 7 Arti?cial sills is mord‘anted as in the above ex ample, ?xed, and then simultaneously dyed and ‘impregnated with ‘methylene. blue (Schultz,v Farbsto?tabellen, 7th edition, volume 1, No. 1038).‘The bath has the following composition: 35 Skelned wool is dyed in the known manner by . means of eriochrome red (Schultz,'Farbsto?tabel ‘ len, 7th edition, volume 1, No. 745) and there upon afterchromed with potassium chromate in A solution of one gram of methylene blue R, acid emulsion, which is made as follows:- f so 500 grams of water-(50° C.) and 5 g. of glacial ‘ acetic acid are ?ltered into an emulsion of 10 g. oi a substance according to Example 5 and 500 ~ .14 parts'of sodium oleate are stirred up with at ordinary temperature) and thereupon rinsed and dried. The water-repelling action of the material treated in this way is very good. by forcing through ducts. The foregoing-emul sion is diluted fourfold and represents the above 40 15 parts oflswollen bone glue and the whole di» luted with water. This solution is then stirred g. of water (50‘ 0.). The material is then intro» , into 500 parts of a solution of for-mate of alumina; ducedat 50° 0. and dyed for one hour at 60° C. having a speci?c gravity of 1.095. . . This emulsion is homogenized at 60 atmos _ It is then ?xed in a 0.1% solution of tartar emetic ' (the treatment being effected for half an hour pheres pressure with the aid of suitable machines emulsion in the condition for use, in which after 60 chroming is carried out. The skeined wool is l'l‘arample 5.--Ncphtol dyeing satisfactorily water-repelling and can be worked Cotton'is bottomed or 30 minutes in a seat . 'up into water-proof? articles of apparel. _ When working in a suitable manner the uni solutionaof sodium naphtholate AS SW (beta hydroxynaphthoic acid; beta—naphthallde) and then rinsed and squeezed out. The fabric treated in this way is thenlntroduced into a bath oi the following composition . 1 Water >____'_ root Parts , ' j , co ‘Water-proo?ng emulsion made as described below _ _ , 10 ‘ dust red m base (d-chlor-o-toluidine rdchults, Fnrbsto?tabehen, 7th edition, volume 1, No. 82) dissolved-in glacial ace; _} ' gm swirl I - After thorough stirring potassium nitrite ‘dissolved in distilled water'is added"IOWSI-r > -' - ample not irrthe presence of dyestuffs which actas tanning agents in acid solution. "Wall<:” 60 yellow (Schultz, Farbsto?tabellen, 7th edition, ‘volume 1, No. 230) has been found to be such a dyestu?. This dyestu? acts in acid solution as a tanning agent, precipitates the glue and breaks 1 down the emulsion. In this/case emulsions are 65 used which are stabilized for example by means 2 after-chroming bath which may be usedkas in I‘ of starch, dextrln, or mucilage. lIowever, in any _ ‘ The emulsion referred to above is made as lol 70 iorrnity oi the dyeing is in all cases perfectly 55 satisfactory. Since most impregnating agents are stabilized with glue or gelatin such products cannot be used for all dyeing processes,‘ for ex the 'aitenchroming bath of Example ‘7, glue containing emulsion may be used.‘ Outstanding 70 waterproo?ng e?ects are. already produced when By saponi?cation oi a mixture of tiling; of fractions of a ‘gram of impregnating agent per fatty acid with 4 kg. oi‘ mineral oil and "hi lag. litre are used. The in'ipregnationdescribed can of paramn an emulsion is obtained to which‘ is be used in the known manner in all dyeing ap added 1.29 lrg. of high class glue dissolved in pliances or apparatus. water. This substance is mined with an alu @ 2,122,109 Eaample 8.—Inda.nthrene "cat A cotton fabric is treated at 60° C. in a hypo-_ sulphite vat of the following composition: 5 15 g. of‘ a substance 500 g. of water warm and twice cold“ Five cos. of an alumina so 2 g. of dyestu? (invdanthrenegolden orange G double paste: Schultz, Farbstoiftabellen, _ 7th edition, volume 1, No.- 1245) 3 g. of hyposulphite (Na2SaO4) 10 g. of common salt _ 5 g. of an emulsion of the following compo sition 15 The fabric is dyed for one hour at about 60° C'., rinsed, soaped in a 0.5% soap solution contain ing 1% of the above emulsion, and rinsed once ‘ 1.5 kg. of 50% aluminium hydroxide. 2.1 kg. of’ formic acid 375 kg. of water ' 2 kg. of tartaric acid 7 . of concentrated ammonia 99 kg. of paramn ' 30 kg. of an oil fatty acid 10 kg. of potash lye (45° Bé.) 20 kg. ofalue , lution of‘ 7° Bé. are added per litre of the last rinsing bath. For a falling height of 30 cm. the waterproof value amounts to 21 drops. What I claim is: 1. A method of simultaneously and uniformly dyeing and waterproo?ng textile materials, com~ 10 prising treating said materials in usual alkaline dyestu? bath containing. also a stable emulsion of substantially. colorless water-repellent sub stances and aluminium formate and a. substance selected from a group consisting of tartaric acid 15 and tartrates, added for the purpose of convert ing the aluminium salt into a complex compound; 2. The method of claim 1, as modi?ed in that the “tartrate” recited therein is tartaric acid. 20 RUDOLF KERN.