US3097043A - New dyeing process - Google Patents

New dyeing process Download PDF

Info

Publication number
US3097043A
US3097043A US3097043DA US3097043A US 3097043 A US3097043 A US 3097043A US 3097043D A US3097043D A US 3097043DA US 3097043 A US3097043 A US 3097043A
Authority
US
United States
Prior art keywords
textile material
group
disperse
dyeing
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
Publication date
Application granted granted Critical
Publication of US3097043A publication Critical patent/US3097043A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/653—Nitrogen-free carboxylic acids or their salts
    • 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
    • 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
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • 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
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D06P3/241—Polyamides; Polyurethanes using acid 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
    • 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
    • D06P3/82—Textiles which contain different kinds of fibres
    • D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
    • 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
    • D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric
    • D06P5/2066—Thermic treatments of textile materials
    • D06P5/2077—Thermic treatments of textile materials after 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
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/924—Polyamide fiber
    • 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
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/927—Polyacrylonitrile fiber

Definitions

  • synthetic polymeric textile materials can be dyed with disperse dyestuffs which are free from sulphonic acid and carboxylic acid groups and which contain at least one reactive halogen atom or other reactive group which is capable of reacting with the synthetic polymeric textile material so that the said disperse dyestuff is fixed to the synthetic polymeric textile material by a chemical bond, whereby dyeings are obtained which have excellent fastness to washing.
  • an improved process for dyeing synthetic polymeric textile materials with disperse reactive dyestuffs which comprises dyeing the synthetic polymeric textile material with an aqueous dispersion of the said dyestuff at a pH less than 7 and subsequently raising the pH during the dyeing process.
  • the process of the invention may be conveniently carried out by immersing the synthetic polymeric textile material in an aqueous dispersion of the disperse reactive dyestulf containing an acid or an acid-salt so that the pH of the aqueous dispersion is less than 7 and is preferably between 3 and 5, heating the dyebath for a period at a suitable temperature, for example at a temperature between 90 to 100 C., adding an alkali or an alkaline salt to raise the pH of the dyebath, preferably to a pH between 9 and 12, and heating for a further period at a suitable temperature, for example at a temperature between 90 and 100 C.
  • the textile material is then removed from the dyebath, rinsed in water and dried.
  • the process or" the invention may be carried out at temperatures above 100 C., for example at temperatures between 100 and 130 C. under superat-mospheric pressure.
  • the process of the invention can be carried out at temperatures below 90 C., for example at temperatures between 70 and 90 C., but, in order that the resulting dyeings shall possess maximum fastness to washing, it is preferred to subsequently subject the dyeing so obtained to a dry heat treatment at a temperature beween 160 and 230 C.
  • a dry heat treatment at a temperature beween 160 and 230 C.
  • organic acids for example aliphatic organic acids and in particular monobasic lower fatty acids such as acetic acid and formic acid and inorganic acid salts such as sodium dihydrogen phosphate
  • alkalis or alkaline salts which may be used in the process of the invention there may be mentioned inorganic alkalis and inorganic alkaline salts such as sodium carbonate, sodium hydroxide, trisodium phosphate, barium hydroxide, lithium hydroxide, sodium silicate, potassium carbonate and potassium hydroxide.
  • mixtures of acids and/or acid salts and/ or mixtures of alkalis and/or alkaline salts may be used in the process of the invention.
  • disperse reactive dyestuff there is meant a disperse or water-insoluble dyestuff which is free from sulphonic acid and carboxylic acid groups and which contains at least one reactive halogen atom or other reactive atom or group, that is to say a halogen atom or other group capable of reacting with the synthetic polymeric textile material.
  • disperse reactive dyestuifs examples include water-insoluble dyestuffs containing a 1:3:5-triazinyl radical carrying one or two chlorine or bromine atoms directly attached to the triazine ring, disperse dyestuffs containing a pyrimidyl radical carrying one or two chlorine or bromine atoms directly attached to the pyrimidine ring, disperse dyestuffs containing at least one 'y-halogeno-[i-hydroxypropylamino group, disperse dyestuffs containing at least one di-(v-ha1ogen0-5- hydroxypropyl)amino group, disperse dyestuffs containing at least one [i-halogenoethylsulphamyl group, disperse dyestuffs containing at least one fi-halogenoethoxy group, disperse dyestuffs containing at least one fl-halogenothioethane groups, disperse dye dyest
  • the disperse reactive dyestuff contains a monohalogenotriazinylamine group such as a 4-chlor-o-6-amino-l :325-triazin-2-ylamino group, or a 'y-halogeno-p-hydroxypropyl group such as a vchloro-,B-hydroxypropylamino group, or a fl-halogenoalkylsulphamyl group such as a ,B-chloroethylsulphamyl or a ,G-bromoethylsulphamyl group.
  • a monohalogenotriazinylamine group such as a 4-chlor-o-6-amino-l :325-triazin-2-ylamino group
  • a 'y-halogeno-p-hydroxypropyl group such as a vchloro-,B-hydroxypropylamino group
  • Disperse dyestuffs containing a dichloro or dibromo- 1:3:5-triazinyl radical may be obtained by reacting one molecular proportion of a disperse dyestutf containing a primary amino or secondary amino group with one molecular proportion of cyanuric chloride or cyanuric bromide
  • Disperse dyestuffs containing a monochloroor monobromo-lz3a5-triazinyl radical may be obtained by reacting one molecular proportion of a disperse dyestuff containing a primary 'amino or secondary amino group with one molecular proportion of a triaziue of the formula:
  • X is a chlorine or bromine atom and Y stands for an alkyl, aryl or amino group or for an organic radical 3 containing a nitrogen, oxygen or sulphur atom through which it is linked to the triazine ring.
  • Disperse dyestuifs containing a pyrimidyl radical carrying one or two chlorine or bromine atoms directly attached to the pyrimidine ring may be obtained by interacting substantially equimolecular proportions of a disperse dyestuff containing a primary amino or secondary amino group and a pyrimidine containing at least two chlorine or bromine atoms in the 2, 4, or 6 positions of the pyrimidine ring.
  • pyrimidines there may be mentioned 2:4:6-trichloropyrimidine, 2:4 dibromopyrimidine, 2:4 dichloro 6 methylpyrimidine, 2:4 dichloro 6 methoxypyrimidine, 2: 4-dichloro-6-phenylpyrimidine, 2 4-dichloro-6-nitropyrimidine, 2 4-dichloro-6-hydroxypyrimidine, 2:4: 6-trichloro--nitropyrimidine and 2:4dichloro-5-nitro-6- methylpyrimidine.
  • Disperse dyestuffs containing at least one 'y-halogeno-flhydroxypropylsulphamyl or B-halogenoethylsulphamyl group may the obtained by treating a disperse dyestufi containing at least one sulphonchloride group with a 'y-halogeno-,B-hydroxypropylamine or a [B-halogenoethylamine respectively.
  • Disperse dyestuffs containing at least one B-halogenoethoxy or ,B-halogenothioethane group may be obtained by treating a disperse dyestufi containing at least one B-hydroxyethoxy or fi-hydroxythioethane group with a halogenating agent.
  • Disperse dyestuiis containing at least one y-halogenofi-hydroxypropylamino or di-('y-halogeno-B-hydroxypropyl)amino group may be obtained by reacting a disperse dyestuit containing one or more primary amino groups with epichlorohydrin and separating the mixture of products so obtained.
  • Disperse dyestuffs containing a propylepoxy group may be obtained by reacting the corresponding dyestuffs containing a y-chloro-fi-hydroxypropyl group With potassium hydroxide.
  • Disperse dyestuffs containing a vinylsulphone group may be obtained by treating with an alkali, for example potassium hydroxide, the corresponding dyestufis containing a fl-sulphatoethylsulphonyl group, which may themselves be obtained by sulphating the corresponding dyestuffs containing a fi-hydroxyethyl group.
  • an alkali for example potassium hydroxide
  • Disperse dyestuffs containing at least one chloracylamino group may be obtained by treating the corresponding dyeusttf containing at least one amino group with a chloroacyl chloride such as chloracetyl chloride.
  • disperse reactive dyestuifs which may be used in the process of the invention are described in British specifications Nos. 822,948 and 825,377, French specification No. 1,177,851, Belgian specifications Nos. 563,862, 571,741, 571,742 and 571,743, and in United States patent specification No. 2,258,977.
  • disperse reactive dyestulfs which may be used in the process of the invention there may be mentioned 2-hydroxy-5-methyl-4'-(4" 6"-dichloro-1: 3 ":5
  • nitrogen-containing synthetic textile materials such as polyamide textile materials for example textile materials comprising polyhex-amethyleneadipamide or the polymer of caprolactam, and modified polyacrylonitrile textile materials.
  • Example 1 1 part of 2-hydroxy-5-methyl-4'-(4"-chloro-6"-di( 3-hydroxyethyDarnino-1:3"z5"-triazin-2"-ylamino)azobenzene is dispersed in 20 parts of water and the dispersion so obtained is added to 4,000 parts of Water containing 4 parts of the condensate of ethylene oxide with a fatty alcohol and 8 parts of sodium dihydrogen phosphate. 100 parts of polyhexamethylene adipamide textile material are placed in the dyebath thus obtained which is then heated to C. and maintained at this temperature for 60 minutes. 9.2 parts of sodium carbonate are then added and dyeing is continued for a further hour at a temperature of 95 C. The dyed fabric is then rinsed in water and dried.
  • the polyhexamethyleneadipamide textile material is uniformly colored a yellow shade possessing superior wash and dry heat fasteness properties to polyhexamethyleneadipamide textile material which was dyed as described above except that the sodium carbonate was omitted from the dyebath.
  • Example 2 1 part of 1:4-di(v-chloro-fl-hydroxypropylamino)anthraquinone is dispersed in 20 parts of water and the dispersion so obtained is added to 4,000 parts of water containing 4 parts of the condensate of ethylene oxide with a fatty alcohol and 1 part of acetic acid. 100 parts of polymerised caprolactam textile material are placed in the dyebath thus obtained which is heated to 95 C. and maintained at this temperature for 60 minutes. 4 parts of barium hydroxide are then added and dyeing is continued for 1 hour at 95 C. The dyed textile material is finally rinsed in water and dried.
  • the textile material is uniformally dyed a blue shade and the fastness properties to wet and dry heat treatments are substantially better than the same fastness properties of a dyeing obtained as described above except that the 1 part of acetic and 1 part of barium hydroxide were omitted from the dyeb ath.
  • Example 3 1 part of 2'-methyl-4-B1chloroethylsulphamyl-4-N:N- di(/8-.hydroxyethyl)aminoazobenzene is dispersed in 2 parts of Water and the dispersion so obtained is added to 4,000 parts of water containing 4 parts of the condensate of ethylene oxide with a fatty alcohol and 4 parts of acetic acid. 100 parts of polyhexamethyleneadipamide textile material are immersed in the dyebath so obtained which is heated to 95 C. and maintained at this temperature for 45 minutes. parts of sodium hydroxide are then added and dyeing is continued for 1 hour at 95 C. The dyed textile material is then rinsed in cold water and dried. The textile material is dyed a uniform orange shade possessing superior wet and dry heat fastness properties to polyhexamethyleneadip-amide textile material which was dyed as described above except that the caustic soda was omitted trom the dyebath.
  • Example 4 In place of the 1 part of 2-hydroxy-5-rnethyl-4-(4"- chloro 6" di(B hydroxyethyl) amino l:3:5 trirazin-2"-y-lamino)azobenzene used in Example 1 there is used 1 part of 2-methyl-4'-fi-chloroethylsulphamyl-4-N 3- hydroxyethylaminoazobenzene.
  • the polyhexamethyleneadipamide textile material is coloured an orange shade possessing excellent wash tastness properties.
  • Example 5 In place of the 1 part of 2-hydroxy-5-methyl-4'-(4- chloro 6 ditt? hydroxyethyDamino 1:3:5 triazin- 2-ylamino)azobenzene used in Example 1 there is used 1 part of l:4-bis('y-bromo-Bhydrox cpropyl-amino)ant-hraquinone.
  • the polyhexamethyleneadipamide textile material is coloured a blue shade possessing excellent wash fastness properties.
  • Example 6 In place of the 1 part of 2-hydroxy-5-met'hyl-4 (4"- chloro 6" di(,B hydroxyethyl)amino 1":3":5" triazin-2-yl-amino)azobenzene used in Example 1 there is used 1 part of 2-methyl-2-chloro-4'-Bchloroethylsulphamyl 4 N'zN di(,B-hydroxyethyl)aminoazobenzone.
  • the polyhexamethylenea-dipamide textile material is coloured a scarlet shade possessing excellent fastness to washing.
  • Example 7 1 part of 1:4-di-(y-chloro-B-hydroxypropylamino)anthraquinone is dispersed in 20 parts of water and the dispersion so obtained is added to 4,000 parts of water containing 8 parts of oleyl sodium sulphate and 8 parts of sodium dihydrogen phosphate. 100 parts of Acrilan, a modified polyacrylonitrile fibre manufactured by the Chemstrand Corporation, are placed in the dyebath thus obtained which is then heated to 95 C. and maintained at this temperature for 60 minutes. 9.2 parts of sodium carbonate are then added and dyeing is continued for a further hour at a temperature of 95 C. The dyed fabric is then rinsed in water and dried. The Acrilan is coloured a blue shade possessing excellent fastness to washmg.
  • Example 8 1 part of l:4-bis('y-chloro-B-hydroxypropylamino)anthraquinone is dispersed in 20 parts of water and the dispersion is added to 4,000 parts of water containing 4 parts of the condensate of ethylene oxide with a fatty alcohol and 8 parts of a 30% aqueous solution of acetic acid.
  • parts of polyhex-amet'hyleneadipamide textile material are placed in the dyebath thus obtained which is then heated at 70 C. and maintained at this tempera ture for 30 minutes.
  • a solution of 8 parts of sodium carbonate in 50 parts of water is then added and dyeing is continued for a further 60 minutes at a temperature of 7 0 C.
  • the tabric is then removed from the dyebath, rinsed in cold water and dried.
  • the dyed polyhex-amethyleneadipamide textile material is then placed in contact for 15 seconds with a metal cylinder which is maintained at a temperature of 220 C.
  • the polyhexamethyleneadipamide textile material is coloured a blue shade possessing superior wash fastness properties to polyhexamethyleneadipamide textile material which was dyed as described above but was not subsequently heated at 220 C.
  • Example 9 In place of the 1 part of 1:4-bis('y chloro-fi-hydroxypropylamino)ranthraquinone used in Example 8 there is used 1 part of 2-methyl-2-chloro-4-,8-chloroethylsulphamyl 4 N:N dim hydroxyethyl)aminoazobenzene.
  • the polyhexamethyleneadipamide textile material is coloured a scarlet shade possessing superior Wash fastness properties to polyhexamethylenea-dipamide textile material which was dyed as described above but was not subjected to the heat treatment at 220 C.
  • Example 10 In place of the 1 part of 1:4-bis(- -cl11oro-fl-hydroxypropylamino)anthraquinone used in Example 8 there is used 1 part of 2-hydroxy-5-methyl-4-(4"-chloro-6"-di(flhydroxyethyhamino, 1:3":5 triazin 2" yla.mino)- azobenzene.
  • the polyhexamethyleneadipamide textile material is thereby coloured a yellow shade possessing superior wash fastness properties to polyhexamethyleneadipamide textile material which was dyed as described above but was not subjected to the heat treatment at 220 C.
  • Example 11 In place of the 1 part of 1z4-bis('y-chloro- ⁇ 8-hydroxypropy-lamino)anthraqui none used in Example 8 there is used 1 part of 2-methyl-4'-B-chloroethylsulpha.myl-4-N:N- di( ,B-hydroxyethyl) aminoazobenzene.
  • polyhexamethyleneadipamide textile material is thereby coloured an orange shade possessing superior wash fiastness properties to polyhexarnethyleneadipamide textile material which was dyed as described above but was not subjected to the heat treatment at 220 C.
  • Example 12 In place of the 1 part of 1c4-bis('wchloro-fl-hydroxypropylamino)a-nthraquin0ne used in Example 8 there is used 1 part of 1-fi-hydroxyethylamino-4-[2 chloro-4'43- chloroethylsulphamylphenylazo] -n aphth alene.
  • the polyhexamethyleneadipamide textile material is thereby coloured a red shade possessing superior wash fastness properties to polyhex-amethyleneadipamide textile material which was dyed as described above but was not subjected to the heat treatment at 220 C.
  • Example 13 In place of the polyhexamethyleneadipamide textile material used in Example 8 there is used a textile material comprising polymerised caprolactam, and instead of heating the dyed textile material at 220 C. for 15 seconds, the dyed textile material is heated at C. for 45 seconds whereby the textile material is coloured a 7, blue shade possessing superior wash fastness properties to the polymerised caprolactam textile material which was dyed. as described above but was not subjected to the heat treatment at 190 C.
  • Process for dyeing nitrogen-containing synthetic polymeric textile materials selected from the class consisting of synthetic linear polyamides and modified polyacrylonitrile textile materials which process comprises dyeing said synthetic polymeric textile material with an aqueous dispersion of a disperse reactive dyestufi' and a member selected from the group consisting of an acid and acid salt, and having a pH in the range of between about 3 and 5, and subsequently, during the dyeing process, adding to said dispersion a member selected from the group consisting of an alkali and alkaline salt, to raise the pH thereof to Within the range of between about'9 and 12.

Description

United States Patent 3,097,043 NEW DYEING PROCESS Walter Percival Mills, Manchester, England, 'assignor to Imperial Chemical Industries Limited, Millbanlr, Lou= don, England, a corporation of Great Britain No Drawing. Filed Nov. 4, 1959, Sci. No. 850,785 Claims priority, application Great Britain Nov. 7, 1958 6 Claims. (Cl. 8-55) This invention relates to a dyeing process and more particularly it relates to a process for dyeing synthetic polymeric textile materials.
It is known that synthetic polymeric textile materials can be dyed with disperse dyestuffs which are free from sulphonic acid and carboxylic acid groups and which contain at least one reactive halogen atom or other reactive group which is capable of reacting with the synthetic polymeric textile material so that the said disperse dyestuff is fixed to the synthetic polymeric textile material by a chemical bond, whereby dyeings are obtained which have excellent fastness to washing.
It has now been found that the fixation of such disperse reactive dyestuffs to the synthetic polymeric textile materials is low when the dyestuffs are applied from a dyebath the pH of which is less than 7 but as the pH rises fixation of the dyestulf rapidly increases. However at pHs above 7 the uptake of the dyestuff onto the synthetic polymeric textile material is uneven and level dyeings are not obtained. It has now been found that this dis advantage can be overcome by commencing the dyeing of the synthetic polymeric textile material with the disperse reactive dyestuffs at a pH less than 7 and subsequently raising the pH during the dyeing operation, whereby level dyeings are obtained possessing excellent fastness to washmg.
According to the invention therefore there is provided an improved process for dyeing synthetic polymeric textile materials with disperse reactive dyestuffs, as hereinafter defined, which comprises dyeing the synthetic polymeric textile material with an aqueous dispersion of the said dyestuff at a pH less than 7 and subsequently raising the pH during the dyeing process.
The process of the invention may be conveniently carried out by immersing the synthetic polymeric textile material in an aqueous dispersion of the disperse reactive dyestulf containing an acid or an acid-salt so that the pH of the aqueous dispersion is less than 7 and is preferably between 3 and 5, heating the dyebath for a period at a suitable temperature, for example at a temperature between 90 to 100 C., adding an alkali or an alkaline salt to raise the pH of the dyebath, preferably to a pH between 9 and 12, and heating for a further period at a suitable temperature, for example at a temperature between 90 and 100 C. The textile material is then removed from the dyebath, rinsed in water and dried.
If desired the process or" the invention may be carried out at temperatures above 100 C., for example at temperatures between 100 and 130 C. under superat-mospheric pressure.
Alternatively the process of the invention can be carried out at temperatures below 90 C., for example at temperatures between 70 and 90 C., but, in order that the resulting dyeings shall possess maximum fastness to washing, it is preferred to subsequently subject the dyeing so obtained to a dry heat treatment at a temperature beween 160 and 230 C. This can be conveniently carried out by placing the dyed synthetic polymeric textile materials in contact with a metal cylinder which is maintained at a temperature between 160 and 230 C.
As examples of the acids or acid salts which may be ice used in the process of the invent-ion there may be mentioned organic acids for example aliphatic organic acids and in particular monobasic lower fatty acids such as acetic acid and formic acid and inorganic acid salts such as sodium dihydrogen phosphate, and as examples of the alkalis or alkaline salts which may be used in the process of the invention there may be mentioned inorganic alkalis and inorganic alkaline salts such as sodium carbonate, sodium hydroxide, trisodium phosphate, barium hydroxide, lithium hydroxide, sodium silicate, potassium carbonate and potassium hydroxide.
If desired mixtures of acids and/or acid salts and/ or mixtures of alkalis and/or alkaline salts may be used in the process of the invention.
By the term disperse reactive dyestuff there is meant a disperse or water-insoluble dyestuff which is free from sulphonic acid and carboxylic acid groups and which contains at least one reactive halogen atom or other reactive atom or group, that is to say a halogen atom or other group capable of reacting with the synthetic polymeric textile material. Examples of classes of such disperse reactive dyestuifs include water-insoluble dyestuffs containing a 1:3:5-triazinyl radical carrying one or two chlorine or bromine atoms directly attached to the triazine ring, disperse dyestuffs containing a pyrimidyl radical carrying one or two chlorine or bromine atoms directly attached to the pyrimidine ring, disperse dyestuffs containing at least one 'y-halogeno-[i-hydroxypropylamino group, disperse dyestuffs containing at least one di-(v-ha1ogen0-5- hydroxypropyl)amino group, disperse dyestuffs containing at least one [i-halogenoethylsulphamyl group, disperse dyestuffs containing at least one fi-halogenoethoxy group, disperse dyestuffs containing at least one fl-halogenothioethane groups, disperse dyestuffs containing at least one '7 halogeno [3 hydroxypropylsulphamyl group, disperse dyestuffs containing at least one chloracylarnino group, disperse dyestuffs containing at least one vinylsulphonyl group and disperse dyestuffs containing at least one epoxy propyl group. The disperse dyestuffs in these classes may be for example nitro dyestuffs or dyestuffs of the azo, anthraquinone or phthalocyanine series which are free from sulphonic and carboxylic acid groups.
It is however preferred that the disperse reactive dyestuff contains a monohalogenotriazinylamine group such as a 4-chlor-o-6-amino-l :325-triazin-2-ylamino group, or a 'y-halogeno-p-hydroxypropyl group such as a vchloro-,B-hydroxypropylamino group, or a fl-halogenoalkylsulphamyl group such as a ,B-chloroethylsulphamyl or a ,G-bromoethylsulphamyl group.
Disperse dyestuffs containing a dichloro or dibromo- 1:3:5-triazinyl radical may be obtained by reacting one molecular proportion of a disperse dyestutf containing a primary amino or secondary amino group with one molecular proportion of cyanuric chloride or cyanuric bromide Disperse dyestuffs containing a monochloroor monobromo-lz3a5-triazinyl radical may be obtained by reacting one molecular proportion of a disperse dyestuff containing a primary 'amino or secondary amino group with one molecular proportion of a triaziue of the formula:
N XO% \GY l O 1';
wherein X is a chlorine or bromine atom and Y stands for an alkyl, aryl or amino group or for an organic radical 3 containing a nitrogen, oxygen or sulphur atom through which it is linked to the triazine ring.
Disperse dyestuifs containing a pyrimidyl radical carrying one or two chlorine or bromine atoms directly attached to the pyrimidine ring may be obtained by interacting substantially equimolecular proportions of a disperse dyestuff containing a primary amino or secondary amino group and a pyrimidine containing at least two chlorine or bromine atoms in the 2, 4, or 6 positions of the pyrimidine ring. As examples of such pyrimidines there may be mentioned 2:4:6-trichloropyrimidine, 2:4 dibromopyrimidine, 2:4 dichloro 6 methylpyrimidine, 2:4 dichloro 6 methoxypyrimidine, 2: 4-dichloro-6-phenylpyrimidine, 2 4-dichloro-6-nitropyrimidine, 2 4-dichloro-6-hydroxypyrimidine, 2:4: 6-trichloro--nitropyrimidine and 2:4dichloro-5-nitro-6- methylpyrimidine.
Disperse dyestuffs containing at least one 'y-halogeno-flhydroxypropylsulphamyl or B-halogenoethylsulphamyl group may the obtained by treating a disperse dyestufi containing at least one sulphonchloride group with a 'y-halogeno-,B-hydroxypropylamine or a [B-halogenoethylamine respectively.
Disperse dyestuffs containing at least one B-halogenoethoxy or ,B-halogenothioethane group may be obtained by treating a disperse dyestufi containing at least one B-hydroxyethoxy or fi-hydroxythioethane group with a halogenating agent.
Disperse dyestuiis containing at least one y-halogenofi-hydroxypropylamino or di-('y-halogeno-B-hydroxypropyl)amino group may be obtained by reacting a disperse dyestuit containing one or more primary amino groups with epichlorohydrin and separating the mixture of products so obtained.
Disperse dyestuffs containing a propylepoxy group may be obtained by reacting the corresponding dyestuffs containing a y-chloro-fi-hydroxypropyl group With potassium hydroxide.
Disperse dyestuffs containing a vinylsulphone group may be obtained by treating with an alkali, for example potassium hydroxide, the corresponding dyestufis containing a fl-sulphatoethylsulphonyl group, which may themselves be obtained by sulphating the corresponding dyestuffs containing a fi-hydroxyethyl group.
Disperse dyestuffs containing at least one chloracylamino group may be obtained by treating the corresponding dyeusttf containing at least one amino group with a chloroacyl chloride such as chloracetyl chloride.
Examples of disperse reactive dyestuifs which may be used in the process of the invention are described in British specifications Nos. 822,948 and 825,377, French specification No. 1,177,851, Belgian specifications Nos. 563,862, 571,741, 571,742 and 571,743, and in United States patent specification No. 2,258,977.
As specific examples of disperse reactive dyestulfs which may be used in the process of the invention there may be mentioned 2-hydroxy-5-methyl-4'-(4" 6"-dichloro-1: 3 ":5
triazin-2"-ylamino) azobenzene, 2-chloro-4-ethanesulphonyl-4'-N-fi-hydroxyethyl-N-/8- (4" 6"-dichloro-1" 3 5 -triaZin-2"-ylamino)- ethylaminoazobenzene, 4-(4:6"-dichloro-l:3":5"-triazin-2"-ylamino)-2- methylazobenzene, 2-hydroxy-5-methyl-4'-(4":6-dibromo-l:3":5-
triazin-2-ylamino -azobenzene, 2-hydroxy-5-methyl-4-(4"-chloro-6"-fi-hydroxyethyla mino-1":3 5-triazin-2"-yl amino) azobenzene, 2-hydroxy-5-methyl-4'-(4"-chloro-6"-anilino-1" 3 5 triazin-2"-y1amino) azobenzene, 2-hydroxy-5-methyl-4-( 4-chloro-6"-amino- 1 3 5 triaZin-2 '-ylamino azobenzene, 2-chloro-4-ethanesulphonyl-4-N-fl-l1ydroxyethyl-N-,B-
ethyl-aminoazobenzene,
4 2-hydroxy-5-methyl-4- (4"-bromo-6"-N N-di (,B-hydroxyethyl) amino-1 3 ":5"-triaZin2"-ylan1ino)azobenzene, 2-hydroxy-5-methyl-4- (4"-chloro-6"-phenyl- 1 "z 3 5 triazin-2' '-ylamino) azob enzene, 4-amino-4'-(4"-chloro-6"-phenoxy-l :3 5 "-triazin-2- ylamino) azobenzene, l-4'-(4":6-dichloro-1:3:5-triazin-2"-ylamino)anilinoanthroquinone,
1-4- (4"chloro-6-phenoxyl 3 5 "-triazin-2"-ylamino) anilinoanthraquinone,
4'-(4"-6-dichloro-l":3":5-triazin-2"-ylamino)2:4-
dinitrodiphenylamine,
4'-(4"-chloro-6"-meth0xytriazin-2"-ylamino)-2:4-dinitrodiphenylamine,
3 4"-chloro-6"-phenoxy-l 3 5 -triazin-2"-ylamino) -2-nitro-4-trifluoromethyldiphenylamine, 2-hydroxy-5-methyl-4- 4" 6"-dichloro-pyrimidine-2"- ylamino) azobenzene, 4'-nitro-4-N N-di y-chloro-fi-hydroxypropyl) aminoazobenzene, 1 :4-bis ('y-chloro-;8-hydroxypropylamine)anthraquinone, 4'-;3-chloroethylsulphamylphenylazo-4-fi-hydroxyethylaminonaphthalene, 4- 3-chloroethylsulphamyl-Z-methyl-5 -N-ethyl-N-fl-hydroxyethylaminoazobenzene, 2-chloro-4-,B-chloroethylsulphamyl-Z'-methyl-5'-di(betahydroxyethyl)aminoazobenzene, l-methylamino-4-;3-chloroethylamino-anthraquinone, l :4'-(4":6-dichloro-1:3:5: :4triaZin-2-ylamino)phenylazo-Z-naphthol, 1-amino-2-/3-bromoethoxy-4-hydroxyanthraquinone, 1-amino-4-hydroXy-2-fi-(tY-chloroethoxy)ethoxyanthraquinoine and 1-amino-4-hydroxy-2-[3-(,B-bromoethoxy)ethoxyanthraquinone.
As examples of synthetic polymeric textile materials which may be dyed by the process of the invention there may be mentioned nitrogen-containing synthetic textile materials such as polyamide textile materials for example textile materials comprising polyhex-amethyleneadipamide or the polymer of caprolactam, and modified polyacrylonitrile textile materials.
By the process of the invention there are obtained on the synthetic polymeric textile materials level dyeings in a Wide range of shades which have excellent fastness to washing and to dry heat treatments.
The invention is illustrated but not limited by the following examples in which the parts and percentages are by weight:
Example 1 1 part of 2-hydroxy-5-methyl-4'-(4"-chloro-6"-di( 3-hydroxyethyDarnino-1:3"z5"-triazin-2"-ylamino)azobenzene is dispersed in 20 parts of water and the dispersion so obtained is added to 4,000 parts of Water containing 4 parts of the condensate of ethylene oxide with a fatty alcohol and 8 parts of sodium dihydrogen phosphate. 100 parts of polyhexamethylene adipamide textile material are placed in the dyebath thus obtained which is then heated to C. and maintained at this temperature for 60 minutes. 9.2 parts of sodium carbonate are then added and dyeing is continued for a further hour at a temperature of 95 C. The dyed fabric is then rinsed in water and dried. The polyhexamethyleneadipamide textile material is uniformly colored a yellow shade possessing superior wash and dry heat fasteness properties to polyhexamethyleneadipamide textile material which was dyed as described above except that the sodium carbonate was omitted from the dyebath.
Example 2 1 part of 1:4-di(v-chloro-fl-hydroxypropylamino)anthraquinone is dispersed in 20 parts of water and the dispersion so obtained is added to 4,000 parts of water containing 4 parts of the condensate of ethylene oxide with a fatty alcohol and 1 part of acetic acid. 100 parts of polymerised caprolactam textile material are placed in the dyebath thus obtained which is heated to 95 C. and maintained at this temperature for 60 minutes. 4 parts of barium hydroxide are then added and dyeing is continued for 1 hour at 95 C. The dyed textile material is finally rinsed in water and dried. The textile material is uniformally dyed a blue shade and the fastness properties to wet and dry heat treatments are substantially better than the same fastness properties of a dyeing obtained as described above except that the 1 part of acetic and 1 part of barium hydroxide were omitted from the dyeb ath.
Example 3 1 part of 2'-methyl-4-B1chloroethylsulphamyl-4-N:N- di(/8-.hydroxyethyl)aminoazobenzene is dispersed in 2 parts of Water and the dispersion so obtained is added to 4,000 parts of water containing 4 parts of the condensate of ethylene oxide with a fatty alcohol and 4 parts of acetic acid. 100 parts of polyhexamethyleneadipamide textile material are immersed in the dyebath so obtained which is heated to 95 C. and maintained at this temperature for 45 minutes. parts of sodium hydroxide are then added and dyeing is continued for 1 hour at 95 C. The dyed textile material is then rinsed in cold water and dried. The textile material is dyed a uniform orange shade possessing superior wet and dry heat fastness properties to polyhexamethyleneadip-amide textile material which was dyed as described above except that the caustic soda was omitted trom the dyebath.
Example 4 In place of the 1 part of 2-hydroxy-5-rnethyl-4-(4"- chloro 6" di(B hydroxyethyl) amino l:3:5 trirazin-2"-y-lamino)azobenzene used in Example 1 there is used 1 part of 2-methyl-4'-fi-chloroethylsulphamyl-4-N 3- hydroxyethylaminoazobenzene. The polyhexamethyleneadipamide textile material is coloured an orange shade possessing excellent wash tastness properties.
Example 5 In place of the 1 part of 2-hydroxy-5-methyl-4'-(4- chloro 6 ditt? hydroxyethyDamino 1:3:5 triazin- 2-ylamino)azobenzene used in Example 1 there is used 1 part of l:4-bis('y-bromo-Bhydrox cpropyl-amino)ant-hraquinone. The polyhexamethyleneadipamide textile material is coloured a blue shade possessing excellent wash fastness properties.
Example 6 In place of the 1 part of 2-hydroxy-5-met'hyl-4 (4"- chloro 6" di(,B hydroxyethyl)amino 1":3":5" triazin-2-yl-amino)azobenzene used in Example 1 there is used 1 part of 2-methyl-2-chloro-4'-Bchloroethylsulphamyl 4 N'zN di(,B-hydroxyethyl)aminoazobenzone. The polyhexamethylenea-dipamide textile material is coloured a scarlet shade possessing excellent fastness to washing.
Example 7 1 part of 1:4-di-(y-chloro-B-hydroxypropylamino)anthraquinone is dispersed in 20 parts of water and the dispersion so obtained is added to 4,000 parts of water containing 8 parts of oleyl sodium sulphate and 8 parts of sodium dihydrogen phosphate. 100 parts of Acrilan, a modified polyacrylonitrile fibre manufactured by the Chemstrand Corporation, are placed in the dyebath thus obtained which is then heated to 95 C. and maintained at this temperature for 60 minutes. 9.2 parts of sodium carbonate are then added and dyeing is continued for a further hour at a temperature of 95 C. The dyed fabric is then rinsed in water and dried. The Acrilan is coloured a blue shade possessing excellent fastness to washmg.
Example 8 1 part of l:4-bis('y-chloro-B-hydroxypropylamino)anthraquinone is dispersed in 20 parts of water and the dispersion is added to 4,000 parts of water containing 4 parts of the condensate of ethylene oxide with a fatty alcohol and 8 parts of a 30% aqueous solution of acetic acid. parts of polyhex-amet'hyleneadipamide textile material are placed in the dyebath thus obtained which is then heated at 70 C. and maintained at this tempera ture for 30 minutes. A solution of 8 parts of sodium carbonate in 50 parts of water is then added and dyeing is continued for a further 60 minutes at a temperature of 7 0 C. The tabric is then removed from the dyebath, rinsed in cold water and dried. The dyed polyhex-amethyleneadipamide textile material is then placed in contact for 15 seconds with a metal cylinder which is maintained at a temperature of 220 C.
The polyhexamethyleneadipamide textile material is coloured a blue shade possessing superior wash fastness properties to polyhexamethyleneadipamide textile material which was dyed as described above but was not subsequently heated at 220 C.
Example 9 In place of the 1 part of 1:4-bis('y chloro-fi-hydroxypropylamino)ranthraquinone used in Example 8 there is used 1 part of 2-methyl-2-chloro-4-,8-chloroethylsulphamyl 4 N:N dim hydroxyethyl)aminoazobenzene. The polyhexamethyleneadipamide textile material is coloured a scarlet shade possessing superior Wash fastness properties to polyhexamethylenea-dipamide textile material which was dyed as described above but was not subjected to the heat treatment at 220 C.
Example 10 In place of the 1 part of 1:4-bis(- -cl11oro-fl-hydroxypropylamino)anthraquinone used in Example 8 there is used 1 part of 2-hydroxy-5-methyl-4-(4"-chloro-6"-di(flhydroxyethyhamino, 1:3":5 triazin 2" yla.mino)- azobenzene. The polyhexamethyleneadipamide textile material is thereby coloured a yellow shade possessing superior wash fastness properties to polyhexamethyleneadipamide textile material which was dyed as described above but was not subjected to the heat treatment at 220 C.
Example 11 In place of the 1 part of 1z4-bis('y-chloro-}8-hydroxypropy-lamino)anthraqui none used in Example 8 there is used 1 part of 2-methyl-4'-B-chloroethylsulpha.myl-4-N:N- di( ,B-hydroxyethyl) aminoazobenzene.
The polyhexamethyleneadipamide textile material is thereby coloured an orange shade possessing superior wash fiastness properties to polyhexarnethyleneadipamide textile material which was dyed as described above but was not subjected to the heat treatment at 220 C.
Example 12 In place of the 1 part of 1c4-bis('wchloro-fl-hydroxypropylamino)a-nthraquin0ne used in Example 8 there is used 1 part of 1-fi-hydroxyethylamino-4-[2 chloro-4'43- chloroethylsulphamylphenylazo] -n aphth alene.
The polyhexamethyleneadipamide textile material is thereby coloured a red shade possessing superior wash fastness properties to polyhex-amethyleneadipamide textile material which was dyed as described above but was not subjected to the heat treatment at 220 C.
Example 13 In place of the polyhexamethyleneadipamide textile material used in Example 8 there is used a textile material comprising polymerised caprolactam, and instead of heating the dyed textile material at 220 C. for 15 seconds, the dyed textile material is heated at C. for 45 seconds whereby the textile material is coloured a 7, blue shade possessing superior wash fastness properties to the polymerised caprolactam textile material which was dyed. as described above but was not subjected to the heat treatment at 190 C.
What I claim is:
1. Process for dyeing nitrogen-containing synthetic polymeric textile materials selected from the class consisting of synthetic linear polyamides and modified polyacrylonitrile textile materials, which process comprises dyeing said synthetic polymeric textile material with an aqueous dispersion of a disperse reactive dyestufi' and a member selected from the group consisting of an acid and acid salt, and having a pH in the range of between about 3 and 5, and subsequently, during the dyeing process, adding to said dispersion a member selected from the group consisting of an alkali and alkaline salt, to raise the pH thereof to Within the range of between about'9 and 12.
2. Process as claimed in claim 1 wherein the dyeing is carried out at a temperature between 90 and 100 C.
3. Process as claimed in claim 1 wherein the dyeing is carried out at a temperature between 100 and 130 C., under superatrnospheric pressure.
4. Process is claimed in claim 1 wherein the nitrogencontaining synthetic polymeric textile material is a polyamide textile material.
5. Process as claimed in claim 1 whereinthe dyeing iscarried out at a temperature between and C. 6. Process as claimed. in claim 5 wherein the dyed textile material is subsequently given a dry heat treatment at a temperature between and 230 C.
References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Schlaeppi: Amer. Dyest. Rep., June 2, 1958, p. 377, 8-542.

Claims (1)

1. A PROCESS FOR DYEING NITROGEN-CONTAINING SYNTHETICPOLYMERIC TEXTILE MATERIALS SELECTED FROM THE CLASS CONSISTING OF SYNTHETIC LINEAR POLYAMIDES AND MODIFIED POLYACRYLONITRILE TEXTILE MATERIALS, WHICH PROCESS COMPRISES DYEING SAID SYNTHETIC POLYMERIC TEXTILE MATERIAL WITH AN AQUEOUS DISPERSION O A DISPERSE REACTIVE DYESTUFF AND A MEMBER SELECTED FROM THE GROUP CONSISTING OF AN ACID AND ACID SALT, AND HAVING A PH IN THE RANGE OF BETWEEN ABOUT 3 AND 5, AND SUBSEQUENTLY, DURING THE DYEING PROCESS, ADDING TO SAID DISPERSION A MEMBER SELECTED FROM THE GROUP CONSISTING OF AN ALKALI AND ALKALINE SALT, TO RAISE THE PH THEREOF TO WITHIN THE RANGE OF BETWEEN ABOUT 9 AND 12.
US3097043D New dyeing process Expired - Lifetime US3097043A (en)

Publications (1)

Publication Number Publication Date
US3097043A true US3097043A (en) 1963-07-09

Family

ID=3451527

Family Applications (1)

Application Number Title Priority Date Filing Date
US3097043D Expired - Lifetime US3097043A (en) New dyeing process

Country Status (1)

Country Link
US (1) US3097043A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3816067A (en) * 1969-04-01 1974-06-11 Hoechst Ag Process for printing and pad dyeing polyamide fibrous materials
US3837802A (en) * 1968-03-28 1974-09-24 Ciba Geigy Ag Process for dyeing
US3980426A (en) * 1974-02-02 1976-09-14 Hoechst Aktiengesellschaft Process for printing or pad-dyeing cellulose/polyester mixed fabrics

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2895785A (en) * 1959-07-21 Naoas
US2900218A (en) * 1956-02-07 1959-08-18 Deering Milliken Res Corp Dyeing proteinaceous and nylon materials
US2903442A (en) * 1956-09-06 1959-09-08 Ciba Ltd Triazine monoazo-dyestuffs
US2914531A (en) * 1957-03-18 1959-11-24 Ciba Ltd New dyestufes of the peri-dicarboxylic acid imide series
US2944870A (en) * 1957-10-04 1960-07-12 Ici Ltd New colouring process
US2944871A (en) * 1957-10-04 1960-07-12 Ici Ltd New colouring process
US2952506A (en) * 1956-08-24 1960-09-13 Chemstrand Corp Process for even and level dyeing of filament nylon fabrics

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2895785A (en) * 1959-07-21 Naoas
US2900218A (en) * 1956-02-07 1959-08-18 Deering Milliken Res Corp Dyeing proteinaceous and nylon materials
US2952506A (en) * 1956-08-24 1960-09-13 Chemstrand Corp Process for even and level dyeing of filament nylon fabrics
US2903442A (en) * 1956-09-06 1959-09-08 Ciba Ltd Triazine monoazo-dyestuffs
US2914531A (en) * 1957-03-18 1959-11-24 Ciba Ltd New dyestufes of the peri-dicarboxylic acid imide series
US2944870A (en) * 1957-10-04 1960-07-12 Ici Ltd New colouring process
US2944871A (en) * 1957-10-04 1960-07-12 Ici Ltd New colouring process

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3837802A (en) * 1968-03-28 1974-09-24 Ciba Geigy Ag Process for dyeing
US3816067A (en) * 1969-04-01 1974-06-11 Hoechst Ag Process for printing and pad dyeing polyamide fibrous materials
US3980426A (en) * 1974-02-02 1976-09-14 Hoechst Aktiengesellschaft Process for printing or pad-dyeing cellulose/polyester mixed fabrics

Similar Documents

Publication Publication Date Title
US3116103A (en) Textile colouration process
US2895785A (en) Naoas
US2914531A (en) New dyestufes of the peri-dicarboxylic acid imide series
US3558621A (en) Anthraquinone reactive dyestuffs
US3459729A (en) Monoazo triazine containing dyestuffs
US4297101A (en) Process for the dyeing of synthetic polyamide fibers with reactive dyes according to the batchwise exhaustion method
US3043650A (en) Process for dyeing cellulose with
US2950165A (en) New dyeing process
US3097043A (en) New dyeing process
US3462410A (en) Sulphonaphthalene - azo - 1 - aryl - 5 - pyrazolone dyestuffs containing a dior trihalopyrimidyl or a mono or dihalotriazinyl radical
US3474084A (en) Reactive monoazo dyestuffs containing two chlorotriazine groups
US2949467A (en) Perinone triazino dyestuffs
US3177214A (en) Resinous triazinylamevo amhua- quinone dyestuffs
US2978289A (en) Process for coloring cellulose with new triazine dyestuffs
US4033943A (en) Fiber reactive water soluble 2,4,6-triamino, 3-cyano pyridine-(5) azo dyestuffs
US3220793A (en) Coloration process
US3057673A (en) Process for dyeing protein fibers with a
CA1097621A (en) Fibre-reactive azo dyestuffs, their manufacture and use
US2940812A (en) New textile treatment process
US3095415A (en) Anthraquinone dyestuffs containing a 2-chloro, 4-hydroxy (lower) alkylamino, triazinylamino group
US3170911A (en) Reactive azo dyestuffs
US3086832A (en) Process for finishing dyeings
US3535072A (en) Dyeing process for polyamide fibers
US2992063A (en) Dyeing process for synthetic textile
US3122531A (en) Dyestuffs containing a sulfonated-1:3:5 triazine