US2893814A - Method of metallizing azoic dyeings - Google Patents
Method of metallizing azoic dyeings Download PDFInfo
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- US2893814A US2893814A US631062A US63106256A US2893814A US 2893814 A US2893814 A US 2893814A US 631062 A US631062 A US 631062A US 63106256 A US63106256 A US 63106256A US 2893814 A US2893814 A US 2893814A
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- 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
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/64—Natural or regenerated cellulose using mordant dyes or metallisable dyes
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- 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
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/68—Preparing azo dyes on the material
Definitions
- fibres may be impregnated with a coupling component and passed into a solution which contains an active diazo, either in the form of a freshly prepared diazo or as a fast-color salt solution under conditions suitable for coupling.
- Fast color salts are diazo compounds which, except for a fewdiazos 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 SnCI etc., ar-yl-sulfonic acids such as naphthalened,S-disulfonic acid and naphthalene-1,3,6-trisulfonic acid, and alsoborofluoric acid.
- metallic salts e.g. MgCl ZnCl SnCI etc.
- ar-yl-sulfonic acids such as naphthalened,S-disulfonic acid and naphthalene-1,3,6-trisulfonic acid, and alsoborofluoric acid.
- an active diazo which includes a freshly prepared diazo or a diazo stabilized as a fast color salt, and then metallizing; with hot water or. preferably with steam.
- the important advantage of this improved method is that a satisfactory metallized product isobtained 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 andheating.
- oxidizing agents may be present in the amount of about 10-100% based on the weight of the metallizing agent.
- the metallizing agents or compound employed in the metallizing of azoic dyeings are salts and hydroxides of copper (cupric). 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 copper salt or copper 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 perequivalent of dye. The preferred amount is about 0.5 mol metal salt per mol of. dye.
- the oxidizing agent maybe addedtothe metallizing solution together with a chelating agent and this solution employeddirectly to treat the fibre alone or in combination
- With'Naphthol AScompounds which are arylides of 2 hydroxy 3-naphthoic acid and related p-hydroXy carboxylic, acid derivatives, acetoacetarylides and related ,3- oxocarboxylic acid arylides and pyrazolones.
- other compounds may be employed. which have active methylene or enolizable ketone groups and are free from Inst ad. of employing.
- the chelated metallizing agent or oxidizing agent can becombined with a naphtholating solution or Rapidogen solution in the products per se or prior to dyeing and printing.
- a chelated metallizing agent in dry form and a suitable oxidizing agent can be incorporated in a dry naphthol or Rapidogen powder.
- the uncoordinated metal salt can be incorporated in a dry naphthol or Rapidogen powder together with suitable oxidizing agent; however such mixture must be pasted with the proper chelating agent prior to use. While the above describes the addition of oxidizing agent to the naphthol or Rapidogen per se, it may be added at any time prior to use.
- the proportions of chelating agent, metallizing compound, Naphthol AS compound or Rapidogen powder are given in my pending patent application Serial No. 601,658. i
- a metallizing solution is first prepared in accordance with the following recipe.
- Example I A metallizing solution containing an oxidizing agent was prepared as follows:
- a padding solution was prepared by mixing the following components:
- the padding solution was poured into 10 cc. of the above copper solution together with 2.5 cc. of caustic soda 34 B. and water to yield a total volume of 133 cc.
- Diazopon AN fatty alcohol-ethylene oxide condensation product used as a protective colloid
- 2 cc. of acetic acid 50% aqueous solution Suflicient water was added to give a total volume of 133 cc.
- Example 11 Example I was repeated with the exception that the 'Naphthol AS in the padding solution was replaced by 2.
- Example III Example III was repeated with the exception that the Naphthol AS was replaced by an equivalent amount of Z-hydroxybenzeneazo-4-resorcinol and the o-dianisidine, tetrazotized and stabilized with zinc chloride, was replaced by an equivalent amount of zinc chloride double salt of diazotized S-chloro-o-anisidine. A brown dyeing was obtained which showed excellent light-, washand chlorine-fastness with no precipitation of metallic copper on the fibre.
- Example IV Example I was again repeated with the exception that the Naphthol AS was replaced by an equivalent amount of 3-hydroxy-2-naphthoic .acid o-toluidide and the o-dianisidine, tetrazotized and stabilized with zinc chloride, was replaced by an equivalent amount of zinc chloride double salt of the diazo from S-n-butyl-sulfamyl-o-anisidine. A red dyeing was obtained which showed excellent light-, washand chlorine-fastness with no evidence whatsoever of copper precipitation on the fibre.
- Example V A metallizing solution was prepared as follows:
- a 10 gram sample of cotton was padded with the above solution and dried. It was then padded with a solution made by dissolving 8 /2 grams of zinc chloride double salt of tetrazotized o-dianisidine, 0.5 cc. of a 40% solution of Diazopon AN solution, 13 cc. of 50% aqueous acetic acid solution and water added to make up a total volume of 133 cc., followed by treatment with steam for 25 seconds.
- a deep jet black dyeing was obtained of excellent wash-, lightand chlorine-fastness with no evidence of deposition of metallic copper on the cotton fibre.
- Example VI Example I was repeated with the exception that 10 cc. of the copper solution described therein was replaced by an equivalent volume of the following copper solution:
- Example VII Example I was repeated with the exception that 10 cc. of the copper solution was replaced by an equivalent volume of the following copper solution:
- Example VIII A solution was prepared from grams of a commercially available Rapidogen, consisting of 11 grams of o-dianisidine tetrazotized and stabilized with methyl taurine; 11; igramslefi :lJrydroxy-Z-naplitlninilide; .10 grams-of sodium hydroxide. (100%),80 cornbin'edwater and; solventsand SO-Tgrams of the'eo'pp'er solution prepared-aria Example 1. 11pm.- of the solution was thickened' with--v m ansct starch tr-agacanth andiaiiiusted l3- parts-ofwateri.
- Example X Example IX was repeated with the exception that 4 grams of the Rapidogen mix was replaced by 4 grams of a Rapidogen mix consisting of an equivalent amount of o-dianisidine tetrazotized and stabilized with methyl taurine, and phenyl methyl pyrazolone and 10 cc. of copper solution of Example I. A tan coloration was produced which showed excellent light-, washand chlorine-fastness with no evidence of metallic copper on the printed cotton fibre.
- Example XI Example IX was again repeated with the exception that 4 grams of the Rapidogen mix was replaced by 4 grams of a R-apidogen mix consisting of an equivalent amount of 4-benzoylamino-2-methoxy-5-rnethylaniline diazotized and stabilized with sarcosine, and 3-hydroxy- Z-naphthanilide. A violet shade somewhat redder than usual was produced having excellent light-, washand chlorine-fastness with no evidence of metallic copper on the printed cotton fibre.
- the process of producing metallized azoic prints and dyeings in situ which comprises treating a cellulosic fibrous material selected from the class consisting of cotton and regenerated cellulose with an azoic coupling component devoid of solubilizing groups and a diazo component derived from an amine base devoid of solubilizing groups to yield an azoic dye component capable of yielding an o,o'-dihydroxy azo configuration at elevated temperatures in the presence of a coordinating agent selected from the class consisting of lower alkylolamines and aliphatic aminoand hydroxy-carboxylic acids, and a metallizing copper compound consisting of soluble and dispersible salts and hydroxides of copper, and an oxidizing agent equivalent to 10l00% based on the weight of the metallizing agent, selected from the class consisting of alkali perborates, alkali chromates, hydrogen peroxide, alkali peroxides and nitrobenzenesulfonic acids and their alkali salts.
- a composition of matter for use in azoic dye manufacture which comprises an azoic coupling component devoid of solubilizing groups, a coordinating agent selected from the class consisting of lower alkylolamines and aliphatic aminoand hydroxy-carboxylic acids, a metallizing copper compound consisting of soluble and dispersible salts and hydroxides of copper, and an oxidizing agent equivalent to Ill-% based on the weight of the metallizing agent, selected from the class consisting of alkali perborates, alkali chromates, hydrogen peroxide, alkali peroxides and nitrobenzenesulfonic acids and their alkali salts in an alkaline solution.
- a composition of matter for use in azoic dye manufacture which comprises an azoic coupling component devoid of solubilizing groups, triethanolamine, copper sulfate and an oxidizing agent equivalent to 10100% based on the weight of the metallizing agent, selected from the class consisting of alkali perborates, alkali chromates, hydrogen peroxide, alkali peroxides and nitrobenzenesulfonic acids and their alkali salts in an alkaline solution.
- composition according to claim 9 wherein the oxidizing agent is sodium chromate.
- composition according to claim 9 wherein the oxidizing agent is potassium chromate.
- composition according to claim 9 wherein the coupling component is Naphthol AS.
- a composition of matter for use in azoic printing which comprises an azoic coupling component devoid of solubilizing groups, a diazoamino compound derived from an amine base devoid of solubilizing groups which has been diazotized and stabilized with a primary and secondary amine containing at least one solubilizing group, which azoic dye components are capable'of yielding an o,o'-dihydroxy 'azo dye configuration in the final dye, a coordinating agent selected from the class consisting of lower alkylolamines and aliphatic aminoand hydroxy-carboxylic acids, and a metallizing copper compound consisting of soluble and dispersible salts and hydroxides of copper, and an oxidizing agent equivalent to 10100% based on the weight of the metallizing agent, selected from the class consisting of alkali perborates, alkali chromates, hydrogen peroxide, alkali peroxides and nitrobenzenesulfonic acids and their alkali salts, in an al
- a composition of matter for use in azoic printing which comprises an azoic coupling component devoid of solubilizing groups, a diazoamino compound derived from an amine base devoid of solubilizing groups which has been diazotized and stabilized with a primary and secondary amine containing at least one solubilizing group, which azoic dye components are capable of yielding an o,o'-dihydroxy azo dye configuration in the final 20 dye, triethanolamine, copper sulfate and an oxidizing agent equivalentto: 10-1009?
- the metallizing agent selected from :the: class consisting of alkali perborates, alkali chromates, hydrogen peroxide, alkali peroxides and nitrobenzenesulfon'ic acids; and their alkali sa1ts,'in an alkaline medium. i i z; 15.
- composition according toclaim 14 wherein the diazois dianisidine tetrazotized and stabilized with methyl taurine, and the coupling. component isiNaphtholAS.
- composition according to claim 14- wherein the diazo is 4-benzoylamino 2-methoxy-5-methy1ani1ine diazotized and stabilizedwith .sarcosine, and, the coupling component is Naphthol v g 7 References Clted in the tile o f thispatent I -FOREIGN. PATENTS 5 Great Britain Mar. 7, 1939 Great Britain Jan. 6,1941
Description
United States Patent METHOD OF METALLIZING AZOIC DYEINGS.
Clemens Streck, Loudonville, N.Y., assignor to General Aniline & Film Corporation, New York, N.Y., a corporation 'of'Delaware No Drawing. Application December 28, 1956 Serial No. 631,062
17 Claims. (Cl. 8-42) Thisinvention relates to an improved process of metallizing .azoic' dyeings and particularly to an improved processwhereby said dyeings are obtained without the precipitation of free metal on the fibre and dyeing apparatus.
Itv is known that fibres may be impregnated with a coupling component and passed into a solution which contains an active diazo, either in the form of a freshly prepared diazo or as a fast-color salt solution under conditions suitable for coupling. Fast color salts are diazo compounds which, except for a fewdiazos 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 SnCI etc., ar-yl-sulfonic acids such as naphthalened,S-disulfonic acid and naphthalene-1,3,6-trisulfonic acid, and alsoborofluoric acid.
One of theoutstanding advantages ofrazoic dyeings is their fastness in contrast to that of the. usual azo dyes. Thefastness of azoic dyeings has recently. been improved by metallizing, i.e.- by treating the-previously dyed fibres with various metallizing agents-such as Cu, Co, Cr, Ni andthelike. In the art as nowpracticed, it isnecessary to dye the fibrous material with an 'azoicdye devoid of solubilizing groups followed'by anafter treatment'with a metallizing agent. The metallizing step represents an extra step and also requires at least 20' minutes. To overcome this, satisfactory metallization of azoic dyeings is achieved by incorporating the metallizingagent in the soaping bath as taught in my. United States patent application (Serial No. 316,305), now United Statesv States Patent 2,768,053.
-' In my United Statespatentapplicatibn Serial No. 601",- 658; filed on August 2, 1956, for Method of Metallizing Azoic Dyeings, I disclose and claim a novel process whereby the azoic color formation is carried out in the presence of the metallizingagent. By this process 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 shade. In this process the: metallizing agent may be dissolved in a naphtholating bath, the fibrous. material impregnated with this bath, usually followed bydrying, and the impregnated fibre padded or printed with an active diazo which includes a freshly prepared diazo or a diazo stabilized as a fast color salt, and then metallizing; with hot water or. preferably with steam. The temperature and moisture conditions of the hot Water or steam-are sufficiently drastic to yield complete metallization together with color development, even when exposed to steamfor less than 1 minute. The important advantage of this improved method is thata satisfactory metallized product isobtained 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 andheating.
Despite the fact that economical dyeings having desirable' characteristics are obtained, the process neverthel'ess lacks one factor which is highly desirable in the dye trade. In conducting numerous experiments with the process described in the aforesaid application, i.e., Serial No. 601,658, I found that under certain conditions, free copper is precipitated. The precipitation may be on the fibre, causing splotchy dyeings, or. in the dyeing apparatus, such as glass, steel, wood, stainless steel, etc. resulting in a metal plating problem. The precipitation is believed to be due tothe presence of certainimpurities or by-products which are'readily oxidizable and inoxidation' cause a reduction of the. loosely coordinated copper salt to free copper. Cleaning oif deposited copper from equipment is diflicult in addition to the poor, uneven dyeings resulting; therefrom.
I have found that precipitation can be very readily remedied by the addition of an inorganic or organic oxidizing agent to the metallizing solution. The metallizing solution and other details with regard to the diazo and coupling components employed in azoic dyeings are fully described in my aforementioned patent application (Serial No. 601,658), .the disclosure of whichfis incorporated herein by reference thereto. The inorganic and organic oxidizing agentswhich I have found particularly useful include allof those'which are soluble in alkaline aqueous solutions, and are. sufficiently stable to withstand the temperature. of padding which ranges from room temperature to 212 F., and will not destroy the diazo com ponents. As illustrative examples of such oxidizing agents, the following may be mentioned:
m-Nitrobenzenesulfonic acid p-Nitrobenzenesulfonic acid Sodium chromate Potassium chromate, Sodium perborate Potassium'perborate Sodium peroxide Potassium peroxide Hydrogen peroxide The foregoing oxidizing agents may be present in the amount of about 10-100% based on the weight of the metallizing agent. As stated in myaforementioned patent application, the metallizing agents or compound employed in the metallizing of azoic dyeings are salts and hydroxides of copper (cupric). 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 copper salt or copper 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 perequivalent of dye. The preferred amount is about 0.5 mol metal salt per mol of. dye.
The oxidizing agent maybe addedtothe metallizing solution together with a chelating agent and this solution employeddirectly to treat the fibre alone or in combination With'Naphthol AScompounds which are arylides of 2 hydroxy 3-naphthoic acid and related p-hydroXy carboxylic, acid derivatives, acetoacetarylides and related ,3- oxocarboxylic acid arylides and pyrazolones. However, other compounds may be employed. which have active methylene or enolizable ketone groups and are free from Inst ad. of employing. a combination of the oxidizing agent, metallizing agent and chelating agent in the treatment, the chelated metallizing agent or oxidizing agent can becombined with a naphtholating solution or Rapidogen solution in the products per se or prior to dyeing and printing. A chelated metallizing agent in dry form and a suitable oxidizing agent can be incorporated in a dry naphthol or Rapidogen powder. Further, the uncoordinated metal salt can be incorporated in a dry naphthol or Rapidogen powder together with suitable oxidizing agent; however such mixture must be pasted with the proper chelating agent prior to use. While the above describes the addition of oxidizing agent to the naphthol or Rapidogen per se, it may be added at any time prior to use. The proportions of chelating agent, metallizing compound, Naphthol AS compound or Rapidogen powder are given in my pending patent application Serial No. 601,658. i
In order to practice one embodiment of the present invention, a metallizing solution is first prepared in accordance with the following recipe.
1 to 200 parts of metallizing compound 5 to 800 parts of water 1 to 30 parts of chelating agent .5 to 80 parts of caustic soda (dry) After formation of the metallizing solution, 100% of an oxidizing agent is added to the solution based on the weight of the metallizing compound.
The following examples will illustrate the preferred embodiments of the present invention. It is to be clearly understood that these examples are illustrative and are not to be considered as limitative.
Example I A metallizing solution containing an oxidizing agent was prepared as follows:
Copper solution 147 grams of copper sulfate 643 grams of water 110 grams of tn'ethanolamine 60 grams of caustic soda (dry) After formation of a blue solution, 40 grams of sodium chromate anhydrous was added.
A padding solution was prepared by mixing the following components:
3 grams of Naphthol AS (3-hydroxy-2-naphthanilide) 6 cc. of ethyl alcohol 1.5 cc. of caustic soda 34 B.
The padding solution Was poured into 10 cc. of the above copper solution together with 2.5 cc. of caustic soda 34 B. and water to yield a total volume of 133 cc.
A 10 gram sample of muslin was padded with the above solution, dried and padded with a solution consisting of:
7 grams of o-dianisidine, tetrazotized and stabilized with zinc chloride,
.5 cc. of Diazopon AN (fatty alcohol-ethylene oxide condensation product used as a protective colloid) and 2 cc. of acetic acid 50% aqueous solution. Suflicient water was added to give a total volume of 133 cc.
Example 11 Example I was repeated with the exception that the 'Naphthol AS in the padding solution was replaced by 2.
grams of phenyl methyl pyrazolone. A tan coloration was produced showing excellent light-, washand chlorine-fastness without any perceivable trace of copper precipitation on the fibre.
Example III Example I was repeated with the exception that the Naphthol AS was replaced by an equivalent amount of Z-hydroxybenzeneazo-4-resorcinol and the o-dianisidine, tetrazotized and stabilized with zinc chloride, was replaced by an equivalent amount of zinc chloride double salt of diazotized S-chloro-o-anisidine. A brown dyeing was obtained which showed excellent light-, washand chlorine-fastness with no precipitation of metallic copper on the fibre.
Example IV Example I was again repeated with the exception that the Naphthol AS was replaced by an equivalent amount of 3-hydroxy-2-naphthoic .acid o-toluidide and the o-dianisidine, tetrazotized and stabilized with zinc chloride, was replaced by an equivalent amount of zinc chloride double salt of the diazo from S-n-butyl-sulfamyl-o-anisidine. A red dyeing was obtained which showed excellent light-, washand chlorine-fastness with no evidence whatsoever of copper precipitation on the fibre.
Example V A metallizing solution was prepared as follows:
Copper solutiongrams of tartaric acid 460 grams of water 100 grams of copper chloride 300 cc. of caustic soda 34 136.
After formation of a blue solution, 40 grams of sodium chromate anhydrous was added.
3 grams of B-hydroxy-Z-naphthanilide and 1 gram of his (acetoacet)-o-tolidide were dissolved in 100 cc. boiling water containing 4.5 cc. caustic soda 34 B. To this solution, cooled to about 140 F., was added 10 cc. of the above copper solution.
A 10 gram sample of cotton was padded with the above solution and dried. It was then padded with a solution made by dissolving 8 /2 grams of zinc chloride double salt of tetrazotized o-dianisidine, 0.5 cc. of a 40% solution of Diazopon AN solution, 13 cc. of 50% aqueous acetic acid solution and water added to make up a total volume of 133 cc., followed by treatment with steam for 25 seconds. A deep jet black dyeing was obtained of excellent wash-, lightand chlorine-fastness with no evidence of deposition of metallic copper on the cotton fibre.
Example VI Example I was repeated with the exception that 10 cc. of the copper solution described therein was replaced by an equivalent volume of the following copper solution:
100 grams of glycine 400 grams of water 100 grams of copper chloride 300 cc. of caustic soda 34 B. 100 grams of sodium perborate Example VII Example I was repeated with the exception that 10 cc. of the copper solution was replaced by an equivalent volume of the following copper solution:
100 grams of glutamic acid 400 grams of water 100 grams of copper sulfate 300 grams of caustic soda 34 B6.
100 grams of m-nitrobenzenesulfonic acid Na salt Example VIII A solution was prepared from grams of a commercially available Rapidogen, consisting of 11 grams of o-dianisidine tetrazotized and stabilized with methyl taurine; 11; igramslefi :lJrydroxy-Z-naplitlninilide; .10 grams-of sodium hydroxide. (100%),80 cornbin'edwater and; solventsand SO-Tgrams of the'eo'pp'er solution prepared-aria Example 1. 11pm.- of the solution was thickened' with--v m ansct starch tr-agacanth andiaiiiusted l3- parts-ofwateri.
A gram samplcof cotton was'printed; with" the pasteysteainedfin acidasteamzin a normalimanri'e'r for 2 minutes," riiisedlandk-dfied'. The blue dyeing obtained showed excellentlightgiwash-r and chlorine-fastness with no evidence of metallic copper on the printed cotton 4 grams of a Rapidogen mix, con g oreanivalent amounts of cresid ine diazotized and stabilized with sarcosine, '-liydroii3-fiitro 2 liaphtliaiiilifle, '4 cc. of ethylene glycol mono ethylgethen i gtrcc. of water, 3 cc. of sodiurnhydroxide 34 Re and 5 cctpf copper solutioir of Example i'were combine arrdlO or. gum tia'g'acanthaddedt'oprintingtlrickrressi A 10 gram sample of cotton cloth was printed with the above paste and developed for 2 minutes in acidified steam. The bordeaux dyeing obtained showed excellent light-, washand chlorine-fastness with no evidence of metallic copper on the printed cotton fibre.
Example X Example IX was repeated with the exception that 4 grams of the Rapidogen mix was replaced by 4 grams of a Rapidogen mix consisting of an equivalent amount of o-dianisidine tetrazotized and stabilized with methyl taurine, and phenyl methyl pyrazolone and 10 cc. of copper solution of Example I. A tan coloration was produced which showed excellent light-, washand chlorine-fastness with no evidence of metallic copper on the printed cotton fibre.
Example XI Example IX was again repeated with the exception that 4 grams of the Rapidogen mix was replaced by 4 grams of a R-apidogen mix consisting of an equivalent amount of 4-benzoylamino-2-methoxy-5-rnethylaniline diazotized and stabilized with sarcosine, and 3-hydroxy- Z-naphthanilide. A violet shade somewhat redder than usual was produced having excellent light-, washand chlorine-fastness with no evidence of metallic copper on the printed cotton fibre.
I claim:
1. The process of producing metallized azoic prints and dyeings in situ which comprises treating a cellulosic fibrous material selected from the class consisting of cotton and regenerated cellulose with an azoic coupling component devoid of solubilizing groups and a diazo component derived from an amine base devoid of solubilizing groups to yield an azoic dye component capable of yielding an o,o'-dihydroxy azo configuration at elevated temperatures in the presence of a coordinating agent selected from the class consisting of lower alkylolamines and aliphatic aminoand hydroxy-carboxylic acids, and a metallizing copper compound consisting of soluble and dispersible salts and hydroxides of copper, and an oxidizing agent equivalent to 10l00% based on the weight of the metallizing agent, selected from the class consisting of alkali perborates, alkali chromates, hydrogen peroxide, alkali peroxides and nitrobenzenesulfonic acids and their alkali salts.
2. The process according to claim 1 wherein the oxidizing agent is sodium chromate.
3. The process according to claim 1 wherein the oxidizing agent is sodium perborate.
4. The process according to claim 1 wherein the oxidizing agent is m-nitrobenzenesulfonic acid.
5. The process according to claim 1 wherein the oxidizing agent is potassium chromate.
l 62 Theprocess of-producingmetallized azoic prints and} dyeings' insitu whichcomprises impregnating ;a cellulosiefibrous material selected from the class con sisting of cotton and regenerated cellulose with an azoic coupling component devoid ofsolubilizing groups ata pH of, more than7 followed by treatment with a diazonium compound derived from an amine base devoid ofsolubilizing groups; and; which azoic component is capable'of yielding.-an o,o dihydroxy azo dye configurationinj-the final dye, followed by treatment at elevated temperatures in the presenceofa coordinating agent selected from the class consisting of lower alkylolamines an'd aliphatic aminoand hydroxy-carboxylic' acids, and a2 metallizing coppercompound consisting ofsoluble and dispersible salts and-hydroxides of copper, an'd'an oxidizing-"agent equivalent to 10-100% based on the Weight of the metallizing agent, selected from the class consist- -ing=o alkali perborates, alkali chrom'ates, hydrogen peroxide, alkali peroxide s, and nitrobenzenesulfonic' acids and-their alkalisalts: 72; The process of:producingmetallized azoic prints, in situ which comprises printing a cellulosic fibrous material selected from the class consisting of cotton and regenerated cellulose with an alkaline paste consisting of an azoic coupling component devoid of solubilizing groups and a diazoamino compound derived from an amine base devoid of solubilizing groups, which has been diazotized and stabilized with a primary and secondary amine which contains at least one solubilizing group, and which azoic dye component is capable of yielding an o,o'-dihydroxy azo dye configuration in the final dye, followed by treatment with acidified steam in the presence of a coordinating agent selected from the class consisting of lower alkylolamines and aliphatic aminoand hydroxy-carboxylic acids, and a metallizing copper compound consisting of soluble and dispersible salts and hydroxides of copper, and an oxidizing agent equivalent to 10-100% based on the weight of the metal- -lizing agent, selected from the class consisting of alkali perborates, alkali chromates, hydrogen peroxide alkali peroxides and nitrobenzenesulfonic acids and their alkali salts.
8. A composition of matter for use in azoic dye manufacture which comprises an azoic coupling component devoid of solubilizing groups, a coordinating agent selected from the class consisting of lower alkylolamines and aliphatic aminoand hydroxy-carboxylic acids, a metallizing copper compound consisting of soluble and dispersible salts and hydroxides of copper, and an oxidizing agent equivalent to Ill-% based on the weight of the metallizing agent, selected from the class consisting of alkali perborates, alkali chromates, hydrogen peroxide, alkali peroxides and nitrobenzenesulfonic acids and their alkali salts in an alkaline solution.
9. A composition of matter for use in azoic dye manufacture which comprises an azoic coupling component devoid of solubilizing groups, triethanolamine, copper sulfate and an oxidizing agent equivalent to 10100% based on the weight of the metallizing agent, selected from the class consisting of alkali perborates, alkali chromates, hydrogen peroxide, alkali peroxides and nitrobenzenesulfonic acids and their alkali salts in an alkaline solution.
10. A composition according to claim 9 wherein the oxidizing agent is sodium chromate.
11. A composition according to claim 9 wherein the oxidizing agent is potassium chromate.
12. A composition according to claim 9 wherein the coupling component is Naphthol AS.
13. A composition of matter for use in azoic printing which comprises an azoic coupling component devoid of solubilizing groups, a diazoamino compound derived from an amine base devoid of solubilizing groups which has been diazotized and stabilized with a primary and secondary amine containing at least one solubilizing group, which azoic dye components are capable'of yielding an o,o'-dihydroxy 'azo dye configuration in the final dye, a coordinating agent selected from the class consisting of lower alkylolamines and aliphatic aminoand hydroxy-carboxylic acids, and a metallizing copper compound consisting of soluble and dispersible salts and hydroxides of copper, and an oxidizing agent equivalent to 10100% based on the weight of the metallizing agent, selected from the class consisting of alkali perborates, alkali chromates, hydrogen peroxide, alkali peroxides and nitrobenzenesulfonic acids and their alkali salts, in an alk-aline medium.
14. A composition of matter for use in azoic printing which comprises an azoic coupling component devoid of solubilizing groups, a diazoamino compound derived from an amine base devoid of solubilizing groups which has been diazotized and stabilized with a primary and secondary amine containing at least one solubilizing group, which azoic dye components are capable of yielding an o,o'-dihydroxy azo dye configuration in the final 20 dye, triethanolamine, copper sulfate and an oxidizing agent equivalentto: 10-1009? based' on fth .weightiof the metallizing agent, selected from :the: class consisting of alkali perborates, alkali chromates, hydrogen peroxide, alkali peroxides and nitrobenzenesulfon'ic acids; and their alkali sa1ts,'in an alkaline medium. i i z; 15. The composition according to' claim .14 whei'ein the oxidizing agent is sodium chromate. r
16. The composition according toclaim 14 wherein the diazois dianisidine tetrazotized and stabilized with methyl taurine, and the coupling. component isiNaphtholAS. I 1
17. The composition according to claim 14- wherein the diazo is 4-benzoylamino 2-methoxy-5-methy1ani1ine diazotized and stabilizedwith .sarcosine, and, the coupling component is Naphthol v g 7 References Clted in the tile o f thispatent I -FOREIGN. PATENTS 5 Great Britain Mar. 7, 1939 Great Britain Jan. 6,1941
Claims (1)
1. THE PROCESS OF PRODUCING METALLIZED AZOIC PRINTS AND DYEING IN SITU WHICH COMPRISES TREATING A CELLULOSIC FIBROUS MATERIAL SELECTED FROM THE CLASS CONSISTING OF COTTONN AND REGENERATED CELLULOSE WITH AN AZOIC COUPLING COMPONENT DEVOID OF SOLUBLIZING GROUPS AND A DIAZO COMPONENT DERIVED FROM AN AMINE BASE DEVOID OF SOLUBILIZING GROUPS TO YEILD AN AZOIC DYE COMPONENT CAPABLE OF YIELDING AN O,O''-DIHYDROXYAZO CONFIGURATION AT ELEVATED TEMPERATURES IN THE PRESENCE OF A COORDINATING AGENT SELECTED FROM THE CLASS CONSISTING OF LOWER ALKYLOLAMINES AND ALIPHATIC AMINO- AND HYDROXY-CARBOXYLIC ACIDS, AND A MELTALLIZING COPPER COMPOUND CONSISTING OF SOLUBLE AND DISPERSIBLE SALTS AND HYDROXIDES OF COPPER, AND AN OXIDIZING AGENT EQUIVALENT TO 10-1000% BASED FROM THE THE WEIGHT OF THE METALLIZING AGENT, SELECTED FROM THE CLASS CONSISTING OF ALKALI PERBORATES, ALKALI CHROMATES, HYDROGEN PERIOXIDE, ALKALI PEROXIDES AND NIRTOBENZENESULFONIC ACIDS AND THEIR ALKALI SALTS.
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Application Number | Priority Date | Filing Date | Title |
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US631062A US2893814A (en) | 1956-12-28 | 1956-12-28 | Method of metallizing azoic dyeings |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US631062A US2893814A (en) | 1956-12-28 | 1956-12-28 | Method of metallizing azoic dyeings |
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US2893814A true US2893814A (en) | 1959-07-07 |
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US631062A Expired - Lifetime US2893814A (en) | 1956-12-28 | 1956-12-28 | Method of metallizing azoic dyeings |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3061397A (en) * | 1957-06-14 | 1962-10-30 | Gen Aniline & Film Corp | Metallizing azoic dyeings |
US3071428A (en) * | 1963-01-01 | Process for the production of water- | ||
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 |
US3257379A (en) * | 1962-08-30 | 1966-06-21 | Otto B May Inc | Monoazo beta-resorcylic acid dyes |
Citations (2)
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 |
-
1956
- 1956-12-28 US US631062A patent/US2893814A/en not_active Expired - Lifetime
Patent Citations (2)
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 (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3071428A (en) * | 1963-01-01 | Process for the production of water- | ||
US3061397A (en) * | 1957-06-14 | 1962-10-30 | Gen Aniline & Film Corp | Metallizing azoic dyeings |
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 |
US3257379A (en) * | 1962-08-30 | 1966-06-21 | Otto B May Inc | Monoazo beta-resorcylic acid dyes |
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