[go: up one dir, main page]

US2867494A - Method of metallizing azoic dyeings - Google Patents

Method of metallizing azoic dyeings Download PDF

Info

Publication number
US2867494A
US2867494A US601658A US60165856A US2867494A US 2867494 A US2867494 A US 2867494A US 601658 A US601658 A US 601658A US 60165856 A US60165856 A US 60165856A US 2867494 A US2867494 A US 2867494A
Authority
US
United States
Prior art keywords
metallizing
solution
diazo
hydroxy
azoic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US601658A
Inventor
Streck Clemens
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GAF Chemicals Corp
Original Assignee
General Aniline and Film Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by General Aniline and Film Corp filed Critical General Aniline and Film Corp
Priority to US601658A priority Critical patent/US2867494A/en
Application granted granted Critical
Publication of US2867494A publication Critical patent/US2867494A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/01—Complex metal compounds of azo dyes characterised by the method of metallisation
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General 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
    • D06P1/02—General 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 azo dyes
    • D06P1/12—General 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 azo dyes prepared in situ

Definitions

  • the fiber may be impregnated with a coupling component and passed into a solution which contains an active diazo either in the form of freshly prepared diazo or as a Fast Color Salt solution under conditions suitable for coupling.
  • a coupling component which, except for a few diazos which are sufficiently stable per se, are diazo compounds which are stabilized by salt formation such as with certain metallic salts, e. g. MgCl ZnCl SnCl etc., arylsulfonic acids such as naphthalene-1,5-disulfonic acid and naphthalene- 1,3,6-trisulfonic acid, and also borofluoric acid.
  • azoic dyeings One of the outstanding advantages of azoic dyeings is their fastness in contrast to that of the usual azo dyes.
  • the fastness of azoicdyeings has recently been improved by metallizing, i. efby treating the previously dyed fibers with various metallizing agents such as Cu, Co, Cr, Ni and the like.
  • metallizing i. efby treating the previously dyed fibers with various metallizing agents such as Cu, Co, Cr, Ni and the like.
  • the metallizing step represents an extra step and also requires at least about 20 minutes.
  • satisfactory metallization of azoic dyeings is achieved by incorporating the metallizing agent in the soaping bath as taught in my United States patent (Serial No. 316,305).
  • the metallizing agent may be dissolved in a naphtholating bath, the fibrous material impregnated with this bath, usually followed by drying, and the impreg- Fast Color Salts are diazo comnated fiber padded or printed with an active diazo which includes afreshly prepared diazo or a diazo stabilized as a Fast Color Salt, and then metallizing with hot water or preferably with steam.
  • the coupling components may, in general, be selected from the Naphthol AS compounds which are arylides of 2-hydroxy-3-naphthoic acid and related S-hydroxy carboxylic acid derivatives, acetoacetarylides and related fl-oxocarboxylic acid arylides and pyrazolones.
  • Naphthol AS compounds which are arylides of 2-hydroxy-3-naphthoic acid and related S-hydroxy carboxylic acid derivatives
  • acetoacetarylides and related fl-oxocarboxylic acid arylides and pyrazolones may be employed which are capable of coupling to yield a component having the required metallizable group in ortho position to the azo linkage.
  • the following coupling components may bev employed; Z-naphthol, 3- hydroxy-2-.(2,5-dimethoxy) naphthanilide, 3-l1ydroxy-2- (N-naphthyl)naphthamide, 3 hydroxy 2 (4'-chloro) naphthanilide, 3 hydroxy 2 (N-2-methoxy-3-diben'zo'- furyl)naphthamide, 3 hydroxyanthraquinone 2 carboX-o-toluidide, 2-hydroxy-3-dibenzofurancarboxylic acid arylides such as 2 hydroxy 3 dibenz'ofuran;(2'.,5;'di
  • the process of the present invention ljijs 'appltcable'to cotton, and regenerated cellulose, which can be dyed by the process of-thepresent invention.
  • -v V i In practicing the present invention 0.1 to 10 parts of a naphthol-type coupling component isdissolved 1 to parts of water containing 0.1 to 5 parts of caustic baa 100% basis. To this solution is added 0.1 to 10 parts of ametal salt whichwaspreviously, dissolved and coordinated Iii order that han-1am -"salt maintain "solubility under the alkaline condition of a naphthol solution any one of the usual and commercially available chelating agents is used in-'--conjunction with the metal salt.
  • the chelating agent is capable of forming a complex with the metallizing agent and acts as a coordinating agent to maintain the soluble metal salt such as copper, cobalt or nickel in the form of chloride, nitrate, sulfate, acetate, and the like.
  • chelating agents include triethanolamine, tartaric acid, glycine, dimethylglycine, glycollic acid, aspartic acid, glutamic acid, lactic acid, a-hydroxybutyric acid and the like.
  • the amount of chelating agentemployed isthat necessary to .maintain solubility of the metal salt under alkaline conditions and may range from 50-250 parts by weightof chelating agent per 100 parts by weight of metal salt.
  • these chelating agents are added in approximately molecularly equivalent amounts to that of the metallizing compound, but in actual practice the aforementioned proportions may be departed from to obtain the most desirable results depending on conditions of dyeing and type of coordinating agent employed. Approximately one mole copper-to two of dye also gives satisfactory improvement.
  • the metallizing compounds are salts and hydroxides of a metal selected from the group consisting of copper (cupic), nickel and cobalt. They are employed in the form of chlorides, sulphates, acetates, formates, nitrates, and the like. Those compounds are preferred which are relatively water soluble or dispersible.
  • The. amount of metal salt or metal hydroxide, to be employed will usually depend on the degree of metallizing desired. Molar ratios are necessary for complete metallization but the amount may range from about a fraction of an. equivalent to an excess of one equivalent of metal per equivalent of dye.
  • the strength of dyeing is generally. of the order of about 0.0 5..l%. based on theweight of. the fiber, depending on the shade desired, about 0.1-8%. being the usual range to give sufiicient and satisfactory dyeing.
  • the diazo may be supplied by an amine freshly diazotiz ed by. treatment with nitrite in the customary manner, or the diazo may be a stabilized diazo, i. e., in the form of diazonium chloride or sulfate, or in theform of the diazo stabilized as a double salt, i. .e., as a zinc chloride, boron trifluoride, tin chloride, naphthalenedisulfonic acid, etc.
  • Example I A naphthol c-ouplin'g solution was made up by dissolving 3 grams of B-hydroxy-Z-naphthoic acid 'anilide in 6 cc. of isopropyl alcohol, 1 /2 cc. of caustic soda 34 B. andy2 cc. of water.
  • a metal containing solution was made by dissolving 25 grams of tartaric acid in 120 cc. of water. To this soluti on was added 25 grams of copper chloride, 75 cc. of caustic soda 34 B. and made up to 250 cc. with water.
  • the naphthol solution was poured into 50 cc. of water containing 2 /2 cc. of caustic soda 34 B., and 10 cc. of the aqueous alkaline copper chloride solution, and made up to 133 cc. by the addition of water.
  • a gram sample of cotton was padded with the naphthol coupling and metal containing solution and dried. It was then padded with a solution made up by dissolving 6 grams of the zinc chloride salt of tetrazotized dianisidine, 0.5 cc. of commercial wetting agent, which is a 40% cc. solution of a fatty alcohol-ethylene oxide condensation product, and 2 'cc. of 50% aqueous acetic acid and water added to make up to a volume of 133 cc. After padding, the material was exposed to steam at atmospheric pressure for 20-60 seconds.
  • Example 11 Example I was repeated with the exception that in the metal containing solution copper chloride was replaced by 25 grams of cobalt chloride. The dyeing obtained was. somewhat redder than a similar dyeing without metallization with considerably betterlight-, washand chl'orine-fastness;
  • Example Ill Example I was repeated with the. exception that the tartaric acid inthe metal containing solution was replaced by 25 gramsofglycine. A dyeing .was obtained which has considerable light-,. washand chlorine-fastnes's.
  • Example IV Example I was again repeated withthe exception that the 3-hydroxy-2-naphthoic acid anilidewas replaced by 2 grams of 1-phenyl-3-methylpyrazolone. A. dyeing having excellent light-, washand chlorine-fastness properties was obtained.
  • Example V Example I was again repeated with the exception that the 3-hydroxy-2-naphthoic acid anilide was replaced by an equivalent amount of S-hydroXy-Z-naphthoic acid toluidide, and the zinc chloride salt of tetrazotized dianisidine was replaced by an equivalent amount of the zinc chloride salt of diazotized 4-benz amido-2,5-dimethoxyaniline. A dyeing was obtained having excellent light-,' washand chlorine-fastness properties.
  • Example Vl Example VII Example I was again repeated with the exception that the 3-hydroxy-2-naphthoic acid anilide was replaced by an equivalent amount of"2-hydroxybenzeneazo-4-resorcinol, and the zinc chloride salt of tetrazotized di-anisidine was replaced by an equivalent amount of the zinc chloride .double salt of the diazoof S-chloro-o-anisidine. A dyeing was obtained havingexcellent light fastness.
  • Example VIII Example I wasagain repeated with the exception that in the metal containing solution copper chloride was replaced by an equivalent amount of nickel chloride. A dyeing of excellent light and washfastness was obtained.
  • Example IX Example I was again repeated with the exception that in the metal containing solution the copper chloride was replaced by an equivalent amount of copper sulfate. A dyeing of excellent lightand wash fastness was obtained.
  • Example X Example I was again repeated with the exception that the 3-hydroxy-2-naphthoic acid was replaced by 1.5 grams of ,B-naphthol. A deep navy shade was obtained of good light-, washand chlorine-fastness.
  • Example XII Example I was again repeated with the exception that after the padding with the Fast Color Salt, the cotton was given a 30 second rinse in boiling water.
  • Example XIII 2.2 grams of 4-(o-hydroxyphenylazo)resorcinol were dissolved in 6 cc.'ethyl'alcoho1, 1% cc. caustic 34.B. and 2 cc. of water.
  • a metal-containing solution was made up containing: 147 grams of copper sulfate, 683 cc. of water, cc. of triethanolamine and 60 grams of dry caustic.
  • the naphthol solution was poured into a solution containing 50 cc. water, 2 /2 cc. caustic soda 34 B., and 10 cc. of the metallizing solution, and made up to 133 cc. with water.
  • Cotton was padded with this solution and dried. It was then padded with Fast Color Salt and treated with steam, as in Example I. A deep brown of good light fastness was obtained.
  • Example XIV A solution was made up as follows:
  • a padding bath was made up as follows:
  • the cotton was padded with this solution and steamed for 25 seconds. A deep navy, fast to light, dyeing was obtained.
  • Therm'etallizing compounds i. e. metal salts
  • the diazoamino compounds are the usual ones,.free from solubilizing groups in the diazo portion, containing at least one solubilizing group in the amino portion, and in addition, containing a hydroxy or a lower alkoxy substituent ortho to the diazo group, except in the rare instance where the coupling components may contain an o,o'-dihydroxy-type azo configuration.
  • Cotton was printed with printing pastesA and B, steamed in acid steam in a normal manner for 2 minutes, rinsed and dried.
  • the dyeing from solution A was slightly redder, and had much better light fastness than a similar unmetallized dyeing-
  • the dyeing from solution B was slightly less red than A, slightly stronger and showed a similar fastness to v light.
  • Example XVI A printing paste was made upas follows:
  • Rapidogen mix (cresidine diazotized and stabilized with sarcosine+3-hydroxy-3 -nitroQ-naphthanilide), 4 cc. ethylene glycol monoethyl ether, 24 cc. water, 3 cc. sodium hydroxide 34 B., 5 cc. copper solution, as em ployed in Example I, gum tragacanth to printing thickness.
  • Cotton cloth was printed 'with'this paste and developed for 2 minutes in acidified steam. A yellower coloration, having excellent lightfastness, was produced than in an unmetallized dyeing.
  • Example XVII Example XVI was repeated with the exception that the Rapidogen mix was replaced by an equivalent amount of a Rapidogen consisting of dianisidine tetrazotized and stabilized with methyl taurine+phenyl methylpyrazolone, and employing 10 cc. of the copper solution of Example XV. In this case a tan coloration was produced which had excellent light fastness properties.
  • Example XVIII 1. The process of metallizing azoic dyeings which comprises impregnating a fibrous material selected from the class consisting of cotton and regenerated cellulose with an alkaline solution of an azoic coupling component, a coordinating agent selected from the class consisting of aliphatic aminoand hydroxy-carboxylic acids, and a metallizing compound ofthe group consisting of soluble and dispersible salts of copper, cobalt, and nickel, and then treating the impregnated fiber with a diazo solution, in which the diazo is free from solubilizing groups, and simultaneously dyeing and metallizing in situ by treatment.atelevated temperatures with an aqueous medium having a pH of not more than 7, the said azoic coupling component and the said diazo yielding an o, o-dihydroxy configuration in the final dyestufi.
  • An alkaline azoic coupling bath for impregnating fibrous materials selected from the class consisting of cotton and regenerated cellulose prior to dyeing with a diazo compound, free from solubilizing groups, which converts to a complex metal compound comprising an alkaline solution of an azoic coupling component, a coordinating agent selected from the group consisting of aliphatic aminoandhydroxy-carboxylic acids, and a metallizing compound of the group consisting of salts and hydroxides of copper, cobalt, and nickel, the said azoic coupling component yielding upon coupling with the said diazo compound a dyestuflcontaining an o,o'-dihydroxy configuration.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)

Description

United States METHOD OF METALLIZIN G AZOIC DYEINGS Clemens Streck, Loudonville, N. Y., assignor to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application August 2, 1956 Serial No. 601,658
12 Claims. (Cl. 842) This invention relates to an" improved process of metallizing azoic dyeings.
The fiber may be impregnated with a coupling component and passed into a solution which contains an active diazo either in the form of freshly prepared diazo or as a Fast Color Salt solution under conditions suitable for coupling. pounds which, except for a few diazos which are sufficiently stable per se, are diazo compounds which are stabilized by salt formation such as with certain metallic salts, e. g. MgCl ZnCl SnCl etc., arylsulfonic acids such as naphthalene-1,5-disulfonic acid and naphthalene- 1,3,6-trisulfonic acid, and also borofluoric acid. v
One of the outstanding advantages of azoic dyeings is their fastness in contrast to that of the usual azo dyes. The fastness of azoicdyeings has recently been improved by metallizing, i. efby treating the previously dyed fibers with various metallizing agents such as Cu, Co, Cr, Ni and the like. In the art as now practiced, it is necessary to dye the fibrous material with an azoic dye devoid of solubilizing groups followed by an after treatment with a metallizing agent. The metallizing step represents an extra step and also requires at least about 20 minutes. To overcome this, satisfactory metallization of azoic dyeings is achieved by incorporating the metallizing agent in the soaping bath as taught in my United States patent (Serial No. 316,305).
I have found that fibrous material dyed with an azoic dye, free from solubilizing groups and capable of conversion into a complex metal compound, is endowed with improved light-, washand chlorine-fastness properties and of improved shades by carrying out azoic color formation in the presence of the metallizing agent. In other words, the metallizing agent may be dissolved in a naphtholating bath, the fibrous material impregnated with this bath, usually followed by drying, and the impreg- Fast Color Salts are diazo comnated fiber padded or printed with an active diazo which includes afreshly prepared diazo or a diazo stabilized as a Fast Color Salt, and then metallizing with hot water or preferably with steam. Thetemperature and moisture conditions of the hot water or steam, are sufficiently drastic to yield complete metallization together with color development, even when exposed to steam for less than 1 I minute; Theflimportant advantage ofthis improved method. is that a satisfactorymetallized product is. obtained without any additional operations other than the usual dyeing steps. By this, procedure, economical dyeings are obtained as contrasted with the present method of after metallizing which requires additional steps, over and above the dyeing steps, i. "e., treatment with the metallizing agent and-heating; Iv lhedi'azosafid the coupling components employed in accordance with this. invention are those which produce dyes-'havinghydroxy groups ortho to the azo linkage or groups which are convertible into hydroxy groups such as lower alkoxy, i. e. methoxy,'ethoxy, propoxy and butoxy,
"which are fr'eefrom-solubiliz'ing {group s such as sulfonic I and carboxylic acids.
2,867,494 Patented .1m... 5.1 4 5 4-benzamido-2,5-dimethoxyaniline 2,5-dimethoxy-4-(p-nitrobenzeneazo) aniline 4-cyano-2,5-dimethoxyaniline 5-diethylsulfa myl-o-anisidine 4-phenylamino-o-anisidine 5-n-butylsulfamyl-o-hydroxyaniline- 5-amino-6-hydroxyquinoline I In the case where the coupling component contains'the o,o'-dihydroxy configuration, the above may be used, as also those free from the o-hydroxy and alkoxy configura: tion, e. g. p-chloroaniline, p-anisidine, benzidine.
The coupling components may, in general, be selected from the Naphthol AS compounds which are arylides of 2-hydroxy-3-naphthoic acid and related S-hydroxy carboxylic acid derivatives, acetoacetarylides and related fl-oxocarboxylic acid arylides and pyrazolones. However, other compounds may be employed which are capable of coupling to yield a component having the required metallizable group in ortho position to the azo linkage. Thus, in addition to the coupling components specificially set forth in the examples, the following coupling components may bev employed; Z-naphthol, 3- hydroxy-2-.(2,5-dimethoxy) naphthanilide, 3-l1ydroxy-2- (N-naphthyl)naphthamide, 3 hydroxy 2 (4'-chloro) naphthanilide, 3 hydroxy 2 (N-2-methoxy-3-diben'zo'- furyl)naphthamide, 3 hydroxyanthraquinone 2 carboX-o-toluidide, 2-hydroxy-3-dibenzofurancarboxylic acid arylides such as 2 hydroxy 3 dibenz'ofuran;(2'.,5;'di
methoxy)carboxanilide, bis(acetoacet)benzidide, bis(acetoacet)tolidide, acylacetarylides such as acetoacet-4-chloro-2,5-dimethoxyanilide, 3 hydroxy 2 carbazolecarboxylic acid arylides such as Ii-hydroxy-Z-carbazole-(p+ chloro)carboxyanilide, terephthaloyl bisacetoacet (3'- chloro-2',4'-dimethoxy)-anilide, pyrazolones, such as lphenyl-3-methyl-5-pyrazolone, 3-h'ydroxy 2 naphthoic acid arylides, 3-hydroxy-2-anthroic acid arylides, 2-hydroXy-4-nitroaniline 2-naphthol, o-hydroXy-anilineresorcinol, 2-hydroxy-S-nitroaniline resorcinol; ,In ...the case of the couplers in the last two examples listed, wherein the o-hydroxyazo linkage is present in the coupler per se, any ordinary diazo compounds may be employed, such asm-chloro-aniline, o'-nitroahiline, l-aminoanthraquinone .and 2-amino-4,4'-dichlorodiphenyloxide. Other similar couples may be employed, "such as those listed in German Patent 618,748;
The process of the present inventionljijs 'appltcable'to cotton, and regenerated cellulose, which can be dyed by the process of-thepresent invention.-v V i In practicing the present invention 0.1 to 10 parts of a naphthol-type coupling component isdissolved 1 to parts of water containing 0.1 to 5 parts of caustic baa 100% basis. To this solution is added 0.1 to 10 parts of ametal salt whichwaspreviously, dissolved and coordinated Iii order that han-1am -"salt maintain "solubility under the alkaline condition of a naphthol solution any one of the usual and commercially available chelating agents is used in-'--conjunction with the metal salt.
The chelating agent is capable of forming a complex with the metallizing agent and acts as a coordinating agent to maintain the soluble metal salt such as copper, cobalt or nickel in the form of chloride, nitrate, sulfate, acetate, and the like. Examples of such chelating agents (coordinating agents) include triethanolamine, tartaric acid, glycine, dimethylglycine, glycollic acid, aspartic acid, glutamic acid, lactic acid, a-hydroxybutyric acid and the like. The amount of chelating agentemployed isthat necessary to .maintain solubility of the metal salt under alkaline conditions and may range from 50-250 parts by weightof chelating agent per 100 parts by weight of metal salt. Theoretically these chelating agents are added in approximately molecularly equivalent amounts to that of the metallizing compound, but in actual practice the aforementioned proportions may be departed from to obtain the most desirable results depending on conditions of dyeing and type of coordinating agent employed. Approximately one mole copper-to two of dye also gives satisfactory improvement.
As stated above the metallizing compounds are salts and hydroxides of a metal selected from the group consisting of copper (cupic), nickel and cobalt. They are employed in the form of chlorides, sulphates, acetates, formates, nitrates, and the like. Those compounds are preferred which are relatively water soluble or dispersible. The. amount of metal salt or metal hydroxide, to be employed will usually depend on the degree of metallizing desired. Molar ratios are necessary for complete metallization but the amount may range from about a fraction of an. equivalent to an excess of one equivalent of metal per equivalent of dye.
The strength of dyeing is generally. of the order of about 0.0 5..l%. based on theweight of. the fiber, depending on the shade desired, about 0.1-8%. being the usual range to give sufiicient and satisfactory dyeing.
The diazo may be supplied by an amine freshly diazotiz ed by. treatment with nitrite in the customary manner, or the diazo may be a stabilized diazo, i. e., in the form of diazonium chloride or sulfate, or in theform of the diazo stabilized as a double salt, i. .e., as a zinc chloride, boron trifluoride, tin chloride, naphthalenedisulfonic acid, etc.
As illustrative examples of Fast Color Salts the following are illustrative:
Fast Blue .Salt BN CH3 Fast "Blue Salt 2BN GQHIC ONH N'-N-Cl.%ZnCh CaHv Fast Red Salt BN N=NO;
OsN SOsH Fast Red Salt TRN 01Q-N=N'Oa8 Y CHa' aH Fast Black Salt K 4 Fast Bordeaux Salt BD Variamin'e Blue Salt BD Fast Red Salt RL' Fast Red Salt FR weight of the fibrous. material employed unless otherwise indicated.
Example I A naphthol c-ouplin'g solution was made up by dissolving 3 grams of B-hydroxy-Z-naphthoic acid 'anilide in 6 cc. of isopropyl alcohol, 1 /2 cc. of caustic soda 34 B. andy2 cc. of water.
A metal containing solution was made by dissolving 25 grams of tartaric acid in 120 cc. of water. To this soluti on was added 25 grams of copper chloride, 75 cc. of caustic soda 34 B. and made up to 250 cc. with water.
The naphthol solution was poured into 50 cc. of water containing 2 /2 cc. of caustic soda 34 B., and 10 cc. of the aqueous alkaline copper chloride solution, and made up to 133 cc. by the addition of water.
A gram sample of cotton was padded with the naphthol coupling and metal containing solution and dried. It was then padded with a solution made up by dissolving 6 grams of the zinc chloride salt of tetrazotized dianisidine, 0.5 cc. of commercial wetting agent, which is a 40% cc. solution of a fatty alcohol-ethylene oxide condensation product, and 2 'cc. of 50% aqueous acetic acid and water added to make up to a volume of 133 cc. After padding, the material was exposed to steam at atmospheric pressure for 20-60 seconds.
A dyeing was obtained which was somewhat redder than a similar dyeing made without metallization with considerably betterlight-, washand chlorine-fastness.
Example 11 Example I was repeated with the exception that in the metal containing solution copper chloride was replaced by 25 grams of cobalt chloride. The dyeing obtained was. somewhat redder than a similar dyeing without metallization with considerably betterlight-, washand chl'orine-fastness;
Example Ill Example I was repeated with the. exception that the tartaric acid inthe metal containing solution was replaced by 25 gramsofglycine. A dyeing .was obtained which has considerable light-,. washand chlorine-fastnes's.
Example IV Example I was again repeated withthe exceptionthat the 3-hydroxy-2-naphthoic acid anilidewas replaced by 2 grams of 1-phenyl-3-methylpyrazolone. A. dyeing having excellent light-, washand chlorine-fastness properties was obtained.
Example V Example I was again repeated with the exception that the 3-hydroxy-2-naphthoic acid anilide was replaced by an equivalent amount of S-hydroXy-Z-naphthoic acid toluidide, and the zinc chloride salt of tetrazotized dianisidine was replaced by an equivalent amount of the zinc chloride salt of diazotized 4-benz amido-2,5-dimethoxyaniline. A dyeing was obtained having excellent light-,' washand chlorine-fastness properties.
Example Vl Example VII Example I was again repeated with the exception that the 3-hydroxy-2-naphthoic acid anilide was replaced by an equivalent amount of"2-hydroxybenzeneazo-4-resorcinol, and the zinc chloride salt of tetrazotized di-anisidine was replaced by an equivalent amount of the zinc chloride .double salt of the diazoof S-chloro-o-anisidine. A dyeing was obtained havingexcellent light fastness.
Example VIII Example I wasagain repeated with the exception that in the metal containing solution copper chloride was replaced by an equivalent amount of nickel chloride. A dyeing of excellent light and washfastness was obtained.
Example IX Example I was again repeated with the exception that in the metal containing solution the copper chloride was replaced by an equivalent amount of copper sulfate. A dyeing of excellent lightand wash fastness was obtained.
Example X Example I was again repeated with the exception that the 3-hydroxy-2-naphthoic acid was replaced by 1.5 grams of ,B-naphthol. A deep navy shade was obtained of good light-, washand chlorine-fastness.
Example XI 3 grams of 3-hydroxy-2-naphthoic acid anilide and 1 grain of bis(acetoacet)o-to1idide were dissolved in 100 cc. boiling water containing 4 /2 cc. caustic soda 34 B. To this solution, cooled to to about 140 F., was added cc. of the copper chloride solution of Example I.
Cotton was padded with this solution and dried.
It was then padded with a solution of 8.5 grams of zinc chloride double salt of tetrazotized dianisidine, 0.5 cc. of a 40% fatty alcohol-ethylene oxide condensation product, 3 cc. of 50% aqueous acetic acid solution and water added to make up to a volume of 133 cc., followed by treatment with steam for 25 seconds. A deep jet black was obtained of improved light fastness.
Example XII Example I was again repeated with the exception that after the padding with the Fast Color Salt, the cotton was given a 30 second rinse in boiling water.
While the metallizing efiect was not quite as good as the dyeing of Example I, i. e. exposed to steam, it was considerably better in light fastness than a dyeing which had not been metallized.
Example XIII 2.2 grams of 4-(o-hydroxyphenylazo)resorcinol were dissolved in 6 cc.'ethyl'alcoho1, 1% cc. caustic 34.B. and 2 cc. of water.
A metal-containing solution was made up containing: 147 grams of copper sulfate, 683 cc. of water, cc. of triethanolamine and 60 grams of dry caustic.
The naphthol solution was poured into a solution containing 50 cc. water, 2 /2 cc. caustic soda 34 B., and 10 cc. of the metallizing solution, and made up to 133 cc. with water.
Cotton was padded with this solution and dried. It was then padded with Fast Color Salt and treated with steam, as in Example I. A deep brown of good light fastness was obtained.
Example XIV A solution was made up as follows:
soda
-An additional metal-containing paste was made up as follows:
1 II A Parts Copper sulfate 14.7 Triethanolamine 11.0 I and II' were mixed together.
A padding bath was made up as follows:
Acetic acid 50% 2 Water up to 1 gal. 1
The cotton was padded with this solution and steamed for 25 seconds. A deep navy, fast to light, dyeing was obtained.
Therm'etallizing compounds, i. e. metal salts, can be incorporated into the Rapidogen printing pastes and solutions,-, and on development in acidified steam the color is developed and metallizing occurs simultaneously.
The diazoamino compounds are the usual ones,.free from solubilizing groups in the diazo portion, containing at least one solubilizing group in the amino portion, and in addition, containing a hydroxy or a lower alkoxy substituent ortho to the diazo group, except in the rare instance where the coupling components may contain an o,o'-dihydroxy-type azo configuration.
The following examples illustrate the foregoing embodirnent:
Example XV Two solutions were made up as follows:
Solution The copper solution contained 147 parts copper sul- 7. fate, 683 parts water, 110 parts triethanolamine and 60 parts dry caustic.
17 grams of A and 20 grams of B were. thickened with starch tragacanth.
Cotton was printed with printing pastesA and B, steamed in acid steam in a normal manner for 2 minutes, rinsed and dried.
The dyeing from solution A was slightly redder, and had much better light fastness than a similar unmetallized dyeing- The dyeing from solution B was slightly less red than A, slightly stronger and showed a similar fastness to v light.
Example XVI A printing paste was made upas follows:
4 grams Rapidogen mix (cresidine diazotized and stabilized with sarcosine+3-hydroxy-3 -nitroQ-naphthanilide), 4 cc. ethylene glycol monoethyl ether, 24 cc. water, 3 cc. sodium hydroxide 34 B., 5 cc. copper solution, as em ployed in Example I, gum tragacanth to printing thickness.
Cotton cloth was printed 'with'this paste and developed for 2 minutes in acidified steam. A yellower coloration, having excellent lightfastness, was produced than in an unmetallized dyeing.
Example XVII Example XVI was repeated with the exception that the Rapidogen mix was replaced by an equivalent amount of a Rapidogen consisting of dianisidine tetrazotized and stabilized with methyl taurine+phenyl methylpyrazolone, and employing 10 cc. of the copper solution of Example XV. In this case a tan coloration was produced which had excellent light fastness properties.
Example XVIII 1. The process of metallizing azoic dyeings which comprises impregnating a fibrous material selected from the class consisting of cotton and regenerated cellulose with an alkaline solution of an azoic coupling component, a coordinating agent selected from the class consisting of aliphatic aminoand hydroxy-carboxylic acids, and a metallizing compound ofthe group consisting of soluble and dispersible salts of copper, cobalt, and nickel, and then treating the impregnated fiber with a diazo solution, in which the diazo is free from solubilizing groups, and simultaneously dyeing and metallizing in situ by treatment.atelevated temperatures with an aqueous medium having a pH of not more than 7, the said azoic coupling component and the said diazo yielding an o, o-dihydroxy configuration in the final dyestufi.
2. The processv according to claim 1 wherein the metallizing compound is copper chloride.
3. The process according to claim lizing compound is cobalt chloride.
4. The process according to claim 1 wherein the metallizing compound is nickel chloride;
5. The process according to claim 1 wherein the metallizing compound is copper sulfate.
' 6. The process according to claim 1 wherein the metallizing compound is cobalt sulfate.
7. An alkaline azoic coupling bath for impregnating fibrous materials selected from the class consisting of cotton and regenerated cellulose prior to dyeing with a diazo compound, free from solubilizing groups, which converts to a complex metal compound comprising an alkaline solution of an azoic coupling component, a coordinating agent selected from the group consisting of aliphatic aminoandhydroxy-carboxylic acids, and a metallizing compound of the group consisting of salts and hydroxides of copper, cobalt, and nickel, the said azoic coupling component yielding upon coupling with the said diazo compound a dyestuflcontaining an o,o'-dihydroxy configuration.
8. A bath for impregnation of fibrous materials according to claim 7 wherein the metallizing compound is copper chloride.
9.A bath for impregnation of fibrous materials according to claim 7 wherein the metallizing compound is cobalt chloride.
10. A bath for impregnation of fibrous materials according to claim 7 wherein the metallizing compound is nickel chloride.
11.'A bath for impregnation of fibrous materials according to claim'7 wherein the metallizing compound is copper sulfate.
12. A bath for impregnation of fibrous materials according to claim 7 wherein the metallizing compound is cobalt sulfate.
1 wherein the metal- References Cited in the tile of this patent FOREIGN PATENTS 502,144 Great Britain Mar. 7, 1939 531,470 Great Britain Jan. 6, 1941

Claims (1)

1. THE PROCESS OF METALLIZING AZOIC DYEINGS WHICH COMPRISES IMPREGNATING A FIBROUS MATERIAL SELECTED FROM THE CLASS CONSISTING OF COTTON AND REGENERATED CELLULOSE WITH AN ALKALINE SOLUTION OF AN AZOIC COUPLING COMPONENT, A COORDINATING AGENT SELECTED FROM THE CLASS CONSISTING OF ALIPHATIC AMINO- AND HYDROXY-CARBOXYLIC ACIDS, AND A METALLIZING COMPOUND OF THE GROUP CONSISTING OF SOLUBLE AND DISPERSIBLE SALTS OF COPPER, COBALT, AND NICKEL, AND THEN TREATING THE IMPREGNATED FIBER WITH A DIAZO SOLUTION, IN WHICH THE DIAZO IS FREE FROM SOLUBILIZING GROUPS, AND SIMULTANEOUSLY DYEING AND METALLIZING IN SITU BY TREATMENT AT ELEVATED TEMPERATURES WITH AN AQUEOUS MEDIUM HAVING A PH OF NOT MORE THAN 7, THE SAID AZOIC COUPLING COMPONENT AND THE SAID DIAZO YIELDING AN O, O-DIHYDROXY CONFIGURATION IN THE FINAL DYESTUFF.
US601658A 1956-08-02 1956-08-02 Method of metallizing azoic dyeings Expired - Lifetime US2867494A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US601658A US2867494A (en) 1956-08-02 1956-08-02 Method of metallizing azoic dyeings

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US601658A US2867494A (en) 1956-08-02 1956-08-02 Method of metallizing azoic dyeings

Publications (1)

Publication Number Publication Date
US2867494A true US2867494A (en) 1959-01-06

Family

ID=24408288

Family Applications (1)

Application Number Title Priority Date Filing Date
US601658A Expired - Lifetime US2867494A (en) 1956-08-02 1956-08-02 Method of metallizing azoic dyeings

Country Status (1)

Country Link
US (1) US2867494A (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3061397A (en) * 1957-06-14 1962-10-30 Gen Aniline & Film Corp Metallizing azoic dyeings
US3192007A (en) * 1962-12-26 1965-06-29 Exxon Research Engineering Co Blending of polypropylene with unmetallized chelating agent to improve dyeability
DE1205049B (en) * 1960-04-28 1965-11-18 Hoechst Ag Process for the production of metal-containing, water-insoluble azo dyes on the fiber
US3236829A (en) * 1962-06-22 1966-02-22 Otto B May Inc Disazo gamma-resorcylic acid dye compositions
US3238189A (en) * 1962-06-06 1966-03-01 Otto B May Inc Trifluoromethyl-benzeneazosalicylic acid dyestuffs
US3244694A (en) * 1962-04-23 1966-04-05 Otto B May Inc Substituted disazo salicylic acid dyestuffs
US3249599A (en) * 1962-07-20 1966-05-03 Otto B May Inc Resorcylic acid azo dye
US3257379A (en) * 1962-08-30 1966-06-21 Otto B May Inc Monoazo beta-resorcylic acid dyes
US3414368A (en) * 1963-07-18 1968-12-03 Teijin Ltd Resist printing method for hydrophobic fibers

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB502144A (en) * 1937-09-07 1939-03-07 Ig Farbenindustrie Ag Manufacture of water-insoluble azo-dyestuffs containing metal
GB531470A (en) * 1938-05-18 1941-01-06 Chem Ind Basel Process of dyeing

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB502144A (en) * 1937-09-07 1939-03-07 Ig Farbenindustrie Ag Manufacture of water-insoluble azo-dyestuffs containing metal
GB531470A (en) * 1938-05-18 1941-01-06 Chem Ind Basel Process of dyeing

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3061397A (en) * 1957-06-14 1962-10-30 Gen Aniline & Film Corp Metallizing azoic dyeings
DE1205049B (en) * 1960-04-28 1965-11-18 Hoechst Ag Process for the production of metal-containing, water-insoluble azo dyes on the fiber
US3244694A (en) * 1962-04-23 1966-04-05 Otto B May Inc Substituted disazo salicylic acid dyestuffs
US3238189A (en) * 1962-06-06 1966-03-01 Otto B May Inc Trifluoromethyl-benzeneazosalicylic acid dyestuffs
US3236829A (en) * 1962-06-22 1966-02-22 Otto B May Inc Disazo gamma-resorcylic acid dye compositions
US3251822A (en) * 1962-06-22 1966-05-17 Otto B May Inc Disazo beta resorcylic acid dyestuffs
US3249599A (en) * 1962-07-20 1966-05-03 Otto B May Inc Resorcylic acid azo dye
US3257379A (en) * 1962-08-30 1966-06-21 Otto B May Inc Monoazo beta-resorcylic acid dyes
US3192007A (en) * 1962-12-26 1965-06-29 Exxon Research Engineering Co Blending of polypropylene with unmetallized chelating agent to improve dyeability
US3414368A (en) * 1963-07-18 1968-12-03 Teijin Ltd Resist printing method for hydrophobic fibers

Similar Documents

Publication Publication Date Title
US2867494A (en) Method of metallizing azoic dyeings
US2148659A (en) Process for the production of fast tints on cellulosic fibers
US2078388A (en) Dyeing process and composition
US2190848A (en) Dyeings
US2893814A (en) Method of metallizing azoic dyeings
US2768053A (en) Aftertreatment of dyed fibrous material
US2526106A (en) Composition comprising a nitroge
US2499800A (en) Azo dyes formed from p-nitroanilines and 2-hydroxy-7-benzo-(c) carbazoles and their formation on the fiber
US3061397A (en) Metallizing azoic dyeings
US2649353A (en) Dyeing of nylon and acetate silk in
US2040927A (en) Coloration of textile materials
US3317273A (en) Metallizing azoic dyeings and prints
US1935657A (en) Manufacture of new dyestuffs and the application thereof
US2104505A (en) Dyeings on cellulosic fibers
US2593930A (en) Process of printing fabrics with aryl sulfonhydrazides
US1483797A (en) Dyeing and printing acetyl silk and materials containing it
US2213193A (en) Process of producing fast dyeings
US3121073A (en) Metalliferous water-insoluble azo-dye-
US3073813A (en) Complex metal compounds of water-
US2926985A (en) Colouring preparations
US2263559A (en) Process of producing fast dyeings and the dyed fiber obtained thereby
US2115136A (en) Dyeing
US2199814A (en) Azo dyestuffs insoluble in water and fiber dyed therewith
US2908679A (en) Azo-dyestuffs insoluble in water
US3189595A (en) Metal comples dies containing 2-dibenzofuranol