US2520105A - Metachrome dyeing procedure - Google Patents

Metachrome dyeing procedure Download PDF

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US2520105A
US2520105A US750886A US75088647A US2520105A US 2520105 A US2520105 A US 2520105A US 750886 A US750886 A US 750886A US 75088647 A US75088647 A US 75088647A US 2520105 A US2520105 A US 2520105A
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dye
dyeing
bath
procedure
dyed
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US750886A
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Henry E Millson
Chester A Amick
Willard H Watkins
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Wyeth Holdings LLC
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American Cyanamid Co
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/673Inorganic compounds
    • D06P1/67333Salts or hydroxides
    • D06P1/6735Salts or hydroxides of alkaline or alkaline-earth metals with anions different from those provided for in D06P1/67341
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/60General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
    • D06P1/607Nitrogen-containing polyethers or their quaternary derivatives
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/673Inorganic compounds
    • D06P1/67333Salts or hydroxides
    • D06P1/67341Salts or hydroxides of elements different from the alkaline or alkaline-earth metals or with anions containing those elements
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02Material containing basic nitrogen
    • D06P3/04Material containing basic nitrogen containing amide groups
    • D06P3/14Wool
    • D06P3/20Wool using mordant dyes using metallisable dyes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/907Nonionic emulsifiers for dyeing
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/916Natural fiber dyeing
    • Y10S8/917Wool or silk
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92Synthetic fiber dyeing
    • Y10S8/924Polyamide fiber

Definitions

  • This invention relates to improved metachrome dyeing processes.
  • the second process is referred to as an after chrome or top chrome procedure in which the fabric is dyed with metallizable dyes and then subjected to an after treatment with a solution of a compound of the metal to be introduced into the dye molecule.
  • the dye is applied the same as an acid dye, and it requires an extra process and extra time for the formation of the metallized complex.
  • the third procedure is the so-called bottom chrome process in which a metal compound is first deposited in the textile fiber and then the dye is applied and the metaliized complex forms in the fiber.
  • this process is an extremely long one requiring several steps.
  • the fourth procedure is the so-called metachrome process in which the metallizable dye and the compound of the metal to be introduced are both present in the dye bath at the start and the metailized dye is formed both in the fiber and in the bath itself and not introduced as a preformed compound.
  • the metachrome process presents many advantages.
  • the dye is not eiiectively utilized when dyeing basic nitrogenous fibers such as the natural animal fibers, Wool, silk, and the like or synthetic fibers of similar type from casein, polyamides, and so forth.
  • Certain dyes give good uniform liber'penetration in a yarn, and others penetrate only some of the fibers.
  • the dyes which do not penetrate all of the fibers or are destroyed during the dyeing operation, particularly in the case of heavier shades, have, therefore, been considered unsuitable for use in the metachron'ie process and have required resort to the process starting out with the preformed inetallized dye or the top or bottom chrome processes With'their attendant disadvantages.
  • 2nd A water dispersible surface active composition containing at least one cationic surface active agent.
  • the pH of the dye bath is sufficiently high initially so that rapid chromation is prevented or retarded, and during the dyeing process the pH is progressively lowered until final chromation results.
  • any one of the three factors referred to above will efiect some improvement either in color value or levelness, but with certain other dyes, both of these improvements in dyeing characteristics are not obtained with metallizable dyes unless all three of the above reaction conditions are present, and the present invention contemplates only processes in which all three factors are efi'ective.
  • the alkaline earth metal'salts or salts to be used are not in the least critical. Any of the common soluble salts may be used.
  • the difierent alkaline earth metal salts will vary to some extent in their effect, and this variation is not the same with all metaliizabie dyes. In general, best results are obtained with magnesium salts, magnesium sulfate being particularly desirable, by reason of its cheapness, ready availability and the excellent results which it gives in the process of the present invention. Accordingly magnesium sulfate represents the preferred alkaline earth metal salt, though in its broader aspects the invention is not limited to its use.
  • the second factor requires .a:.water. dispersible surface active composition containing-at least one cationic surface active agent. It is also .desirable that any insoluble reaction products of the cationic surfaceactive' agent be likewise dispersible. Thisdispersibility of the surface active composition may be'effected in-several'ways.
  • the presentinvention is not concerned with the particular methods of achieving dispersibility of the surface active component, this forming the subject matter of the applications above referred to. .On the contrary, the presentinvention is concerned only with water dispersible cationic surface active compositions when associated with the other twofactors of the processof the present invention, namely, the presence of the alkalineearth metalsalt, and the initial high pH of the dye bath.
  • the third factor namely, high initial pH, is also not a. critical operating procedure. It will vary quite widely with different dyestuffs and with difierentfabrics. In general it will never be lower than 5.5 andthe upper limit is from about 8 to 9.5. Theupper limit is. defined, not So much bythe reaction, itself, as by the fabric, because it is necessary to maintain the pH below the point at which thebasic, nitrogenous fibers areiciu q, e era he ni hpfis be chosen uf i ient yhish tar tmrd-imtim chr- These mation.
  • the pH initially should be high enough so that the complex, if there be one present, is not decomposed until the dyeing of the fiber'has proceededto the desired extent.
  • the pH of the dye bath is lowered by the dyeing procedure itself, probably because of a reaction of the basic nitrogenous fiber with the alkali present, this lowering is usually insufficient, hence in the majority of cases.it-is;desirable ;to.'add--small .amountsof acid or acid salts as the dyeing proceeds.
  • the .acid is added in.parts- .1after. onehalf houraboiling, and' after an,hour s boiling.
  • The-exact amountwf addition -of. acid and .the timeand.portionsare not critical but optimum results .will vary a little with different colors. This is entirely consistent with.
  • Example 1 One part of the condensation pro'ductof octadecyl uanidine bicarbonate and ethylene oxide (1 mole to 6 moles) aredissolved in an excess of organic solvent, e. g., ether. 20 parts .of Epsom salts are. added and the ether evaporated slowly with constant stirring to deposit the cationic agent on theEpsom salts base. .Finally theproduct isvacuum dried. When the drying is completed, the product is grindaole. 52.5 parts of this product is dry-blended with 3 parts of powdered K2C1207 .togive a mordant. Twelve percent of thisproduct (based on the weight of the wool) is used with 2% of the ordinary commercial chrome types to give a satisfactory dyens. The. dyeinais. made as. follows:
  • a 5 gram woolen piece or skein is pre-wet with water and entered into the dye bath at 120 F.
  • the dye liquor is gradually brought to the boil in hour with frequent turning of the wool to insure uniform dyeing.
  • Boiling and turning are continued for hour, after which 2% of 28% acetic acid is added.
  • 4% of 28% acetic acid is added.
  • Dyeing is continued at the boil for a third half-hour making a total dyeing time of two hours.-
  • the color of the dyed skein is blue-black and the dyeing has good fastness and is very level. Ordinarily this color can be dyed satisfactorily only by the very cumbersome top or bottom chrome method.
  • Example 2 37.5 parts of corn dextrine made by dextrinizing corn starch with hydrochloric acid, 37.5 parts of Epsom salts, 3.75 parts of the cationic agent of Example 1, 4.5 parts of KQCI2O'1 and about parts of water are wet-blended in a Warner-Pfleiderer mixer until uniform. This gives a thick plastic magma. The product is then transferred to enameled trays and dried in a vacuum dryer, ground and screened through a 140 mesh screen. 12% of this product is substituted for the material in Example 1 and dyeings are carried out in the same way with essentially the. same results.
  • the chrome equivalent amount of KzCrOx can be used in place of the K2CI2O'1.
  • Example 3 The product of Example 2 is used in making a dying of the dye C. I. 652, using the dyeing formula of Example 1. This dye gives an excellent color value which is superior to that obtained by ordinary metachrome dyings or even top chrome dyeings.
  • Example 5 and screened through a 140 mesh screen producing a colloidized mordant.
  • a dye bath is prepared as follows:
  • the dye liquor is gradually brought to the boil in hour with frequent turning of the wool to insure uniform dyeing. Boiling and turning are continued for /2 hour after which of H2SO4 is added. Dying is continued at the boil for a second half hour, after which of H2SO4 is added. Dyeing is then continued for a third half-hour at the boil making a total dyeing time of two hours.
  • the color of the dyed skein is blue-black and the dyeing has good fastness and is fiber level. Ordinarily this color can be dyed satisfactorily only by the very cumbersome top or bottom chrome method.
  • Example 6 The dyeing procedures of the preceding example is repeated using the dye C. I. 652 instead of the dye of Example 5.
  • the dye gives an excellent color value which is superior to that obtained by ordinary metachrome dyeings or top chrome dyeings.
  • Example 7 500 parts of the dextrine of Example 2 and parts of the cationic surface active agent described in Example 5 are colloidized in a Werner- Pfieiderer mixer with just suificient water to give a stiff plastic magma. The product is then dried, ground and screened as described in Example 5. 30 parts of the screened material are dry-blended with 100 parts of Epsom salts and 6 parts of potassium bichromate.
  • a dye bath is prepared with 13.5% of the above mordant and 2% of 28% ammonia (both on the .'eight of the wool) and 2% of dye having C. I. 203 are added, and the dyeing is carried out by the procedure of Example 1 or Example 5.
  • the dyeing produces a blue-black shade which is fiber level and has excellent fastness properties.
  • Example 8 A dye bath is prepared as described in Example 4 using 7% of mordant and 6% of dye. Wool is dyed in the bath and builds up with the increased amount of color to give a very dark, blue-black shade of excellent fastness properties and fiber levelness.
  • Example 9 500 parts of the dextrine of Example 2 and 100 parts of cationic surface active agent as described in Example '7 are colloidized and vacuum dried. 30 parts of the product are blended with 35 parts of 100 mesh Epsom salts and 8.3 parts of potassium bichromate until a uniformly blended product is obtained.
  • Example 2 parts of the dyeCt'IrZM; andonepartof'the condensation product-of*2-mols of polyethylene oxide (molecular weight 4000) and ,1 mol of the .dimerized'. acidobtained by heat treating gsoya bean acids and distilling off the monomericacids are dry blended. 3% oflthissproduct;6%ofthe mordant of Example 4 and:2% of:28%rammoni'a are dissolved in 400 parts of water and wool is dyed therein by the,proce'dure of Example 1. A good, bright orange'color'is obtained and the dyed wool has good fastness and levelness.
  • Theprocedureof Examplee is repeated,- except the dye is C.I. -652 andthe material'is nylon. A strong, bright red shade is, obtained.
  • Example 14 The procedure of the-preceding example is repeated except thedye is C.--I..292. 'A good slate .greenshade is obtained which is commercially satisfactory.
  • Example 15 50.,parts of the. dextrine of Example -2'.and 10 parts of the condensation..product -of.octadecyl guanidine bicarbonate .andethylene oxide (5-1) are colloidized-andvacuum dried. .Thisaproduct .isathen .ground, screened throughma 100 mesh screen,..and dry blended with 40 parts of the commercial dye havingColor- Index. N o. v203.
  • A' dyeingis prepared as follows:
  • the bath is brought 'to. the boil gradually in 30 minutes, boiled 30 minutes, after which 3% of the 28% acetic a'cidis added. After ana'dditional 30 minutes at the boil, a secondadditl'on of 3% ofi28% acetic acid isadded and the boilm continued for another"30 minutes.
  • Wool dyed as above' has a brilliant yellow color, showing excellent levelne'ssand good 'fa'st- 'ne'ss properties.
  • Example] ? .
  • The, procedure of Example 1 is'repeated except the dye C. I.. 1085 is ,used instead of C. L202 of Example ,1.
  • the dyeing produces -.a .blueblack shade which is levelaand'has excellent fast- :ness properties.
  • a dye bath is preparedzasifollows, all weights being based on the wool.
  • Example 19 The procedure: of Example No; 18 is repeated except the dye-having Color-Index 'No. 652 is used instead of the dye havingColor'InderNo. 202. 'Wool dyed by-this color and procedure gives excellent strength and levelness, usually superior to the conventionaltopchrome methods of dyeing.
  • Example- No. .18. isxrepeate'd except the dye havinglColorIndex No. 9835 used in place of thedyehaving Colorlndex No. 202 Wool dyed'bythis color and.procedure has-er- :cellent strength and fiberlevelness, .beingtequal usually to .a top :chrome :d-yeingas; made by the conventional methods.
  • Example 21 The procedure of Example No. 18 is repeated except the dye having Color Index No. 1085 is used in place of the dye having Color Index No. 202. Wool dyed by this color and procedure has good color value and fiber levelness.
  • Example 22 The procedure of Example No. 18 is repeated except the dye having Color Index No. 201 is used in place of the dye having Color Index No. 202. Wool dyed by this dye and procedure is stronger and brighter than wool dyed with an equivalent amount of dye which is dyed by the conventional top chrome procedure.
  • Example 23 The procedure of Example 18 is repeated except the dye having Color Index 274 is used in place of the dye having Color Index No. 202. Wool so dyed has excellent color value, is bright and has good fiber levelness.
  • Example 24 400 parts of yellow corn dextrine and 100 parts of the cationic surface active agent described in Example 1 are intimately mixed and vacuum dried as described. parts of this material are then-dissolved in 95 parts of water to give a 1% solution of the cationic surface active agent.
  • a dye bath is then prepared as follows:
  • Epsom salts 0.6% potassium bichromate
  • a 5-gram pre-wet wool skein is then dyed therein, using the dyeing procedure on Example No. 1 and the strength and shade of the dyed wool is very fiber level and is usually stronger than equivalent dyeings made by the conventional top chrome procedure.
  • Magnesium acetate or magnesium chloride may be substituted for the Epsom salts.
  • the addition of the ammonium hydroxide generally changes the pH to 9-9.6 depending upon the pH of the water added to the dyebath.
  • the shade of the dye having Color Index No. 203 is plum colored or reddish after the addition of the water to make up the dyebath, particularly if distilled water having a pH lower than '7 is used. After the addition of the ammonium hydroxide, the shade of this color becomes greenish-blue.
  • the Epsom salts the color of the dye solution becomes a cherry red, although there is no appreciable change in pH. During the subsequent dyeing, this dyebath exhausts very rapidly, much more so than when a similar dyeing is made except the Epsom salts is omitted.
  • Example 25 The procedure of Example 24 is repeated, except 10% of calcium nitrate .4 B is substituted for the Epsom salts of Example 24.
  • the shade of the dyed wool is slightly grayer than that obtained when Epsom salts is used.
  • the addition of 10% of the calcium nitrate .4: H2O based on the weight of the wool to the dyebath likewise caused no appreciable change in pH but did cause the blue green shade of the dye solution to become a brighter red. l
  • Example 26 The procedure of Example 24 is repeated except 10% of barium nitrate is used instead of the Epsom salts.
  • the wool dyed from this bath is slightly bluer and brighter than that dyed by the procedure of Example 24.
  • Example 27 The procedure of Example is repeated except the dye having Color Index No. 652 is used instead of the dye having Color Index No. 203. A good strong red dyeing is obtained. If desired, the calcium nitrate may be replaced with strontium chloride.
  • Example 28 The procedure of Example 18 is repeated exactly except 0.5% of the surface active agent, tertiary amine hydroacetate, prepared according to U. S. P. 2,200,815 is used instead of the surface active agent prepared by the condensation of octa decyl guanidine bicarbonate and ethylene oxide (6:1) which was used in Example 2. W001 dyed with this procedure shows good strong blueblack color with good penetration.
  • Example 29 The procedure of the preceding example is followed exactly except the surface active agent, cetyl pyridinium chloride, is used instead of the tertiary amine hydroacetate of the preceding example. A good strong bright blue-black dyeing is obtained.
  • Example 30 The procedure of the preceding experiment is repeated except the surface active agent, cetyl trimethyl ammonium bromide is used instead of the cetyl pyridinium chloride. A good strong bright blue-black dyeing is obtained.
  • Example 31 The procedure of Example 18 is repeated exactly except the surface active non-ionic agent of Example 18 is replaced by 1% of beta hydrotriethoxy-propyl-lauramide. A good bright blue black dyeing which showed excellent penetration is obtained.
  • Example 32 The procedure of the preceding example is repeated exactly except the beta-hydro-triethoxypropyl-lauramide is replaced with 1% of p-hexadecyl phenyl ether of polyethylene glycol.
  • Example 33 The procedure of Example 18 is repeated except the non-ionic surface active agent of Ex-. ample 18 is replaced with the condensation product of stearyl alcohol with 8 moles of ethylene oxide liquified with 30% E20. Wool dyed by this procedure gives a bright blue-black shade showing excellent penetration and ood fiber levelness.
  • Example 34 l l shades this gives the best results. However, in some cases, particularly with dark-shades .
  • the improved results obtainabletby, meansof the present invention are not always the same with each dye.
  • improved strength and penetration result: in other cases, the levelness is better while with some dyes; improvements in both characteristics are observed; The degree of improvement in various characteristics varies with the dye.
  • theprocess of the present invention shows less'irarked advantages with some yellow dyes than-with dyes of other shades.
  • dyestuff'mixtures havebeen colloidized by working'in a relativel stiff paste with carbohydrates. suchasdextrine and dried at a low temperature so that the individual particles on contact with waterdispersedrapidly without violent agitation to form a colloidal solution.
  • Such product have been described in'the specification as colloidized. This term is used in the claims in no other sense.
  • a sol ble alka neeart m t l salt, a water-disnersihle surface-a ct ve c mposition containin at le st one cation c surface active ag nt.
  • a method of dyeing which comprises sub jecting substantially unmetallized basic nitrogenous fibers to the action of 'a dye bath formed bymixing a chromable dye, a soluble chromium containing salt, a soluble alkaline earth metal salt, a water-dispersible surface active composition containin at'least'one cationic surface activeagent, water, and suificient alk l 170 1 3 the bath alkaline ancl'to cause said dye to react With-.said valkaline'earth metal salt ,t0..f0rm-an alkaline eanthmetalicomplexof saiddye and in: sufficient tomaterially damage thefibers,.par.-.
  • a chromable dye bymixing a chromable dye; a soluble chromium containing salt,- magnesiium sulfate, a waterdispersible surface-active composition containing at least one cationic surface active agent, water, and sufiicient alkali to make the bat-halkalinc andito cause said dye to reactwith said alkaline.
  • a vcln'on'iable dye by mixing a vcln'on'iable dye, a soluble chromium containingsalt, .a.-solub1e alkaline earth metal salt, a water-dispersiblelsurfaceeactive composition containing at least one cationic surface active agent, water, and suificient. alkali to make the. -.bath.,alkaline, but .with apI-lnot greater than 9.5, and to cause saiddye to react with said alkaline earth metal salt to form.
  • alkaline earth metal complex of said and-.imufiicient to materially damage the fibers partially dyeing said fibers from said complex, gradually lowering the pI-lof said bath to a point where decomposition -ofsaid complex and chromation take place, and completing-the dyeing at lowered :pH.
  • 6.-'A-method -of dyeing which comprises subjecting substantially unmetallized basic nitrogenous fibers to the action of a dye bath formed by mixing a chr mable dye, a soluble chromium containing salt, magnesium sulfate, a waterdispersible surface-active composition containing at least one cationic surface active agent, water, and sufficient alkali to make the bath alkaline, but.
  • a method according to claim 1 in which the cationic surface active-agent is a condensation product of octadecyl guanidine and ethylene oxide.
  • the cationic surface active agent is a condensation product of octadecyl guanidine and ethyleneox-- ide.
  • the cationic surface active agent is a condensation 2,520,105 13 14 product of octadecyl guanidine and ethylene oX- OTHER REFERENCES ide.

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Description

Tatented Aug. 22,
UNITED STATES PATENT OFFICE METACHROME DYEING PROCEDURE No Drawing. Application May 2'7, 1947, Serial No. 750,886
10 Claims.
This invention relates to improved metachrome dyeing processes.
In the past there have been four general procedures employed in dyeing with metallizable dyes. The first utilizes preformed metallized dyes and requires the formation of the metallized dye before it is introduced. into the dye bath. Practically all of the metallizable dyes may be utilized in this process, but it is subject to a number of disadvantages. The dye is not very efficiently used, the dye bath is poorly exhausted, and the color value is not as high as desirable in some cases.
The second process is referred to as an after chrome or top chrome procedure in which the fabric is dyed with metallizable dyes and then subjected to an after treatment with a solution of a compound of the metal to be introduced into the dye molecule. As the name implies, the dye is applied the same as an acid dye, and it requires an extra process and extra time for the formation of the metallized complex.
The third procedure is the so-called bottom chrome process in which a metal compound is first deposited in the textile fiber and then the dye is applied and the metaliized complex forms in the fiber. Here again this process is an extremely long one requiring several steps.
The fourth procedure is the so-called metachrome process in which the metallizable dye and the compound of the metal to be introduced are both present in the dye bath at the start and the metailized dye is formed both in the fiber and in the bath itself and not introduced as a preformed compound.
The metachrome process presents many advantages. However, in many cases the dye is not eiiectively utilized when dyeing basic nitrogenous fibers such as the natural animal fibers, Wool, silk, and the like or synthetic fibers of similar type from casein, polyamides, and so forth. Certain dyes give good uniform liber'penetration in a yarn, and others penetrate only some of the fibers. The dyes which do not penetrate all of the fibers or are destroyed during the dyeing operation, particularly in the case of heavier shades, have, therefore, been considered unsuitable for use in the metachron'ie process and have required resort to the process starting out with the preformed inetallized dye or the top or bottom chrome processes With'their attendant disadvantages.
According to the present invention it is found that markedly increased strength and levelness of dyeing is obtained if three factors are present in the process. These three factors are:
let: The presence of a salt of an alkaline earth metal.
2nd: A water dispersible surface active composition containing at least one cationic surface active agent.
3rd: The pH of the dye bath is sufficiently high initially so that rapid chromation is prevented or retarded, and during the dyeing process the pH is progressively lowered until final chromation results.
With certain dyes any one of the three factors referred to above will efiect some improvement either in color value or levelness, but with certain other dyes, both of these improvements in dyeing characteristics are not obtained with metallizable dyes unless all three of the above reaction conditions are present, and the present invention contemplates only processes in which all three factors are efi'ective.
The alkaline earth metal'salts or salts to be used are not in the least critical. Any of the common soluble salts may be used. The difierent alkaline earth metal salts will vary to some extent in their effect, and this variation is not the same with all metaliizabie dyes. In general, best results are obtained with magnesium salts, magnesium sulfate being particularly desirable, by reason of its cheapness, ready availability and the excellent results which it gives in the process of the present invention. Accordingly magnesium sulfate represents the preferred alkaline earth metal salt, though in its broader aspects the invention is not limited to its use.
The reason for the improved results obtainable wi'th alkaline earth metal salts, and particularly the increased strength of dyeing which follows their use, has not been completely determined and, therefore, the present invention is not intended to be limited to any theory of the action of the alkaline earth metal salts. Certain observations with certain dyestuffs make it appear very probable, that at least with some dyestuffs, magnesium or the other alkaline earth metal salts actually form metal complexes with the dye,\which complexes are only stable in solutions of high pH. Some of the dyes change their color very strikingly when they are introduced into a dye bath containing the alkaline earth metal salt. Such a great change in color, which is again reversed as the dyeing proceeds and the pH fails to sufiiciently low Values, makes it almost certain that there is an actual chemical change in the dye molecule. The conditions unexplanation is advanced, therefore, as probable in the case of some at least of-"the'metallisable dyes which may be used in the processv of the present invention.
It is an advantage of the invention: that the amount of the added alkalinecearthrmetal salts.
is not critical. It should, however, be realized that the action appears to be in no sensecatalytic. Relatively substantial amounts of alkaline earth metal salt must be added. Normally the amount added is at least, equal to the weight of the.,dye,-althQugh-.this figure does notrepresent a sharp or critical dividin line. ;S maller-amounts will.exert effect, but -onewhich rapidly diminishes as the amount of salt becomes inadequate. .It;has..been found; that the amount of alkaline earth.:meta1 salt-maybe advantageously correspondingly greater than the Weightmf the dyestuff. .Eor. example, .the .use..of, five times as much alkaline earthmetal .salt gives excellent. results,- and:since thealkaline earth .metal .salts, are relatively. cheap. chemicals-tit is. preferred, to .use them in excess of the weight of the dyestufi-,..although the inventionds notbroadly limited to this preferred amount.
The second factor requires .a:.water. dispersible surface active composition containing-at least one cationic surface active agent. It is also .desirable that any insoluble reaction products of the cationic surfaceactive' agent be likewise dispersible. Thisdispersibility of the surface active composition may be'effected in-several'ways. For-instance; the cationic surface active agent may be colloidized-eithei =by itselfor in combination with the dyestuff .or-alka-line earth metal salt -or-with --the 'chromating mordant. methods --.are I described in--Patent--*No. 2,434,178 issued January-6, i948 to-Royerand-'Amick. -Another method ofbbtaining waterdispersibi-lity-is to associate-the cationic surface'active agent with nonionic surface active'agents as is described in' the Millson an dRoyer application SerialNo 42p;50e, filed November 26,1941.
The presentinvention is not concerned with the particular methods of achieving dispersibility of the surface active component, this forming the subject matter of the applications above referred to. .On the contrary, the presentinvention is concerned only with water dispersible cationic surface active compositions when associated with the other twofactors of the processof the present invention, namely, the presence of the alkalineearth metalsalt, and the initial high pH of the dye bath.
.The third factor, namely, high initial pH, is also not a. critical operating procedure. It will vary quite widely with different dyestuffs and with difierentfabrics. In general it will never be lower than 5.5 andthe upper limit is from about 8 to 9.5. Theupper limit is. defined, not So much bythe reaction, itself, as by the fabric, because it is necessary to maintain the pH below the point at which thebasic, nitrogenous fibers areiciu q, e era he ni hpfis be chosen uf i ient yhish tar tmrd-imtim chr- These mation. With dyestuffs with which it seems probable that a complex is formed with the alkaline earth metal salt, the pH initially should be high enough so that the complex, if there be one present, is not decomposed until the dyeing of the fiber'has proceededto the desired extent.
.,As the fibers, are dyed-.andxthe normal-heating of the bath continues, there is a definite lower- ,ing of pH, the bath becoming more and more acid. When the pH gets low enough, both dyeing and chromation proceed more rapidly, and a final dyeing of "high strength and good levelness results. Thus. it -.is.--now possible to obtain deep .shades,.-.such.-;as\adeep chrome black, by a true metachrome process.
.While, as vpointed out above, the pH of the dye bath is lowered by the dyeing procedure itself, probably because of a reaction of the basic nitrogenous fiber with the alkali present, this lowering is usually insufficient, hence in the majority of cases.it-is;desirable ;to.'add--small .amountsof acid or acid salts as the dyeing proceeds. :Preferably the .acid: is added in.parts- .1after. onehalf houraboiling, and' after an,hour s boiling. The-exact amountwf addition -of.=acid and .the timeand.portionsare not critical but optimum results .will vary a little with different colors. This is entirely consistent with. normal dyeing practice .wvhereit .is usually necessaryto make some changes .insthe dyeing time, temperature, and pI-Iwith difierent dyes andsdifierenhfibers in order.to get the best results. .The same typeof adjustment is employed in the proeesszofthe present ,inventio .:which is an advantageas .the dyer. doespnot have. to learmnewtechniques.
.While .-the .process of the .present .invention giyes, important improvementindyeing. withordinary dyes.:by.:the metachrome.method, producing stron shades with .axhigh .degreeof .levelness.-and excellenceolifastness to. lightand ful1ing,.a. further; advantagalies .in .the fact that -certain chromable dyes, .which .are rdyeable. in; the .metachrome-process only when the woolhhas been modifiedby oneofgtne .various non-feltingtreatments ysuch ,as chlorination, can ,be dyed by the present;p10,0$ on, ordinary wool. This ,is important as it opens 1 11a new, field for thesedyes. In addition, to the improved results obtained by the process of the present invention, a, further advantage. lies in the material saving whichcan be effected in the amountof chromium containing salt used. In ,iavorable cases this may amount to 40 or The invention will ,be described in greaterdetail in conjunction with the following specific examples. Theparts are by weight.
Example 1 "One part of the condensation pro'ductof octadecyl uanidine bicarbonate and ethylene oxide (1 mole to 6 moles) aredissolved in an excess of organic solvent, e. g., ether. 20 parts .of Epsom salts are. added and the ether evaporated slowly with constant stirring to deposit the cationic agent on theEpsom salts base. .Finally theproduct isvacuum dried. When the drying is completed, the product is grindaole. 52.5 parts of this product is dry-blended with 3 parts of powdered K2C1207 .togive a mordant. Twelve percent of thisproduct (based on the weight of the wool) is used with 2% of the ordinary commercial chrome types to give a satisfactory dyens. The. dyeinais. made as. follows:
2% dye (C. I. 202) predispersed, in boiling water was admixedwith'12% of the mordant and a sumcient amount of ammonia or ammonia and ammonium salt such as ammonium dihydrogen phosphate, to produce a pH of about 8.5 to 9.0 in a 400ccfvolurrie, sufficient Water being used to make the necessary dilution.
A 5 gram woolen piece or skein is pre-wet with water and entered into the dye bath at 120 F. The dye liquor is gradually brought to the boil in hour with frequent turning of the wool to insure uniform dyeing. Boiling and turning are continued for hour, after which 2% of 28% acetic acid is added. After another half-hour on the boil, 4% of 28% acetic acid is added. Dyeing is continued at the boil for a third half-hour making a total dyeing time of two hours.- The color of the dyed skein is blue-black and the dyeing has good fastness and is very level. Ordinarily this color can be dyed satisfactorily only by the very cumbersome top or bottom chrome method.
Example 2 37.5 parts of corn dextrine made by dextrinizing corn starch with hydrochloric acid, 37.5 parts of Epsom salts, 3.75 parts of the cationic agent of Example 1, 4.5 parts of KQCI2O'1 and about parts of water are wet-blended in a Warner-Pfleiderer mixer until uniform. This gives a thick plastic magma. The product is then transferred to enameled trays and dried in a vacuum dryer, ground and screened through a 140 mesh screen. 12% of this product is substituted for the material in Example 1 and dyeings are carried out in the same way with essentially the. same results.
The chrome equivalent amount of KzCrOx can be used in place of the K2CI2O'1.
Example 3 The product of Example 2 is used in making a dying of the dye C. I. 652, using the dyeing formula of Example 1. This dye gives an excellent color value which is superior to that obtained by ordinary metachrome dyings or even top chrome dyeings.
Example .4
500 parts of the dextrine of Example 2 .and 100 parts of the condensation product of octadecyl guanidine bicarbonate and ethylene oxide (1 mole to 6 moles) are blended in a Werner-Pficiderer mixer with sufiicient water to give a stifi plastic magma. The well mixed material is then transferred to enameled trays and vacuum dried. It is then ground and screened through a 140 mesh screen. parts of this product, 24 parts of 100- mesh Epsom salts, and 6 parts of 140 mesh KzCrzO'z are dry-blended to give a mordant. 6% of this mordant and 2% of 28% NH4OH (both on the weight of the wool) and 100 mg. of the dye having C. I. 203 are dyed on a 5 gram woolen skein as in Example 1. The dyeing obtained is blueblack, has excellent fastness properties and is fiber level.
Example 5 and screened through a 140 mesh screen producing a colloidized mordant.
A dye bath is prepared as follows:
0.1 g. dye (C. I. 202) predispersed in boiling Water, approximately 2% of 28% NH/LOH to give a pH not greater than 9.5
12% colloidized mordant 400 cc. dye bath volume A 5 gram woolen piece or skein is pre-wet with 'water and entered into the dye bath at 120 F.
The dye liquor is gradually brought to the boil in hour with frequent turning of the wool to insure uniform dyeing. Boiling and turning are continued for /2 hour after which of H2SO4 is added. Dying is continued at the boil for a second half hour, after which of H2SO4 is added. Dyeing is then continued for a third half-hour at the boil making a total dyeing time of two hours.
The color of the dyed skein is blue-black and the dyeing has good fastness and is fiber level. Ordinarily this color can be dyed satisfactorily only by the very cumbersome top or bottom chrome method.
The same results are obtained if the potassium bichromate is substituted by a chromium equivalent amount of potassium chromate.
Example 6 The dyeing procedures of the preceding example is repeated using the dye C. I. 652 instead of the dye of Example 5. The dye gives an excellent color value which is superior to that obtained by ordinary metachrome dyeings or top chrome dyeings.
Example 7 500 parts of the dextrine of Example 2 and parts of the cationic surface active agent described in Example 5 are colloidized in a Werner- Pfieiderer mixer with just suificient water to give a stiff plastic magma. The product is then dried, ground and screened as described in Example 5. 30 parts of the screened material are dry-blended with 100 parts of Epsom salts and 6 parts of potassium bichromate.
A dye bath is prepared with 13.5% of the above mordant and 2% of 28% ammonia (both on the .'eight of the wool) and 2% of dye having C. I. 203 are added, and the dyeing is carried out by the procedure of Example 1 or Example 5. The dyeing produces a blue-black shade which is fiber level and has excellent fastness properties.
Example 8 A dye bath is prepared as described in Example 4 using 7% of mordant and 6% of dye. Wool is dyed in the bath and builds up with the increased amount of color to give a very dark, blue-black shade of excellent fastness properties and fiber levelness.
Example 9 500 parts of the dextrine of Example 2 and 100 parts of cationic surface active agent as described in Example '7 are colloidized and vacuum dried. 30 parts of the product are blended with 35 parts of 100 mesh Epsom salts and 8.3 parts of potassium bichromate until a uniformly blended product is obtained.
7% of the mordant produced and 2% of 28% ammonia together with 2% of the dye C. I. 292 are made into a dye bath. Wool is dyed in skein form as described in the foregoing examples, and astrong green dyeing is obtained having excellent fastness properties.
Example 2 parts of the dyeCt'IrZM; andonepartof'the condensation product-of*2-mols of polyethylene oxide (molecular weight 4000) and ,1 mol of the .dimerized'. acidobtained by heat treating gsoya bean acids and distilling off the monomericacids are dry blended. 3% oflthissproduct;6%ofthe mordant of Example 4 and:2% of:28%rammoni'a are dissolved in 400 parts of water and wool is dyed therein by the,proce'dure of Example 1. A good, bright orange'color'is obtained and the dyed wool has good fastness and levelness.
.Example 11 A dye'bath is prepared: with l'partof the .dye having" the i Color Index #203 (pure presscake) idispersed'in.20001parts ofgboilingwater. This-is then diluted with an equal amount. of water containing'6 parts of the'mordant of Example' 4'' and? parts of. 28 ammonia. Fifty .parts of pre=wet wool'arethenientered' and dyed as inExample 5. A black shaderof' goodfiberlevelness is obtained.
Example 12 The procedure of Example eis-repeated, except the dyeinggis'made -on-synthetic'casein fiber and the dyeis nitro amino phenol diazotized and coupled with-metaphenylene diamine which is diazotized and coupledto=5-sulfo a-naphthol, Prototype 14. obtained.
Example: 13
Theprocedureof Examplee is repeated,- except the dye is C.I. -652 andthe material'is nylon. A strong, bright red shade is, obtained.
Example 14 .The procedure of the-preceding example is repeated except thedye is C.--I..292. 'A good slate .greenshade is obtained which is commercially satisfactory.
Example 15 50.,parts of the. dextrine of Example -2'.and 10 parts of the condensation..product -of.octadecyl guanidine bicarbonate .andethylene oxide (5-1) are colloidized-andvacuum dried. .Thisaproduct .isathen .ground, screened throughma 100 mesh screen,..and dry blended with 40 parts of the commercial dye havingColor- Index. N o. v203.
.A batchof. woolen fabric is dyed in a commer cial dye, kettle as follows:
10% of the above blendedcolor ammonium acetate 3.3% Epsom salts 0.7% potassium dichromate .The cloth was entered into the .dye kettle, and .wetv outwith water. If necessary, vthe cloth.-is treated to make it neutral, after which the :treating water was discharged from the kettle, refilled, heated to 120 F. and the above ingredients added 'in the order given. The starting pH was about 5-.5 as determined by Universal indicator paper. The dye liquor was slowly heated to. 207 to 208 F. at which time the .pH wasjabout 6.0 and runabout loyminutes, after which 2% of 28% acetic acidwas ied'on and the pH idropped to'5'.0. After dyeing for an additional i0 minutes, 2% of 28%-acetic. acid wasaddeda second time, .and thepHiremained about'5;0.
When the dyeing was .completed,-the woolen "fabric was dyed a; .black .color. having. goodfast- "ness and levelness.
An excellent brown dyeing is "A :dyeing composition is prepared 'fby dry blending 60-parts'of the colloidized cationic surfaceactive agent of the preceding example-with 40 parts-of the yel1ow"dyestuff"prepared bydlazotizing sulfanilic-acid and coupling to 2=hydroxy-i-amino benzoic acid.
A' dyeingis prepared as follows:
,All weights'are based uponthe weight :of .the
.wool to be dyed 5% of the blended dye prepared as 'in themeceding paragraph 10% ammonium sulfate 0.6%v potassium dichromate Bath ratio: -1
-The-starting pH'of this'dye solution wlll'vary from a pH" of5.0-6;0 depending uponthe-previoushistory of the-wool and how thoroughly it has been neutralized after the" preceding operation.
The bath is brought 'to. the boil gradually in 30 minutes, boiled 30 minutes, after which 3% of the 28% acetic a'cidis added. After ana'dditional 30 minutes at the boil, a secondadditl'on of 3% ofi28% acetic acid isadded and the boilm continued for another"30 minutes.
Wool dyed as above'has a brilliant yellow color, showing excellent levelne'ssand good 'fa'st- 'ne'ss properties.
Example]? .The, procedure of Example 1 is'repeated except the dye C. I.. 1085 is ,used instead of C. L202 of Example ,1. The dyeing produces -.a .blueblack shade which is levelaand'has excellent fast- :ness properties.
.Examplell A dye bath is preparedzasifollows, all weights being based on the wool.
2%.dye having Color Index No..-202 2 %.;of .28 ammonium hydroxide 1%. of the non-ionic agentpreparediyrreactlng ,;2 moles of poly-ethylenezoxide (M.-W.-.4000) and 1 mole of the dimerized acidmbtainemby heat treating soya bean acids and distilling on the monomeric acid 0.5%. of .the. cationic-activeagent--of Example -No. 1 10% Epsom salts 0i6.%..potassium dichromate The dye bath isthen made up to 40000. with water, after which a 5-gram 'woole'n piece or ske'in'is .p're-Wet and dyed as'in Example No..-1 orNo. 5'andthe strength and shade of the dyed piece .is rgenerallylikethat obtaine'dirom Eia'm'ple No. 1
Example 19 The procedure: of Example No; 18 is repeated except the dye-having Color-Index 'No. 652 is used instead of the dye havingColor'InderNo. 202. 'Wool dyed by-this color and procedure gives excellent strength and levelness, usually superior to the conventionaltopchrome methods of dyeing.
'ExampZe'ZO The procedure :of Example- No. .18. isxrepeate'd except the dye havinglColorIndex No. 9835 used in place of thedyehaving Colorlndex No. 202 Wool dyed'bythis color and.procedure has-er- :cellent strength and fiberlevelness, .beingtequal usually to .a top :chrome :d-yeingas; made by the conventional methods.
Example 21 The procedure of Example No. 18 is repeated except the dye having Color Index No. 1085 is used in place of the dye having Color Index No. 202. Wool dyed by this color and procedure has good color value and fiber levelness.
Example 22 The procedure of Example No. 18 is repeated except the dye having Color Index No. 201 is used in place of the dye having Color Index No. 202. Wool dyed by this dye and procedure is stronger and brighter than wool dyed with an equivalent amount of dye which is dyed by the conventional top chrome procedure.
Example 23 The procedure of Example 18 is repeated except the dye having Color Index 274 is used in place of the dye having Color Index No. 202. Wool so dyed has excellent color value, is bright and has good fiber levelness.
Example 24 400 parts of yellow corn dextrine and 100 parts of the cationic surface active agent described in Example 1 are intimately mixed and vacuum dried as described. parts of this material are then-dissolved in 95 parts of water to give a 1% solution of the cationic surface active agent. A dye bath is then prepared as follows:
2% of the dye having Color Index No. 203 predissolved in 100 ml. water 300 ml. of water 2% of 28% ammonium hydroxide 2.5 ml. of the 1% solution of cationic surface active agent described above.
% Epsom salts 0.6% potassium bichromate A 5-gram pre-wet wool skein is then dyed therein, using the dyeing procedure on Example No. 1 and the strength and shade of the dyed wool is very fiber level and is usually stronger than equivalent dyeings made by the conventional top chrome procedure. Magnesium acetate or magnesium chloride may be substituted for the Epsom salts.
The addition of the ammonium hydroxide generally changes the pH to 9-9.6 depending upon the pH of the water added to the dyebath. The shade of the dye having Color Index No. 203 is plum colored or reddish after the addition of the water to make up the dyebath, particularly if distilled water having a pH lower than '7 is used. After the addition of the ammonium hydroxide, the shade of this color becomes greenish-blue. Upon the addition of the Epsom salts the color of the dye solution becomes a cherry red, although there is no appreciable change in pH. During the subsequent dyeing, this dyebath exhausts very rapidly, much more so than when a similar dyeing is made except the Epsom salts is omitted.
Example 25 The procedure of Example 24 is repeated, except 10% of calcium nitrate .4 B is substituted for the Epsom salts of Example 24. The shade of the dyed wool is slightly grayer than that obtained when Epsom salts is used. The addition of 10% of the calcium nitrate .4: H2O based on the weight of the wool to the dyebath likewise caused no appreciable change in pH but did cause the blue green shade of the dye solution to become a brighter red. l
10 Example 26 The procedure of Example 24 is repeated except 10% of barium nitrate is used instead of the Epsom salts. The wool dyed from this bath is slightly bluer and brighter than that dyed by the procedure of Example 24.
Example 27 The procedure of Example is repeated except the dye having Color Index No. 652 is used instead of the dye having Color Index No. 203. A good strong red dyeing is obtained. If desired, the calcium nitrate may be replaced with strontium chloride.
Example 28 The procedure of Example 18 is repeated exactly except 0.5% of the surface active agent, tertiary amine hydroacetate, prepared according to U. S. P. 2,200,815 is used instead of the surface active agent prepared by the condensation of octa decyl guanidine bicarbonate and ethylene oxide (6:1) which was used in Example 2. W001 dyed with this procedure shows good strong blueblack color with good penetration.
iii
Example 29 The procedure of the preceding example is followed exactly except the surface active agent, cetyl pyridinium chloride, is used instead of the tertiary amine hydroacetate of the preceding example. A good strong bright blue-black dyeing is obtained.
Example 30 The procedure of the preceding experiment is repeated except the surface active agent, cetyl trimethyl ammonium bromide is used instead of the cetyl pyridinium chloride. A good strong bright blue-black dyeing is obtained.
Example 31 The procedure of Example 18 is repeated exactly except the surface active non-ionic agent of Example 18 is replaced by 1% of beta hydrotriethoxy-propyl-lauramide. A good bright blue black dyeing which showed excellent penetration is obtained.
Example 32 The procedure of the preceding example is repeated exactly except the beta-hydro-triethoxypropyl-lauramide is replaced with 1% of p-hexadecyl phenyl ether of polyethylene glycol.
Example 33 The procedure of Example 18 is repeated except the non-ionic surface active agent of Ex-. ample 18 is replaced with the condensation product of stearyl alcohol with 8 moles of ethylene oxide liquified with 30% E20. Wool dyed by this procedure gives a bright blue-black shade showing excellent penetration and ood fiber levelness.
Example 34 l l shades, this gives the best results. However, in some cases, particularly with dark-shades .such
as maroon; brown,- navy and black; it is. some times advantageous 'to addsmallamounts of ad-.
ditional -bichromates, ior example, .3 to :.5%., to
the bath after it has beenrboiling for about onehalf hour or so. The additional chromium makes the dark shades somewhat'richer and in many cases improves fastness' towet finishing. The
addition of small amounts of the chromatesto the bath after the dyeing has proceeded for some time is therefore included'in the scope of. the present invention.
The improved results obtainabletby, meansof the present inventionare not always the same with each dye. In many cases improved strength and penetration result: in other cases, the levelness is better while with some dyes; improvements in both characteristics are observed; The degree of improvement in various characteristics varies with the dye. In general, theprocess of the present invention shows less'irarked advantages with some yellow dyes than-with dyes of other shades.
In the examples. dyestuff'mixtures havebeen colloidized by working'in a relativel stiff paste with carbohydrates. suchasdextrine and dried at a low temperature so that the individual particles on contact with waterdispersedrapidly without violent agitation to form a colloidal solution. Such product have been described in'the specification as colloidized. This term is used in the claims in no other sense.
We claim.
.1. A. m t d o dyeinrz'wh h compr se subjectingsubstant ally unmetal ized basic nitrogenous fibers to the action of a -dye-bath:-formed. by m xing a-c romable dye. a soluble chromium-.
containin sa t. a sol ble alka neeart m t l salt, a water-disnersihle surface-a ct ve c mposition containin at le st one cation c surface active ag nt. water, and sufli'cient alk l to make the bath alkaline and'to cau e said dye to react w th said a kal ne earth metal salt to'form an alkaline earth meta complex of said dye andinsufficient to materiallv damage the-fibers; partially dyeing said fibers from said complex, gradually lowering t e pH of said hath toqarpoint' to materially damage the fibers, partiallydyeing said fibers from said complex, gradually lowering the pH of said bath to a point where decomposition of said complex and 'chromation take place, and completing the dyeingat said lowered pH.
3. A method of dyeing which comprises sub jecting substantially unmetallized basic nitrogenous fibers to the action of 'a dye bath formed bymixing a chromable dye, a soluble chromium containing salt, a soluble alkaline earth metal salt, a water-dispersible surface active composition containin at'least'one cationic surface activeagent, water, and suificient alk l 170 1 3 the bath alkaline ancl'to cause said dye to react With-.said valkaline'earth metal salt ,t0..f0rm-an alkaline eanthmetalicomplexof saiddye and in: sufficient tomaterially damage thefibers,.par.-. tiallydyeingsaidfibers .from said complex, grade ually loweringthe-pH ofsaidbathby the addition of successive small portions of acid to a point where decompositionof said complex and chromation take placeyandcompleting the dyeingat said lowered pH..-
4. A method of dyeing which comprises: subjectingxsubstantially -unmetallized. basic nitrogenous=fibers to the-action of afdye bath formed.
bymixing a chromable dye; a soluble chromium containing salt,- magnesiium sulfate, a waterdispersible surface-active composition containing at least one cationic surface active agent, water, and sufiicient alkali to make the bat-halkalinc andito cause said dye to reactwith said alkaline.
earth .metalpsalt toform an alkalineearth metalcomplexof said dyeandinsuificient tc materially damage the fiberspartially dyeing'said fibers from said complex, gradually lowering the pH of said bath by the addition of successive small portions of acid to-a'point where decomposition ofrsaidcomplex and chromation take place, and. completing thedyeing at saidlowered pH.
5: Ainethod of dyeing which comprises subjecting-substantially unmetallized 'basic nitrog-:
enousfibers to'the action of a dye bath formed.
by mixing a vcln'on'iable dye, a soluble chromium containingsalt, .a.-solub1e alkaline earth metal salt, a water-dispersiblelsurfaceeactive composition containing at least one cationic surface active agent, water, and suificient. alkali to make the. -.bath.,alkaline, but .with apI-lnot greater than 9.5, and to cause saiddye to react with said alkaline earth metal salt to form. an. alkaline earth metal complex of said and-.imufiicient to materially damage the fibers, partially dyeing said fibers from said complex, gradually lowering the pI-lof said bath to a point where decomposition -ofsaid complex and chromation take place, and completing-the dyeing at lowered :pH.
6.-'A-method -of dyeing which comprises subjecting substantially unmetallized basic nitrogenous fibers to the action of a dye bath formed by mixing a chr mable dye, a soluble chromium containing salt, magnesium sulfate, a waterdispersible surface-active composition containing at least one cationic surface active agent, water, and sufficient alkali to make the bath alkaline, but. witha'pI-I not greater than 9.5, and to cause said dye to react withsaid alkaline earth metal salt to form: analkaline earth metal complex of said dye and insufiicient to materially damage the -fibers,'par-tially dyeing saidfibers from said complex, gradually lowering the pH of said bath toua point where decomposition of said complexand chromation takeplace, and-completing the dyeing at said lowered pH.-
7; A method according to claim 1 in which the cationic surface active-agentis a condensation product of octadecyl guanidine and ethylene oxide.
8. A-method according to'claim 2 in whichthe cationic surface active agent is .-a condensation product of octadecyl guanidine and ethylene oxide.
9.- A method according to claim 4 in which the cationic surface active agent is a condensation product of octadecyl guanidine and ethyleneox-- ide.
10. A method according to claim 6 in which the cationic surface active agent is a condensation 2,520,105 13 14 product of octadecyl guanidine and ethylene oX- OTHER REFERENCES ide.
Theory and Practice of W001 Dyemg by C. L. Bird, published in London in 1947 by the Society of Dyers and Colourists, pages 87, 88.
WILLARD WATKINS 5 Application of Coal Tar Dyestuffs, by C. M. Whittaker, published in London 1919 by Balliere, REFERENCES CITED Tindall and Cox, pages 59-61, inclusive.
The foliowing references are of record in the Applicatign of Dyestuffs by Matthews file 0f t S P t 10 published in New York by John Wiley 8: Sons,
UNITED STATES PATENTS 1920. Pages 356-358.
Metachrome Method of Dyeing, by C. H. A.
Number Name Date Schmitt, article in Amer. Dyes. Reporter for 941,399 Winslow Nov. 30, 1909 J 26 1939 P336 P341 1,511,359 Onnertz Oct. 14, 1924 Pages 2,434,178 Royer Jan. 6, 1948 15

Claims (1)

1. A METHOD OF DYEING WHICH COMPRISES SUBJECTING SUBSTNATIALLY UNMETALLIZED BASIC NITROGENOUS FIBERS TO THE ACTION OF A DYE BATH FORMED BY MIXING A CHROMABLE DYE, A SOLUBLE CHROMIUM CONTAINING SALT, A SOLUBLE ALKALINE EARTH METAL SALT, A WATER-DISPERSIBLE SURFACE-ACTIVE COMPOSITION CONTAINING AT LEAST ONE CATIONIC SURFACE ACTIVE AGENT, WATER, AND SUFFICIENT ALKALI TO MAKE THE BATH ALKALINE AND TO CAUSE SAID DYE TO REACT WITH SAID ALKALINE EARTH METAL SALT TO FORM AN ALKALINE EARTH METAL COMPLEX OF SAID DYE AND INSUFFICIENT TO MATERIALLY DAMAGE THE FIBERS, PARTIALLY DYEING SAID FIBERS FROM SAID COMPLEX, GRADUALLY LOWERING THE PH OF SAID BATH TO A POINT WHERE DECOMPOSITION OF SAID COMPLEX AND CHROMATION TAKE PLACE, AND COMPLETING THE DYEING AT SAID LOWERED PH.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2763529A (en) * 1956-09-18 Compositions and process for dyeing
US3097044A (en) * 1960-04-04 1963-07-09 Geigy Chem Corp Process for coloring polypropylene
US3148936A (en) * 1963-04-12 1964-09-15 Exxon Research Engineering Co Blending polyolefin with chelating agent to improve dyeability

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US941399A (en) * 1908-12-19 1909-11-30 Cassella Color Company Process of dyeing wool.
US1511359A (en) * 1922-05-15 1924-10-14 Anilin Fabrikation Ag Process for dyeing wool with dyestuffs capable of being chromed
US2434178A (en) * 1948-01-06 Metachkome dyeing with a colloid

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2434178A (en) * 1948-01-06 Metachkome dyeing with a colloid
US941399A (en) * 1908-12-19 1909-11-30 Cassella Color Company Process of dyeing wool.
US1511359A (en) * 1922-05-15 1924-10-14 Anilin Fabrikation Ag Process for dyeing wool with dyestuffs capable of being chromed

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2763529A (en) * 1956-09-18 Compositions and process for dyeing
US3097044A (en) * 1960-04-04 1963-07-09 Geigy Chem Corp Process for coloring polypropylene
US3148936A (en) * 1963-04-12 1964-09-15 Exxon Research Engineering Co Blending polyolefin with chelating agent to improve dyeability

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