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US3320020A - Composition for and dyeing cellulose copper and nickel tetrazaporphin-betaine dye compositions and reactive dyeing cellulose therewith - Google Patents

Composition for and dyeing cellulose copper and nickel tetrazaporphin-betaine dye compositions and reactive dyeing cellulose therewith Download PDF

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Publication number
US3320020A
US3320020A US348791A US34879164A US3320020A US 3320020 A US3320020 A US 3320020A US 348791 A US348791 A US 348791A US 34879164 A US34879164 A US 34879164A US 3320020 A US3320020 A US 3320020A
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parts
dye
dyes
tetrazaporphin
alkaline
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US348791A
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English (en)
Inventor
Tartter Arnold
Blum Adolf
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BASF SE
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BASF SE
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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
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
    • C09B47/12—Obtaining compounds having alkyl radicals, or alkyl radicals substituted by hetero atoms, bound to the phthalocyanine skeleton
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/916—Natural fiber dyeing
    • Y10S8/918—Cellulose textile

Definitions

  • T denotes the radical of a copper or nickel tetrazaporphin
  • CH --X denotes an amino acid internal salt group with X representing a nitrogen atom quaternized by a hydrocarbon structure which in turn bears at least one free or functionally modified snlphonic acid group or carboxylic acid group
  • n denotes one of the whole numbers from 1 to 8.
  • betaine dyes because of their similarity in-structure to the class of organic bases known as betaines.
  • the invention also relates to alkaline dyeing or coloring compositions containing said betaine dyes and to cellulosic textile materials which have been dyed and/or printed by the new processes.
  • textile material or paper can be dyed or printed with so-called onium dyesi.e. dyes which contain quaternary ammonium, ter tiary sulfonium or isothiuronium salt groups attached to the aromatic nucleus of the dyes by way of methylene bridges-if the dyes are applied in the presence of wealdy acid reacting agents and the textile material or'paper is treated with alkaline reacting agents before, during or after such application, or if the dyes are used in the presence of a mixture of a weak acid or an acid salt and an alkali metal salt of a weak acid.
  • onium dyes i.e. dyes which contain quaternary ammonium, ter tiary sulfonium or isothiuronium salt groups attached to the aromatic nucleus of the dyes by way of methylene bridges-if the dyes are applied in the presence of wealdy acid reacting agents and the textile material or'paper is treated with alkaline reacting agents before,
  • One object of the present invention is to provide new methods of dyeing or printing on cellulosic textile materials by using specific alkaline dyeing compositions capable of avoiding the problems of poor dye stability and lack of fastness properties evidenced by prior methods and compositions.
  • Another object of the invention is to provide stable alkaline dyeing compositions of a tetrazaporphin dye which can be used to advantage in combination with various known reactive dyes, discharge dyes, vat dyes, aniline black and naphthol dyes in otherwise "conventional dyeing and/or printing procedures.
  • Still another object of the invention is to provide high quality cellulosic textile products which have been dyed and/or printed according to the processes described hereinafter in order to achieve dyeings or printed patterns which are fast to washing, soda boiling, or similar wet treatments, which are also fast to rubbing or bleeding and which are especially fast to chlorine.
  • textile materials such as fibers, filaments, threads, flock, woven fabrics and knitted fabrics of native and/ or regenerated cellulose
  • an'alkaline dyeing composition comprising (A) a tetrazaporphin dye of the formula: I
  • T, X and n have the meanings given above and usual for vat dyes.
  • Cellulosic textile material may also be dyed and/or printed fast to rubbing and wet treatment in a simple way by applying said tetrazaporphin betaine dyes togethel with other reactive dyes in the presence of the alkaline agent on the cellulosic textile material and fixing the re sulting dye mixture in the way usual for reactive dyes.
  • the new process may also be used for discharge printing by printing dyes of the betaine type according to-this invention in the presence of the alkaline agent and a con ventional discharging agent onto cellulosic textile materia dyed with a dischargeable dye and then heating the mate rial to temperatures between 98 and 106 C.
  • Dyes according to this invention may also be printer in the presence of an alkaline agent and a reducing agen onto cellulosic textile material which has previously beet padded or impregnated with aniline black or treated ac cording to the so-called naphthol process with compound: capable of being coupled, the material then heated at tem peratures between 98 and 106 C., and the dyeings the: finished off in the conventional way for resist pi'inting be neath aniline black or naphthol paddings.
  • v onventional discharging agents are specified in the literature, for example in the above-mentioned Lehrbuch der Textilchemie" on pages 560 to 563 and in the abovernentioned book The Principles and Practice of Textile Printing" on pages 1009 to 1012.
  • Dischargeable dyes are given in the literature, for example in the above-mentioned Handbuch desmaschinebuchs" in volume II on pages 756 to 757,' in the textbook The Chemistry of Synthetic Dyes and Pigments by H. A. Lubs (New York, 1955) on pages 134 to 141 and in the Color Index" (2nd edition 1956) in volume 11 on pages 2001 to 2360 and 2569 to 2678.
  • Dyes of the type used according to this invention are obtained in a simple manner, for example according to the process disclosed in German patent specification No. 843,725 by the reaction of derivatives of copper or nickel tetrazaporphin containing halomethyl groups with tertiary amines which contain at least one free or functionally modified sulphonic acid group or carboxylic acid group.
  • the tetrazaporphin dyes used according to this invention are preferably derivatives of tetrabenzotetrazaporphins, especially of copper phthalocyanine and its phenylated and advantageously low halogenated derivatives. Especially bright shades are obtained with these dyes.
  • Other tetrazaporphins may however also form the basis of the "betaine" dyes used according to this invention.
  • T denotes the radical of a copper or nickel tetrazaporphin
  • Y denotes the radical of the formula:
  • n denotes one of the whole numbers from 1 to 8.
  • the alkaline dyeing composition of the invention includes as essential ingredients (A) a betaine dye as defined above and (B) an alkaline-reacting agent capable of fixing the dye under heat treatment to a cellulosic textile material.
  • the alkaline dyeing composition may be in the form of a dye bath or a printing paste in which the ingredients are dispersed or dissolved in water.
  • Other additives which are conventional for the preparation of aqueous baths or pastes of known dyes may also be included in the compositions of this invention, e.g. various known thickening agents, finishing agents or the like.
  • compositions of this invention therefore exclude such substances as formic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, diglycolic acid, citric acid, lactic acid, tartaric acid, maleic acid and oxalic acid, or acid-reacting salts such as sodium dihydrogen phosphate.
  • acid-reacting agents must not be present when the betaine dyes of the invention are applied to the cellulosic material.
  • Alkaline-reacting agents for this invention may be of an organic or inorganic nature, inorganic alkaline-reacting agents being preferred.
  • organic alkalinereacting agents are water-soluble aliphatic amines with a boiling point of, or advantageously above, C., as for example Z-hydroxyethylamine, 2- or 3-hydroxypropyl amine, tri-(Z-hydroxyethyl)-amine, tri-(Z- or 3-hydroxypropyl)-arnine or triethylenetetramine.
  • inorganic alkaline-reacting agents are hydroxides or carbonates of alkali metals oralkaline earth metal hydroxides, such as lithium hydroxide, rubidium hydroxide, rubidium carbonate, cesium hydroxide, barium hydroxide and preferably the hydroxides and carbonates of sodium and potassium which are especially economical'and convenient to use.
  • the alkaline-reacting agents can also be used in admixture with each other. Mixtures of tW or more tetrazaporphin dyes of the above-mentioned betaine type and/or mixtures of two or more alkaline agents may also be used for the new compositions and processes.
  • Dyeings and/or prints of the betaine dyes are fixed in the presence of the alkaline agent by heating for about 0.5 to 10 minutes at temperatures between 50 and C., preferably between 98 and 106 C. according to the new process. Fixation may be carried out by dry heating or advantageously by steaming.
  • Dyeings and/or prints obtainable according to this invention have excellent fastness properties, especially very good fastness to washing and soda boiling, and prints do not exhibit any bleeding.
  • betaine dyes used according to this invention which differ from the oniurn dyes used in the above-mentioned dyeing and printing methods only in their capability of forming internal salts between the quaternized nitrogen atom and the sulphonic acid or carboxylic acid radicals, would have a substantially lower sensitivity to alkalinereacting agents.
  • Alkaline solutions, padding liquors or prinitnig pastes containing the dyes used according to this invention are characterized as a rule on the one hand by high stability and do not deposit any insoluble constituents.
  • the dyes characteristic of the present invention are completely converted into a water-insoluble form on the material to be dyed or printed in the presence of alkaline reagents by steaming or dry heating and thus fixed in the fibers in a manner fast to rubbing, washing and 'soda boiling.
  • a special advantage of the new process is that the same results areobtained when different amounts or different kinds of alkaline-reacting agents are used. The new process is therefore of special importance for industry by reason of its simplicity.
  • betaine derivatives of copper of nickel tetrazaporphin used according to this invention can be fixed, even in the presence of vatting agents, without difliculty and without destruction of the dye onto cellulosic textile materials in an excellent way in the presporphin dyes of the above-mentioned betaine type together with van dyes for dyeing and/or printing cellulosic textile materials and the fixation of the dye mixtures in the way usual for vat dyes.
  • the dyes used according to this invention are stable to discharging, they are especially suitable for use in so-called discharge printing processes.
  • a fabric advantageously dyed with a dischargeable dye
  • a printing paste which contains, besides the usual printing auxiliaries, a dye of the kind used according to this invention. and an alkaline-react ng agent and one of the usual discharge agents, for example sodium formaldehyde sulphoxylate, and the material dried and steamed.
  • the printed parts of the fabric are locally dyed, following this process. in the shade of the dye used according to this invention, whereas the remaining parts of the fabric have the shade of the dischargeable dye.
  • the betaine. dyes used according to this invention may also be used in so-called resist printing processes, either as resists under aniline black or as resists under naphthol dyein'gs.
  • the dye aniline black is onlydevelopec'i by an acid reaction so that the parts of the fabric which have been treated with an alkaline printing paste com taining one of the 'betaine dyes according to this invention prevent the formation of aniline black and these parts of the fabric are dyed exclusively in the shade of the betaine dye used.
  • the resist action is based on the fact that after steaminga fabric which has been padded or impregnated with a coupling component usual for naphthol dyeing, as for example C. I. Azoic Coupling Component 2 (Colour Index, 2nd edition 1956. volume 3, page 3326, C. I. No. 37,705) and printed with an alkaline betaine dye according to'this invention, no coupling takes place at the printed parts during treatment with a diazotized amine, for example C. I. Azoic Diazo Component B (Colour Index, 2nd edition 1956, volume 3, page 3321, C. I. No. 37,125), by reason of the alkali content and the reducing agent content of the printing paste.
  • the printed parts of the fabric are therefore dyed only in the shade of the betaine dye and not in the shade of the azo dye to be formed.
  • Example 1 T being copper tetrazaporphin
  • 600 parts of a 10% aqueous solution of starch ether 60 parts of anhydrous sodium carbonate and 300 parts of water.
  • the fabric is then dried, steamed for seven minutes at 102 C. and then soaped at the boil. Prints having excellent fastness properties are obtained in bright turquoise blue shades on a white ground.
  • Potassium carbonate, sodium hydroxide or potassium hydroxide may also be used instead of sodium carbonate, the procedure otherwise being as above.
  • Example 2 T being copper tetrazaporphin
  • parts of sodium carbonate 60 parts of sodium formaldehyde sulphoxylate, 300 parts of a 10% wheat starch thickening, 300 parts of a 6% tragacanth mucilage and 220 parts of water.
  • the dye paste used in the first paragraph of this example is prepared as follows: 100 parts of an aqueous filtered product containing 24 parts of tetrachloromethyl copper phthalocyanine, and a solution of 24 parts of dimethylglycocoll potassium in 38 parts of water are stirred together for about one to two hours at 90 to 95 C., until a sample withdrawn and diluted with water is clearly soluble.
  • the dye solution which can easily be stirred while it is hot, becomes pasty when cooled.
  • Example 3 Spun rayon fabric is printed with a printing paste consisting of 40 parts of the blue dye paste used in Example 2, 300 parts of a thickening or carob bean fiuor ether, 400 parts of a starch ether thickening, 40 parts of a aqueous paste of the dye C.I. Vat Yellow (Colour Index, 2nd edition 1956, volume 3 page 3527, CL No. 68,420) and 220 parts of water.
  • the fabric After the fabric has been dried it is impregnated on a padding machine with a solution of 80 parts of sodium hydrosulphite and 90 parts of aqueous caustic soda solution of 38 Baum strength in 1000 parts of water and then steamed for 30 seconds with air-free steam at 110 C. Since the blue betaine dye has fastness properties of a comparable standard to those of the yellow vat dye used, very fast prints in green shades are obtained.
  • Example 5 v A spun rayon fabric is impregnated with Z-hydroxynapthalene-3-carboxylic acid anilide and then printed with a printing paste of the following composition:
  • Example 6 Cotton fabric is padded at 30 C. with an aqueous solution which contains per liter 20 grams of the dye described in Example .1 of German patent specification No. 843,725 in the form of an about 50% paste, 20 grams of anhydrous sodium carbonate and 50 grams of a 10% alginate thickening, and then dried at 50 to 60 C.
  • the dyed fabric is then steamed for six minutes at 100 C. or subjected to 3 a treatment with hot air at 150 to 160 C.
  • the dye ng is then finished off as usual by rinsing, soaping and drying'. Very fast dyeings in bright turquoise blue shades are thus obtained.
  • Example 7 Cotton fabric is printed with a printing paste of which each 1000 parts consists of:
  • Example 8 Cotton fabric is printed with a printing paste which contains, in 1000 parts:
  • Example 1 60 parts of the turquoise blue dye used in Example 1 10 parts of the blue reactive dye of the formula SOICHaCHaOSOtH O NH described in Example 4 on page 6 of British patent specification No. 867,546 20 parts of sodium carbonate 10 parts of aqueous caustic soda solution (38 Be.) 500 parts of 10% alginate thickening and 400 parts of water
  • the printed fabric is then dried and steamed for five minutes at 100 to 103 C.
  • the printed fabric is then rinsed, soaped and dried. Wet fast prints are obtained in bright bluish torquoise shades.
  • Example 9 20 parts of the yellow reactive dye used in Example 7 40 parts of the dye suspension described in the second paragraph of this example 50 parts of urea and 50 parts of sodium carbonate are dissolved in 1000 parts of water. Cotton fabric is impregnated with this solution by means of a padding machine, the liquor take-up being The fabric is then dried by means of a hot-air dryer at 80 C. and
  • the dye suspension used in'the first paragraph of this example is prepared as follows: 50 parts of an aqueous filtered product containing 10 parts of a mixture of irischloromethyl and tetrakischloromethyl copper phthalocyanine, 10 parts of dimethylglycocoll sodium and parts of water are stirred together for about two to three hours at 90 to 95 C. until-a sample of the reaction product is clearly soluble in water.
  • the mobile dye suspension thusobtained is used for dyeing in the way specified in the first paragraph of this example.
  • Example Cotton fabric is printed'with a paste which in 1000 parts contains parts of the dye prepared as described in the following paragraph, 600 parts of an about 10% aqueous solution of starch ether, 50 parts of anhydrous potassium carbonate and 330 parts of water. After drying the fabric is steamed for 10 minutes at 102 C., soaped at the boil and rinsed, blue prints having good fastness properties being obtained.
  • Example 1 Cotton batiste is printed in conventional manner with a printing paste which in 1000 parts contains parts of the dye prepared as described in this exaruple, 550
  • the dye herein used is prepared in the following manner:
  • the moist filtrate is stirred with a solution of 20 parts of dimethyl glycocoll potassium in 50 parts of water and the mixture is heated to 90 to 95 C.
  • Dye formation is-complete after a few hours.
  • a sample diluted with water dissolves completely.
  • the dye is precipitated by stirring the cold dye paste into ethanol, filtered off by suction and dried. It is obtained in an amount of about 23 parts and is soluble in water.
  • a process for dyeing and printing cellulosic textile material which comprises applying to said textile material a composition comprising (A) a tetrazaporphin dye of the formula in which T denotes a member selected from the class consisting of copper tetrazaporphin and nickel tetrazaporphin, Y denotes the radical of the formula and n denotes one of the whole numbers from 1 to 8 and (B) an alkaline-reacting agent, and then heating the material thus treated at a temperature between about and 150 C.
  • said textile material having been previously impregnated with aniline black, and the textile material is then heated to a temperature between about 98 to 106 C.
  • a coloring composition comprising a tetrazaporphin dye of the formula in which T denotes a member selected from the class consisting of copper tetrazaporphin and nickel tetrazaporphin, Y denotes the radical of the formula 11 12 CH; wherein the tetrazaporphin dye has the formula -i 1 -omooo CH: CH
  • n denotes one of the whole numbers from 1 to 8, a 3 e vat dye and an alkaline-reacting agent.
  • C 2 CHrCOO C 2 CHrCOO
  • a coloring composition comprising a tetrazaporphin dye of the formula 2 )n in which T denotes a member selected from the class wherem T copper tetrazaporphm' consisting of copper tetrazaporphin and nickel tetrazaporphin, Y denotes the radical of the formula References Cited by the Examiner UNITED STATES PATENTS 1,e e 15 2,599,371 6/1952 Chadderton et al.
  • n denotes one of the whole numbers from 1 to 8, a 843,725 7/ 1952 Germany. reactive dye and an alkalinereacting agent. 3 035 1 953 Great B i i 11.

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US348791A 1960-12-22 1964-03-02 Composition for and dyeing cellulose copper and nickel tetrazaporphin-betaine dye compositions and reactive dyeing cellulose therewith Expired - Lifetime US3320020A (en)

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DEB60586A DE1154789B (de) 1960-12-22 1960-12-22 Verfahren zum Faerben und bzw. oder Bedrucken von Textilgut aus Cellulose

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3787176A (en) * 1970-11-20 1974-01-22 Hoechst Ag Process for space-dyeing of cellulose fibers

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2599371A (en) * 1947-07-10 1952-06-03 Ici Ltd Printing with onium dyestuffs and buffer mixtures
DE843725C (de) * 1950-05-27 1952-07-10 Basf Ag Verfahren zur Herstellung von wasserloeslichen Farbstoffen der Phthalocyaninreihe
GB686036A (en) * 1950-07-04 1953-01-14 William Clarke New colouring process to give patterned or differential colour effects on textile materials

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2599371A (en) * 1947-07-10 1952-06-03 Ici Ltd Printing with onium dyestuffs and buffer mixtures
DE843725C (de) * 1950-05-27 1952-07-10 Basf Ag Verfahren zur Herstellung von wasserloeslichen Farbstoffen der Phthalocyaninreihe
GB686036A (en) * 1950-07-04 1953-01-14 William Clarke New colouring process to give patterned or differential colour effects on textile materials

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3787176A (en) * 1970-11-20 1974-01-22 Hoechst Ag Process for space-dyeing of cellulose fibers

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