US3129052A - New dyeing process - Google Patents

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US3129052A
US3129052A US3129052DA US3129052A US 3129052 A US3129052 A US 3129052A US 3129052D A US3129052D A US 3129052DA US 3129052 A US3129052 A US 3129052A
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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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • 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
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • 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
    • 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
    • D06P1/34—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 natural dyestuffs
    • 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
    • D06P1/38—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 reactive dyes
    • 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
    • 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
    • Y10S8/917—Wool or silk
    • 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
    • Y10S8/934—High temperature and pressure dyeing

Definitions

  • This invention relates to a dyeing process and more particularly it relates to a process for dyeing natural and regenerated protein textile materials.
  • the carbon atom may form part of an aryl ring present in the dyestuif molecule or may form part of an alkyl chain which is itself attached to an aryl ring.
  • the dyestufl may be a member of the azo, which may be monoazo or polyazo, nitro, anthraquinone and phthalocyanine, which may be metal-containing phthalocyanine such as copper phthalocyanine, series which contains a water-solubilising group such as a sulphamyl or carboxylic acid group and preferably a sulphonic acid group.
  • the azo dyestuiis may contain coordinately bound metal such as coordinately bound copper, chromium or cobalt.
  • alkyl radicals for example lower alkyl radicals such as methyl, ethyl, propyl and butyl radicals which may contain substituents such as hydroxy, methoxy and ethoxy groups, aralkyl radicals for example benzyl and fl-phenylethyl radicals, cycloalkyl radicals for example cyclohexyl radicals and aryl radicals for example monocyclic aryl radicals such as phenyl, tolyl and methoxyphenyl radicals. It is however preferred that R represents a hydrogen atom.
  • the process of the invention may be conveniently carried out by immersing the natural and regenerated protein textile material in an aqueous solution of the said dyestuii containing an acid or an acid salt so that the pH of the aqueous solution is less than 7 and is preferably between 2 and 7, heating the dyebath for a period at a suitable temperature, for example at a temperature betweeen 80 C. and 100 C., adding an alkyl, an alkaline salt, or a salt which becomes alkaline when heated, to raise the pH of the dyebath, preferably to a pH of between 4.5 and 8, and heating for a further period at a suitable temperature, for example at a temperature beice tween C. and C.
  • the dyed textile material is then removed from the dyebath, rinsed in water and dried. If desired the dyed textile material may be given a soaping treatment, for example by heating the dyed textile material in an aqueous solution of soap or synthetic detergent, the aqueous solution optionally containing an alkali such as sodium carbonate.
  • a soaping treatment for example by heating the dyed textile material in an aqueous solution of soap or synthetic detergent, the aqueous solution optionally containing an alkali such as sodium carbonate.
  • acids or acid salts which may be used in the process of the invention there may be mentioned sulphuric acid, acetic acid, formic acid, phosphoric acid and sodium dihydrogen phosphate, and as examples of the alkalis, alkaline salts, or salts which become alkaline when heated, which may be used in the process of the invention there may be mentioned sodium carbonate, sodium bicarbonate, sodium acetate, sodium hydroxide, trisodium phosphate, disodium hydrogen phosphate, sodium trichloroacetate, barium hydroxide, lithium hydroxide, sodium silicate, potassium carbonate and potassium hydroxide.
  • mixtures of acids and/or acid salts or mixtures of alkalis and/or alkaline salts may be used in the process of the invention.
  • the process of the invention may be carried out at a temperature above 100 C., for example at temperatures between 100 C. and C. under superatmospheric pressure.
  • dyebath substances which are commonly used in the dyeing of natural and regenerated protein textile materials, such as sodium sulphate or urea, or there may be present anionic surfaceactive agents such as the disodium salt of methylene dinaphthalene sulphonic acid, and non-ionic agents such as condensates of ethylene oxide with an amine fatty alcohol or an alkylphenol.
  • the dyestuffs used in the process of the invention wherein X represents may be obtained by reacting the corresponding watersoluble dyestufr containing at least one group with acryloyl chloride.
  • the dyestuffs used in the process of the invention wherein X represents SO may be obtained by treating the corresponding dyestuff containing at least one SO CH CH OH group with sulphuric acid to form the sulphate ester and subsequently treating with sodium hydroxide.
  • textile materials which may be dyed by the process of the invention there may be mentioned textile materials com- 3 prising wool and 'silk fibres and regenerated protein fibres made from casein or ardein, and leather.
  • Example 1 0.2 part of the dyestuff disclosed in Example 6 of British specification No. 712,037 is dissolved in 20 parts of water and the solution so obtained is added to 1000 parts of water containing 1.6 parts of a sulphuric acid and 2 parts of sodium sulphate. 20 parts of wool serge are placed in the dyebath thus obtained which is then heated to 100 C. and maintained at this temperature for 30-minutes. 6 parts of trisodium phosphate are then added and dyeing is continued for a further 45 minutes at a temperature of 100 C. The dyed Wool serge is then removed from the dyebath, rinsed in water and dried.
  • the wool serge is dyed a uniform bright blue shade possessing much better fastness to Wet treatments than Wool serge which was dyed as described above except that the trisodium phosphate was not added to the dyebath.
  • Example 2 0.2 part of the sodium salt of 1-(4-acryloylaminophenyl -3-methyl-4-(o-sulphophenylazo -5-pyrazolone is dissolved in 20 parts of water and the solution so obtained is added to 1000 parts of water containing 0.6 part of sulphuric acid and 2 parts of sodium sulphate. 20 parts of wool serge are immersed in the dyebath thus obtained which is then heated to 100 C. and maintained at this temperature for 30 minutes. 1.5 parts of trisodium phosphate are then added and dyeing is continued for a further 45 minutes at a temperature of 100 C. The dyed wool serge is then removed from the dyebath, rinsed in water and dried.
  • the wool serge is dyed a uniform bright greenishyellow shade possessing much better fastness to wet treatments than wool serge which was dyed as described above except that the trisodium phosphate was not added to the dyebath.
  • the dyestufi used in the above example may be obtained by coupling diazotised orthanilic acid with l-(4- acryloylaminophenyl)-3-methyl-5-pyrazolone.
  • Example 3 A solution of 0.2 part of the monosodium salt of 2 acryloylamino-7-(2-methoxyphenylazo)-8-naphthol-6- sulphonic acid in 20 parts of water is added to 1000 parts of water containing 0.6 part of phosphoric acid and 2 parts of sodium sulphate. 20 parts of wool serge are immersed in the dyebath thus obtained which is then heated to 100 C. and maintained at this temperature for 30 minutes. An aqueous solution containing 2 parts of disodium hydrogen phosphate crystals are then added and dyeing is continued for a further 60 minutes at a temperature of 100 C. The dyed wool serge is then removed from the dyebath, rinsed in water and dried.
  • the wool serge is dyed a uniform bright bluish-red shade possessing much better fastness to wet treatments than wool serge which was dyed as described above except that the aqueous solution of disodium hydrogen phosphate was not added to the dyebath.
  • the dyestuif used in the above example may be obtained by coupling diazotised o-anisidine with 2-acryloylamino-8- naphthol-6-sulphonic acid in alkaline medium.
  • Example 4 20 parts of worsted yarn are immersed in a dyebath comprising a solution of 0.2 part of the monosodium salt of 1-acryloylamino-8-(2-sulphophenylazo)-7-naphthol, 1 part of sulphuric acid and 2 parts of sodium sulphate in 1000 parts of water, and the dyebath is then heated to C., and maintained at this temperature for 30 minutes. 3 parts of sodium trichloroacetate are then added and dyeing is continued for a further hour at 100 C. The dyed yarn is then removed from the dyebath, rinsed in water and dried.
  • the worsted yarn is dyed a uniform reddish-orange shade possessing much better fastness to Wet treatments than worsted yarn which was dyed as described above except that the 3 parts of sodium trichloroacetate were not added to the dyebath.
  • the dyestulf used in the above example may be obtained by coupling diazotised orthanilic acid with l-acryloylamino-7-naphthol in alkaline medium.
  • Example 5 A solution of 0.5 part of the lz2-chromium complex of l-acryloylamino-8-(2'-hydroxy-4'-sulpamylphenylazo)- 7-naphthol in 20 parts of water is added to 4000 parts of water containing 3 parts of ammonium acetate. 100 parts of wool serge are immersed in the dyebath so obtained which is then heated to 100 C. during 30 minutes. Disodium hydrogen phosphate is then added until the pH of the dyebath is 7.5 and dyeing is continued for a further 15 minutes at 100 C. The dyed Wool serge is then removed from the dyebath, rinsed in water and dried.
  • the wool serge is dyed a uniform grey shade possessing much better fastness to a potting treatment than wool serge which was dyed as described above except that the disodium hydrogen phosphate was not added to the dyebath.
  • Example 6 20 parts of wool serge are immersed in a dyebath comprising a solution of 0.2 part of the disodium salt of l-amino-4-[4-acryloylarnino 3 sulphoanilino]-anthra quinone-Z-sulphonic acid, 0.6 part of sulphuric acid and 2 parts of sodium sulphate in 1000 parts of water, and dyeing is then carried out for 30 minutes at 100 C. 1.5 parts of trisodium phosphate are then added and dyeing is continued for 1 /2 hours at 100 C. The dyed wool serge is then removed from the dyebath, rinsed in water and dried. The wool serge is dyed a uniform bright greenish-blue shade possessing much better fastness to wet treatments than wool serge which was dyed as described above except that the trisodium phosphate was not added to the dyebath.
  • the dyestuff used in the above example may be obtained by treating 1-amino-4-(4'-arnino-3'-sulphoanilino) anthraquinone-Z-sulphonic acid with acryloyl chloride in the presence of pyridine and converting the resulting product to the disodium salt.
  • Example 7 In place of the 0.2 part of the dyestuif used in Example 6 there is used 0.2 part of the sodium salt of l-[fi- (2' carboxyphenylazo)acetoacetylamino] 4 acryloylaminobenzene whereby the wool serge is dyed a uniform bright greenish-yellow shade.
  • the dyestulf used in the above example may be obtained by coupling diazotised anthranilic acid with l-acetoacetylamino-4-acryloylaminobenzene.
  • the following table gives further examples of dyeings obtained on wool serge by the method described in Example 5 above except that the 0.5 part of the dyestutt' used in Example 5 is replaced by 0.5 part of the dyestuffs obtained by diazotising the amines listed in the second column of the table, coupling with the coupling components listed in the third column of the table and subsequently converting the resulting monoazo compounds to the 1:2-metal complexes by heating with a solution of the acetate of the metal listed in the fourth column of the table.
  • the fifth column of the table indicates the shades obtained on wool.
  • Amine Coupling Component Metal Shade 4-methoxy-2-aminophenol 1-acryloy1amine-7-naphthol chromium-.- Greenish-grey. 4-nitro-2-aminopheuo1 2-acryloylamino-fi-naphthol cobalt Reddish-brown. 2-aminophenol-5-sulnhonamide o ohromiu m Reddish-grey.
  • Example 17 In place of the 05 part of the dyestuff used in Example 5 there is used 0.5 part of the mixed 1:2-chromium complex of 1-acryloylamino-3-(2'-hydroxy-5'-nitrophenylazo)-4-naphthol and l-(2'-hydroxynaphth-1-ylaz0)-6-ni tro-2-naphthol-4-sulphonic acid whereby the wool is dyed a uniform black shade.
  • Example 18 20 parts of wool serve are immersed in a dyebath comprising a solution of 1 part of copper phthalocyanine 3- sulphon N-(3'-acryloylaminophenyl)amidesulphonamide sulphonic acid, 0.6 part of sulphuric acid, 0.2 part of cetyl trimethylammom'um bromide and 0.4 part of a fatty alcohol/ethylene oxide condensate in 1000 parts of water, and the dyebath is then heated to 100 C. and maintained at this temperature for 30 minutes. 1.8 parts of trisodium phosphate are then added and dyeing is continued for a further hour at 100 C. The dyed wool serge is then removed from the dyebath, rinsed in Water and dried.
  • a dyebath comprising a solution of 1 part of copper phthalocyanine 3- sulphon N-(3'-acryloylaminophenyl)amidesulphonamide sulphonic acid, 0.6 part of sulphuric acid, 0.2 part
  • Wool serge is dyed a uniform greenish-blue shade prossessing much better fastness to wet treatments then wool serge which was dyed as described above except that the trisodium phosphate was not added to the dyebath.
  • the dyestutf used in the above example may be obtained by reacting copper phthalocyanine tetra3-sulphonchloride with m-acetylamino-aniline in aqueous medium in the presence of ammonia, heating with an aqueous solution of hydrochloric acid to hydrolyse the N-acetyl group, and subsequently condensing with acryloyl chloride in aqueous medium.
  • Process for dyeing natural and regenerated protein textile materials with a water-soluble dyestufr of the class 5 consisting of azo, nitro, anthraquinone, and phthalocyanine, and which contain an acryloylarnino group attached to a carbon atom of the dyestufi which process comprises treating the textile material with an aqueous solution containing, as essential ingredients, said dyestuif and a member selected from the class consisting of acids and acid salts in sufiicient amount so that the pH of the solution is less than 7, heating the solution While said textile material is treated therewith, thereafter adding a material selected from the class consisting of alkalis, alkaline salts, and salts which become alkaline on heating, in sufficient quantity so that the pH of the solution is raised to a level of about 4.5 to 8, and then continuing heating said solution until the dyeing is completed.

Description

United States Patent 3,129,052 NEW DYEING PROCESS Timothy Leslie Dawson and Walter Percival Mills, Manchester, England, assignors to Imperial Chemical Industries Limited, London, England, a corporation of Great Britain No Drawing. Filed Oct. 24, 1960, Ser. No. 64,285 Claims priority, application Great Britain Nov. 13, 1959 4 (Ilaims. (Cl. 8-54) This invention relates to a dyeing process and more particularly it relates to a process for dyeing natural and regenerated protein textile materials.
According to the invention there is provided a process for dyeing natural and regenerated protein textile materials with a water-soluble dyestulf which contains at least one group of the formula: XCH=CH wherein X represents a --SO or group and R repreesents a hydrogen atom or a substituted or unsubstituted hydrocarbon radical, which comprises dyeing the natural and regenerated protein textile material with an aqueous solution of the said dyestuff at a pH less than 7 and subsequently raising the pH during the dyeing process.
Each of the groups of the formula: XCH=CH is attached to a carbon atom present in the dyestufi" molecule. The carbon atom may form part of an aryl ring present in the dyestuif molecule or may form part of an alkyl chain which is itself attached to an aryl ring. The dyestufl may be a member of the azo, which may be monoazo or polyazo, nitro, anthraquinone and phthalocyanine, which may be metal-containing phthalocyanine such as copper phthalocyanine, series which contains a water-solubilising group such as a sulphamyl or carboxylic acid group and preferably a sulphonic acid group. If desired the azo dyestuiis may contain coordinately bound metal such as coordinately bound copper, chromium or cobalt.
As examples of the substituted or unsubstituted hydrocarbon radicals represented by R there may be mentioned alkyl radicals for example lower alkyl radicals such as methyl, ethyl, propyl and butyl radicals which may contain substituents such as hydroxy, methoxy and ethoxy groups, aralkyl radicals for example benzyl and fl-phenylethyl radicals, cycloalkyl radicals for example cyclohexyl radicals and aryl radicals for example monocyclic aryl radicals such as phenyl, tolyl and methoxyphenyl radicals. It is however preferred that R represents a hydrogen atom.
The process of the invention may be conveniently carried out by immersing the natural and regenerated protein textile material in an aqueous solution of the said dyestuii containing an acid or an acid salt so that the pH of the aqueous solution is less than 7 and is preferably between 2 and 7, heating the dyebath for a period at a suitable temperature, for example at a temperature betweeen 80 C. and 100 C., adding an alkyl, an alkaline salt, or a salt which becomes alkaline when heated, to raise the pH of the dyebath, preferably to a pH of between 4.5 and 8, and heating for a further period at a suitable temperature, for example at a temperature beice tween C. and C. The dyed textile material is then removed from the dyebath, rinsed in water and dried. If desired the dyed textile material may be given a soaping treatment, for example by heating the dyed textile material in an aqueous solution of soap or synthetic detergent, the aqueous solution optionally containing an alkali such as sodium carbonate.
As examples of the acids or acid salts which may be used in the process of the invention there may be mentioned sulphuric acid, acetic acid, formic acid, phosphoric acid and sodium dihydrogen phosphate, and as examples of the alkalis, alkaline salts, or salts which become alkaline when heated, which may be used in the process of the invention there may be mentioned sodium carbonate, sodium bicarbonate, sodium acetate, sodium hydroxide, trisodium phosphate, disodium hydrogen phosphate, sodium trichloroacetate, barium hydroxide, lithium hydroxide, sodium silicate, potassium carbonate and potassium hydroxide.
If desired mixtures of acids and/or acid salts or mixtures of alkalis and/or alkaline salts may be used in the process of the invention.
If desired the process of the invention may be carried out at a temperature above 100 C., for example at temperatures between 100 C. and C. under superatmospheric pressure.
There may also be present in the dyebath substances which are commonly used in the dyeing of natural and regenerated protein textile materials, such as sodium sulphate or urea, or there may be present anionic surfaceactive agents such as the disodium salt of methylene dinaphthalene sulphonic acid, and non-ionic agents such as condensates of ethylene oxide with an amine fatty alcohol or an alkylphenol.
The dyestuffs used in the process of the invention wherein X represents may be obtained by reacting the corresponding watersoluble dyestufr containing at least one group with acryloyl chloride.
The dyestuffs used in the process of the invention wherein X represents SO may be obtained by treating the corresponding dyestuff containing at least one SO CH CH OH group with sulphuric acid to form the sulphate ester and subsequently treating with sodium hydroxide.
Specific examples of water-soluble dyestuffs containing at least one group of the formula --X-CH=CH wherein X has the meaning stated above, which may be used in the process of the invention are described in British specifications Nos. 712,037, 776,265, 787,986 and 831,128, and in Belgian specifications Nos. 565,279, 565,447, 569,- 964, 573,862, 576,105 and 577,140. It is however preferred that the dyestuifs used in the process of the invention are Water-soluble dyestuffs containing at least one acryloylamino group.
As examples of natural and regenerated protein textile materials which may be dyed by the process of the invention there may be mentioned textile materials com- 3 prising wool and 'silk fibres and regenerated protein fibres made from casein or ardein, and leather.
By the process of the invention there are obtained on natural and regenerated protein textile materials uniform dyeings in a wide range of bright shades which are free from the fibre to fibre unlevelness known to the trade as skitteriness and which have excellent fastness to rubbing and to wet treatments such as washing and milling.
The invention is illustrated but not limited by the following examples in which the parts and percentages are by weight:
Example 1 0.2 part of the dyestuff disclosed in Example 6 of British specification No. 712,037 is dissolved in 20 parts of water and the solution so obtained is added to 1000 parts of water containing 1.6 parts of a sulphuric acid and 2 parts of sodium sulphate. 20 parts of wool serge are placed in the dyebath thus obtained which is then heated to 100 C. and maintained at this temperature for 30-minutes. 6 parts of trisodium phosphate are then added and dyeing is continued for a further 45 minutes at a temperature of 100 C. The dyed Wool serge is then removed from the dyebath, rinsed in water and dried.
The wool serge is dyed a uniform bright blue shade possessing much better fastness to Wet treatments than Wool serge which was dyed as described above except that the trisodium phosphate was not added to the dyebath.
Example 2 0.2 part of the sodium salt of 1-(4-acryloylaminophenyl -3-methyl-4-(o-sulphophenylazo -5-pyrazolone is dissolved in 20 parts of water and the solution so obtained is added to 1000 parts of water containing 0.6 part of sulphuric acid and 2 parts of sodium sulphate. 20 parts of wool serge are immersed in the dyebath thus obtained which is then heated to 100 C. and maintained at this temperature for 30 minutes. 1.5 parts of trisodium phosphate are then added and dyeing is continued for a further 45 minutes at a temperature of 100 C. The dyed wool serge is then removed from the dyebath, rinsed in water and dried.
The wool serge is dyed a uniform bright greenishyellow shade possessing much better fastness to wet treatments than wool serge which was dyed as described above except that the trisodium phosphate was not added to the dyebath.
The dyestufi used in the above example may be obtained by coupling diazotised orthanilic acid with l-(4- acryloylaminophenyl)-3-methyl-5-pyrazolone.
Example 3 A solution of 0.2 part of the monosodium salt of 2 acryloylamino-7-(2-methoxyphenylazo)-8-naphthol-6- sulphonic acid in 20 parts of water is added to 1000 parts of water containing 0.6 part of phosphoric acid and 2 parts of sodium sulphate. 20 parts of wool serge are immersed in the dyebath thus obtained which is then heated to 100 C. and maintained at this temperature for 30 minutes. An aqueous solution containing 2 parts of disodium hydrogen phosphate crystals are then added and dyeing is continued for a further 60 minutes at a temperature of 100 C. The dyed wool serge is then removed from the dyebath, rinsed in water and dried.
The wool serge is dyed a uniform bright bluish-red shade possessing much better fastness to wet treatments than wool serge which was dyed as described above except that the aqueous solution of disodium hydrogen phosphate was not added to the dyebath.
The dyestuif used in the above example may be obtained by coupling diazotised o-anisidine with 2-acryloylamino-8- naphthol-6-sulphonic acid in alkaline medium.
Example 4 20 parts of worsted yarn are immersed in a dyebath comprising a solution of 0.2 part of the monosodium salt of 1-acryloylamino-8-(2-sulphophenylazo)-7-naphthol, 1 part of sulphuric acid and 2 parts of sodium sulphate in 1000 parts of water, and the dyebath is then heated to C., and maintained at this temperature for 30 minutes. 3 parts of sodium trichloroacetate are then added and dyeing is continued for a further hour at 100 C. The dyed yarn is then removed from the dyebath, rinsed in water and dried.
The worsted yarn is dyed a uniform reddish-orange shade possessing much better fastness to Wet treatments than worsted yarn which Was dyed as described above except that the 3 parts of sodium trichloroacetate were not added to the dyebath.
The dyestulf used in the above example may be obtained by coupling diazotised orthanilic acid with l-acryloylamino-7-naphthol in alkaline medium.
Example 5 A solution of 0.5 part of the lz2-chromium complex of l-acryloylamino-8-(2'-hydroxy-4'-sulpamylphenylazo)- 7-naphthol in 20 parts of water is added to 4000 parts of water containing 3 parts of ammonium acetate. 100 parts of wool serge are immersed in the dyebath so obtained which is then heated to 100 C. during 30 minutes. Disodium hydrogen phosphate is then added until the pH of the dyebath is 7.5 and dyeing is continued for a further 15 minutes at 100 C. The dyed Wool serge is then removed from the dyebath, rinsed in water and dried.
The wool serge is dyed a uniform grey shade possessing much better fastness to a potting treatment than wool serge which was dyed as described above except that the disodium hydrogen phosphate was not added to the dyebath.
Example 6 20 parts of wool serge are immersed in a dyebath comprising a solution of 0.2 part of the disodium salt of l-amino-4-[4-acryloylarnino 3 sulphoanilino]-anthra quinone-Z-sulphonic acid, 0.6 part of sulphuric acid and 2 parts of sodium sulphate in 1000 parts of water, and dyeing is then carried out for 30 minutes at 100 C. 1.5 parts of trisodium phosphate are then added and dyeing is continued for 1 /2 hours at 100 C. The dyed wool serge is then removed from the dyebath, rinsed in water and dried. The wool serge is dyed a uniform bright greenish-blue shade possessing much better fastness to wet treatments than wool serge which was dyed as described above except that the trisodium phosphate was not added to the dyebath.
The dyestuff used in the above example may be obtained by treating 1-amino-4-(4'-arnino-3'-sulphoanilino) anthraquinone-Z-sulphonic acid with acryloyl chloride in the presence of pyridine and converting the resulting product to the disodium salt.
Example 7 In place of the 0.2 part of the dyestuif used in Example 6 there is used 0.2 part of the sodium salt of l-[fi- (2' carboxyphenylazo)acetoacetylamino] 4 acryloylaminobenzene whereby the wool serge is dyed a uniform bright greenish-yellow shade.
The dyestulf used in the above example may be obtained by coupling diazotised anthranilic acid with l-acetoacetylamino-4-acryloylaminobenzene.
The following table gives further examples of dyeings obtained on wool serge by the method described in Example 5 above except that the 0.5 part of the dyestutt' used in Example 5 is replaced by 0.5 part of the dyestuffs obtained by diazotising the amines listed in the second column of the table, coupling with the coupling components listed in the third column of the table and subsequently converting the resulting monoazo compounds to the 1:2-metal complexes by heating with a solution of the acetate of the metal listed in the fourth column of the table. The fifth column of the table indicates the shades obtained on wool.
Amine Coupling Component Metal Shade 4-methoxy-2-aminophenol 1-acryloy1amine-7-naphthol chromium-.- Greenish-grey. 4-nitro-2-aminopheuo1 2-acryloylamino-fi-naphthol cobalt Reddish-brown. 2-aminophenol-5-sulnhonamide o ohromiu m Reddish-grey.
11- 4-acryloylarnino-2-aminonhenn1 fl-rmphfhfil cobalt Violet.
12 2-aminophenol-4-fl-hydroxyethyl-sul- 1-(4-acryloylaminophenyl)-3-methy1- ehromium Reddish-orauge.
phone. fi-pyrazolone.
13 Mixture of 4-nitro-2-amino-pheno1 and 1-phenyl3-methyl-5-pyrazolone do Bluish-red.
4-aoryloylamino-Z-aminobenzoic acid.
14 4-nitro-2-aminophenol 1-(4-acr aloylaminophenyl)-3-methy1-5- do Reddish-orange.
' pyrazo one.
15 authranilie acid 1-(2-methyl-5-aeryloylaminophenyl)-3- do Greenish-yellow.
methyl-5-pyrazolone. 16 5-nitro-2-aminophenol do cobalt Red.
Example 17 In place of the 05 part of the dyestuff used in Example 5 there is used 0.5 part of the mixed 1:2-chromium complex of 1-acryloylamino-3-(2'-hydroxy-5'-nitrophenylazo)-4-naphthol and l-(2'-hydroxynaphth-1-ylaz0)-6-ni tro-2-naphthol-4-sulphonic acid whereby the wool is dyed a uniform black shade.
Example 18 20 parts of wool serve are immersed in a dyebath comprising a solution of 1 part of copper phthalocyanine 3- sulphon N-(3'-acryloylaminophenyl)amidesulphonamide sulphonic acid, 0.6 part of sulphuric acid, 0.2 part of cetyl trimethylammom'um bromide and 0.4 part of a fatty alcohol/ethylene oxide condensate in 1000 parts of water, and the dyebath is then heated to 100 C. and maintained at this temperature for 30 minutes. 1.8 parts of trisodium phosphate are then added and dyeing is continued for a further hour at 100 C. The dyed wool serge is then removed from the dyebath, rinsed in Water and dried.
The Wool serge is dyed a uniform greenish-blue shade prossessing much better fastness to wet treatments then wool serge which was dyed as described above except that the trisodium phosphate was not added to the dyebath.
The dyestutf used in the above example may be obtained by reacting copper phthalocyanine tetra3-sulphonchloride with m-acetylamino-aniline in aqueous medium in the presence of ammonia, heating with an aqueous solution of hydrochloric acid to hydrolyse the N-acetyl group, and subsequently condensing with acryloyl chloride in aqueous medium.
What we claim is:
1. Process for dyeing natural and regenerated protein textile materials with a water-soluble dyestufr of the class 5 consisting of azo, nitro, anthraquinone, and phthalocyanine, and which contain an acryloylarnino group attached to a carbon atom of the dyestufi, which process comprises treating the textile material with an aqueous solution containing, as essential ingredients, said dyestuif and a member selected from the class consisting of acids and acid salts in sufiicient amount so that the pH of the solution is less than 7, heating the solution While said textile material is treated therewith, thereafter adding a material selected from the class consisting of alkalis, alkaline salts, and salts which become alkaline on heating, in sufficient quantity so that the pH of the solution is raised to a level of about 4.5 to 8, and then continuing heating said solution until the dyeing is completed.
2. Process, as claimed in claim 1, wherein said pH is initially at least 2.
3. Process, as claimed in claim 1, wherein said solution is heated at each stage at a temperature within the range of about 80 C. to about 100 C., during said process.
4. Process, as claimed in claim 1, wherein said textile material is a Woollen textile material.
References Cited in the file of this patent UNITED STATES PATENTS 2,784,204 Heyna et a1. Mar. 5, 1957 3,049,392 Casty et a1. Aug. 14, 1962 FOREIGN PATENTS 712,037 Great Britain July 14, 1954 733,471 Great Britain July 13, 1955 965,902 Germany Sept. 19, 1957 565,279 Belgium Mar. 15, 1958 565,447 Belgium Sept. 6, 1958 569,964 Belgium Ian. 31, 1959

Claims (1)

1. PROCESS FOR DYEING NATURAL AND REGENERATED PROTEIN TEXTILE MATERIALS WITH A WATER-SOLUBLE DYESTUFF OF THE CLASS CONSISTING OF AZO, NITRO, ANTHRAQUINONE, AND PHTHALOCYANINE, AND WHICH CONTAIN AN ACRYLOYLAMINO GROUP ATTACHED TO A CARBON ATOM OF THE DYESTUFF, WHICH PROCESS COMPRISES TREATING THE TEXTILE MATERIAL WITH AN AQUEOUS SOLUTION CONTAINING, AS ESSENTIALY INGREDIENTS, SAID DYESTUFF AND A MEMBER SELECTED FROM THE CLASS CONSISTING OF ACIDS AND ACID SALTS IN SUFFICIENT AMOUNT SO THAT THE PH OF THE SOLUTION IS LESS THAN 7, HEATING THE SOLUTION WHILE SAID TEXTILE MATERIAL IS TREATED THEREWITH, THEREAFTER ADDING A MATERIAL SELECTED FROM THE CLASS CONSISTING OF ALKALIS, ALKALINE SALTS, AND SALTS WHICH BECOME ALKALINE ON HEATING, IN SUFFICIENT QUANTITY SO THAT THE PH OF THE SOLUTION IS RAISED TO A LEVEL OF ABOUT 4.5 TO 8, AND THEN CONTINUING HEATING SAID SOLUTION UNTIL THE DYEING IS COMPLETED.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3291556A (en) * 1962-11-23 1966-12-13 Ciba Ltd Process for dyeing wool yarn and preparations for use therein
US3356445A (en) * 1963-08-29 1967-12-05 Ciba Ltd Process for dyeing or printing natural nitrogenous fibrous material
US4555348A (en) * 1984-06-28 1985-11-26 Sybron Chemicals Inc. Liquid buffer system
US4885360A (en) * 1982-12-20 1989-12-05 Ciba-Geigy Corporation Reactive dyes containing a sulfonyl and an aliphatic acyl reactive radical
US5102459A (en) * 1987-10-13 1992-04-07 Hoechst Aktiengesellschaft Use of colorants for recording fluids
US5523397A (en) * 1993-10-12 1996-06-04 Ciba-Geigy Corporation Reactive dyes, process for their preparation and the use thereof

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BE565279A (en) * 1957-03-01
BE565447A (en) *
GB712037A (en) * 1950-01-09 1954-07-14 Hoechst Ag A process for producing fast dyeings and the manufacture of dyestuffs for use therein
GB733471A (en) * 1949-07-18 1955-07-13 Hoechst Ag A process for fixing organic compounds on fibrous materials
US2784204A (en) * 1952-06-09 1957-03-05 Hoechst Ag Diphenylamine-vinylsulfone
DE965902C (en) * 1949-07-19 1957-09-19 Hoechst Ag Process for fixing water-soluble organic compounds on substrates with a fibrous structure
US3049392A (en) * 1962-08-14 Process for dyeing nitrogenous mate-

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Publication number Priority date Publication date Assignee Title
BE569964A (en) *
BE565447A (en) *
US3049392A (en) * 1962-08-14 Process for dyeing nitrogenous mate-
GB733471A (en) * 1949-07-18 1955-07-13 Hoechst Ag A process for fixing organic compounds on fibrous materials
DE965902C (en) * 1949-07-19 1957-09-19 Hoechst Ag Process for fixing water-soluble organic compounds on substrates with a fibrous structure
GB712037A (en) * 1950-01-09 1954-07-14 Hoechst Ag A process for producing fast dyeings and the manufacture of dyestuffs for use therein
US2784204A (en) * 1952-06-09 1957-03-05 Hoechst Ag Diphenylamine-vinylsulfone
BE565279A (en) * 1957-03-01

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3291556A (en) * 1962-11-23 1966-12-13 Ciba Ltd Process for dyeing wool yarn and preparations for use therein
US3356445A (en) * 1963-08-29 1967-12-05 Ciba Ltd Process for dyeing or printing natural nitrogenous fibrous material
US4885360A (en) * 1982-12-20 1989-12-05 Ciba-Geigy Corporation Reactive dyes containing a sulfonyl and an aliphatic acyl reactive radical
US4555348A (en) * 1984-06-28 1985-11-26 Sybron Chemicals Inc. Liquid buffer system
US5102459A (en) * 1987-10-13 1992-04-07 Hoechst Aktiengesellschaft Use of colorants for recording fluids
US5523397A (en) * 1993-10-12 1996-06-04 Ciba-Geigy Corporation Reactive dyes, process for their preparation and the use thereof
US5597904A (en) * 1993-10-12 1997-01-28 Ciba-Geigy Corporation Reactive dyes, process for their preparation and the use thereof

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