US3198595A - Step-wise process for coloring anb fin- ishing cellulose materials wherein a cationic dye-fixing agent is employed with the resin finishing agent - Google Patents

Step-wise process for coloring anb fin- ishing cellulose materials wherein a cationic dye-fixing agent is employed with the resin finishing agent Download PDF

Info

Publication number
US3198595A
US3198595A US3198595DA US3198595A US 3198595 A US3198595 A US 3198595A US 3198595D A US3198595D A US 3198595DA US 3198595 A US3198595 A US 3198595A
Authority
US
United States
Prior art keywords
parts
agent
fabric
resin
acid
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 US3198595A publication Critical patent/US3198595A/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
    • 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
    • D06P1/52—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 using compositions containing synthetic macromolecular substances
    • D06P1/56—Condensation products or precondensation products prepared with aldehydes
    • 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
    • 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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/22—Effecting variation of dye affinity on textile material by chemical means that react with the fibre

Definitions

  • a cationic dye-fixing agent we mean an organic compound free from anionic water-solubilising groups such as sulphonic acid groups, but containing one or more ammonium groups, and frequently, but not always, an aliphatic chain of 6 or more carbon atoms.
  • anionic water-solubilising groups such as sulphonic acid groups, but containing one or more ammonium groups, and frequently, but not always, an aliphatic chain of 6 or more carbon atoms.
  • a reactive dyestuft we mean a water-soluble dyestun which contains a reactive halogen atom or other substituent capable of reacting with the resin or fibre so that the remainder of the dyestuff becomes attached to the resin or fibre through a covalent bond.
  • dyestuffs there may be mentioned, for example, dyestufis containing s-triazinyl or pyrimidyl radicals carrying labile atoms or groups directly attached to the ring, and dyestuffs containing a beta-halogenopropionyl, betahalogenoethylsulphonyl, beta halogenoethylsulphamyl, beta-sulphatoethylsulphonyl, beta hydroxyethylsulphonyl, chloro-acetylamino, beta-(chloromethyl)-beta-sulphatoethylsulphamyl, acryloylamino, beta-(alkyland aryl-sulphonyloxy) alkyl sulphonyl, beta-acyloxyalkylsulphonyl, vinylsulphonyl, alkyl phosphite or sulphon fluoride radical.
  • a labile atom or group By a labile atom or group, We means an atom or group which is bound by a covalent bond to a carbon atom of the pyrinn'dine or triazine nucleus but which readily dissociates under the influence of heat or alkalis, especially in the presence of moisture, to form an ion or an uncharged molecule.
  • atoms or groups there may be mentioned, for example, bromine, or, preferably, chlorine atoms, sulphonic acid groups, thiocyano groups, negatively substituted aryloxy and arylthio groups, such as sulphophenoxy, sulphophenylthio, nitrosulphophenoxy, disulphophenoxy and sulphonaphthoxy groups, quaternary ammonium groups, groups of the formula:
  • Y represents the group of atoms necessary to form a 5- or 6-membered heterocyclic ring which may carry substituents or form part of a fused ring system;
  • R and R each represents the same or different aikyl, cycloalkyl, aryl or aralkyl groups, or R and R together form, together with the nitrogen atom, a 5- or 6-membered heterocyclic ring; and groups of the formula:
  • dyestuffs contain metal in complex formation.
  • suitable dyestuffs are described in United Kingdom specification No. 209,723 in Examples 1 and 2, United Kingdom specification No. 298,494 in Example 1, in United Kingdom specifications Nos. 460,224, 733,471, 740,533, 775,308, 772,030, 774,925, 780,591, 781,930, 785,120, 785,222, 802,198, 805,562, 826,689 and 852,604, and 937,182 and 924,990.
  • dyestuffs containing hydroxyl, amino, hydroxyalkylamino, guanyl hydrazide, semicarbazide r thiosemicarbazide groups linked to a triazine nucleus or hydroxyalkylamino groups linked to a pyrimidine nucleus or to the alkyl radical of an alkylsulphonyl, alkylsulphamyl, alkylcarbonyl or alkylcarbonamide group.
  • Dyestuffs of these types have been described, for example in United Kingdom specification No. 209,723 in Example 1, in United States Patent No. 2,768,158 and United Kingdom specifications 904,227,
  • the dyestuif is applied to the textile material by immersion of the material in an aqueous solution of the dyestulf preferably by padding or by application of a printing paste containing .the dyestuif.
  • the printing paste may be applied by any of the usual methods, such as by roller, block, screen or stencil.
  • the dyestuff solution may contain other additions commonly used in the .art of dyeing with reactive dyestuffs, for example, urea,
  • wetting agents such as alkali metal alkylated naphthalene sulphonates and condensates of ethylene oxide with alkylated phenols, fatty alcohols or fatty amines, migration inhibitor such as sodium chloride, sodium sulphate or sodium alginate and, usually, an acid binding agent to aid reaction with the fabric.
  • the acid-binding agent is only necessary to achieve reaction with the fabric, and where the dyestuff is capable of reaction with the resin, there is no need to use an acid-binding agent. It is preferred to use a mild alkali, such as sodium carbonate or bicarbonate, as the acid-binding agent to minimise neutralisation of any acid or acid salt which may be used as curing catalyst in the subsequent processing.
  • the fabric After application of the dyestulf solution, the fabric is preferably dried at atmospheric temperature, but may also be dried at elevated temperatures for example by .treating with hot air at a temperature of between 50 to 150 C. or by treatment with steam in a steamer at a temperature of 100 to 105 C. for about 2 to 20 minutes.
  • fabric which has been dyed, particularly when containing viscose rayon is advantageously allowed to stand in a moist condition for a period of time, which may be from minutes to 24 hours, preferably from 30 minutes to 2 hours, the treatment leading to improved fixation and diffusion of the dyestuif into the fibres, and hence to improved quality and appearance of dyeing.
  • the printing pastes containing the dyestulf may also contain the additives usually used with reactive dyestuffs such as urea, sodium, m-nitro-benzene sulphonate, wetting agents of the types indicated above and thickening agents such as sodium alginate, ethyl cellulose, starch, locust bean gum, and, preferably, oil-in-water emulsions and water-in-oil emulsions.
  • reactive dyestuffs such as urea, sodium, m-nitro-benzene sulphonate, wetting agents of the types indicated above and thickening agents such as sodium alginate, ethyl cellulose, starch, locust bean gum, and, preferably, oil-in-water emulsions and water-in-oil emulsions.
  • the fabric is preferably dried, for example by passage over heated rollers, and may, if desired, then be baked or steamed for, for example, from 2 to minutes.
  • the dried textile fabric is then treated with the resinfinishing agent, for example by padding the material through an aqueous solution or suspension of the agent.
  • the solution or suspension may contain other commonly-used additives for example curing-catalysts for for about 1 minute.
  • the resin-finishing agent which may be acidic or alkaline as necessary, anionic and nonionic surface active agents, lubricating agents, softening agents, water repellentsand stiffening or bodying agents, as well as the cationic dyefixing agents.
  • Suitable compounds include, for example monomeric nitrogen compounds such as urea, thiourea, substituted ureas and thioureas, dicyandiamide, dicyandiarnidine, biguanides, amides, carbamates, allophanates and heterocyclic compounds such as aminotriazines, urons, ureins, ureides, imidazolidones, triazones and hydantoins or mixtures of such compounds, and polymeric nitrogen compounds such as the polymeric amides made by the reaction of dibasic acids with diamines.
  • the lower alkyl ethers of the methylol derivatives of these compounds include for example the methyl, ethyl, propyl and butyl ethers.
  • Other resin-finishing agents which may be used are condensation products of ketones with aldehydes, in particular, CI-I O.
  • acid catalysts which may be used there may be mentioned salts formed from weakbases and mineral acids such as zinc chloride, ammonium sulphate and ammonium chloride, mineral acid salts of organic amines, weak acids, for example organic acids such as oxalic acids and substantially neutral substances which develop acidity on heating or steaming, such as magnesiumchloride and ammonium thiocyanate; mixtures of such catalysts may be used.
  • weakbases and mineral acids such as zinc chloride, ammonium sulphate and ammonium chloride, mineral acid salts of organic amines, weak acids, for example organic acids such as oxalic acids and substantially neutral substances which develop acidity on heating or steaming, such as magnesiumchloride and ammonium thiocyanate; mixtures of such catalysts may be used.
  • alkaline catalyst which may be used there may be mentioned sodium bicarbonate and sodium carbonate.
  • the aqueous solution used for application of the resinforming composition may contain between 3% and 40% and preferably between 5% and 30% of the resin-forming compositionsand between 0.1% and 5% and preferably between 0.5% and 3.0% of acid or alkali catalyst.
  • lubricating and softening agents which may be used, there may be mentioned, for example dispersions of natural or synthetic waxes, methylol stearamide and the quaternary ammonium salts of United Kingdom specification No. 808,265 (which in low concentration act as lubricants rather than as cationic dye-fixing agents).
  • the amount of dye-fixing agent used can vary within wide limits, in some cases as little as 0.005 gram per litre of padding liquor being effective whilst in other cases as much as 1.5 grams per litre is required. These amounts are those at which a reasonable effect is shown and the use of higher quantities up to to grams per litre will give improved results.
  • the baking stage may be carried out at a wide range of temperatures, provided the temperature is sufficiently high to cure the resin.
  • the timesof baking will depend upon the temperature used, a short period of heating, for example, about 10 seconds, being suificient at temperatures of the order of 200 C. whilst a period of about 1 to 5, usually 3, minutes is required at a temperature of about 155 C.
  • the baking temperatures are preferably maintained at between C. and 200 C. adjusting the time to minimise thermal degradation of the cellulose.
  • the textile material can be given a short washing treatment, for example, a treatment in a weakly alkaline aqueous solution of soap or detergent at the 'boil
  • This washing treatment serves the purpose of removing small amounts of unpolymerised resin-forming agent and the residual acidity caused by the acid catalyst or the decomposition products thereof.
  • Example 1 100 parts of viscose rayon fabric are padded with a solution containing parts of the copper complex of 2- (5' sulpho-2'-hydroxyphenylazo)-6-(2",4"-dichloro-6"- s-triazinylamino)1-naphthol-3,S-disulphonic acid, 10 parts of sodium bicarbonate and 5 parts of sodium triisopropyl naphthalene sulphonate in 975 parts of Water, squeezed, maintained in a moist condition at atmospheric temperature for 1 hour and dried at 70 C. in a hot air drier.
  • 2- (5' sulpho-2'-hydroxyphenylazo)-6-(2",4"-dichloro-6"- s-triazinylamino)1-naphthol-3,S-disulphonic acid 10 parts of sodium bicarbonate and 5 parts of sodium triisopropyl naphthalene sulphonate in 975 parts of Water, squeezed, maintained in
  • the fabric is then padded through 1000 parts of a solution containing 400 parts of a 60% aqueous solution of a urea-formaldehyde precondensate (obtained by stirring a mixture of 1 mole of urea and 1.6 moles of formaldehyde at pH 8.5 and 20 C. for 4 /2 hours), parts of ammonium dihydrogen phosphate, parts of the condensate of dicyandiamide, formaldehyde and ammonium chloride obtained as described in Recipe 1 of United United Kingdom specification No. 808,265.
  • the fabric 1 is then squeezed, dried on a pin stenter at 100 C. and baked at 150 C. for 3 minutes.
  • the fabric is dyed a bluish-red shade having good fastness to severe Washing treatments and is resistant to creasing.
  • Dyestufi Resin-finishing agent Acid catalyst Cationic dyte-fixing Shade agen 2. Disodium i-amino t-(3--sulphatoethylsulphonylaniline) an- As in Example 1- As in Example 1 As in Example 1. Bright redthraquinone-2-sulphonate, 5 parts. dish-blue.
  • azonaphthalene-l,3,5-trisulphonic acid 10 parts. ride, 12 parts. higuazrde p501 mer, par s.
  • disulphonic acid 5 parts. tion of hexamethride, 15 parts. bromide, 20 parts.
  • the copper complex of 8-(2-amiuo-4-chloro-s-triazinyl)aminoaque us S Z1110 trate, 10 As in Example 1-.-- Royal blue.
  • Dyestuft Resin-finishing agent Acid catalyst Cationic dyte-fixing Shade agen 15. 2-(2-methoxy-5-fi-sulphatocthylsulphonylphenylazo)-1- As in Example 1 Zinc nitrate, 10 As in Example 1 Red.
  • Example 17 In this example, the procedure followed is that of Example 1, with the exception that the sodium bicarbonate is omitted from the first padding solution.
  • the coloured fabric so obtained has a lower fastness to severe Washing treatments, but has a commercially satisfactory standard of fastness to the mild washing treatments normally recommended for viscose rayon fabrics.
  • Example 1 The following table lists dyestuffs which can be used in the above procedure in place of these named in Example 1.
  • the second padding liquor can be formulated in accordance with any of those described in Examples 1 to 16 inclusive.
  • Example Dycstutf Shade 18 The product obtained by condensing copper Turquoise. phthaloeyaniue tetra- (3')- sulphonchloride with 1.5 moles of B-chloroethylaminc in the presence of ammonia.
  • the product obtained by condensing copper phthalocyanine tri- (3)- sulphonchloride mouosulphonic acid with 1.5 moles of 5 ehloroethylamin e.
  • Example 28 chloride obtained as described in Recipe 1 of United King-- dom specification No. 651139, 1.15 parts of aqueous ammonia of specific gravity 0.88, 5 parts of a 50% aqueous dispersion of methylol stearamide, 1 part of the product obtained by condensing cetyl alcohol with 17 moles of The fabric is then squeezed, dried on a stenter at C.
  • the fabric is then washed at 100 C. for 1 minute with a solution contining 3 parts of sodium carbonate and 1 part of the reaction product of octyl phenol with 8 moles of ethylene oxide per 1000 parts water, rinsed and dried.
  • the fabric is dyed a greenish-blue shade which is fast to severe washing treatments and resistant to creasing.
  • the fabric is dyed a fast greenish-yellow shade and is resistant to creasing.
  • Example 29 A printing paste containing:
  • the printed fabric is then padded in the resin pad liquor described in Example 28, dried and heat baked for 3 minutes at 150 C.
  • the fabric is then washed as described in Example 28 and finally dried.
  • a bluish-red print is obtained on the cotton which possesses good fastness to' light and washing and which is resistant to creasing.
  • the emulsion thickening used in the above example may be obtained by adding 80 parts of white spirit to a rapidly stirred mixture of 5 parts of a 26.5% aqueous solution of the condensate of octyl phenol with 8 moles of ethylene oxide, 7 /2 parts of a 20% aqueous solution of the condensate of cetyl alcohol with 17 moles of ehtylene oxide, and 7 /2 parts of water.
  • Example 30 In place of the dyestuif used in Example 29 there are used 2 parts of the dyestuif of Example 2 of specification No. 83 8,335 and the resultant printing paste is printed on viscose rayon. The fabric is dried at 70 C. and then heat treated for 3 minutes at C.
  • the printed fabric is then padded in the resin pad liquor described in Example 1 and heat treated for 3 minutes at C.
  • the fabric is then washed as described in Example 28, rinsed in water and finally dried.
  • a bright reddish-blue print is obtained on the viscose fabric possessing good fastness to light and washing and which is similar in strength to an unsoaped print produced by the same method.
  • Example 31 100 parts of a mercerised cotton poplin fabric are padded with a solution containing 5 parts of the copper complex of the compound of the formula:
  • Thefabric is then squeezed, dried on a stenter at 100 C. and baked at 150 C. for 5 minutes.
  • the fabric is then washed at 80 C. for 1 minute with a solution containing 3 parts of sodium carbonate and 1 part of the reaction product of octyl phenol with 3 moles of ethylene oxide per 1000 parts of Water, rinsed and dried.
  • the fabric is dyed a purple shade which is fast to severe washing treatments and the fabric is resistant to creasing.
  • Example 32 100 parts of bleached mercerised plain weave cotton fabric are padded, at 100% expression, with a solution containing, per 1000 parts, 10 parts of the copper complex of 6-(dichloro-s-triazinylamino)-2-[4'-(2",5"- disulphophenylazo) methyl 2' hydroxyphenylazo1- l-naphthol-3,5-disulphonic acid, parts of sodium bicarbonate, 5 parts of sodium triisopropyl naphthalene sulphonate and is then dried in warm air at 70 C.
  • a solution containing, per 1000 parts, 10 parts of the copper complex of 6-(dichloro-s-triazinylamino)-2-[4'-(2",5"- disulphophenylazo) methyl 2' hydroxyphenylazo1- l-naphthol-3,5-disulphonic acid, parts of sodium bicarbonate, 5 parts of sodium triisopropyl na
  • the fabric is then padded, at 100% expression, through a solution containing, per 1000 parts, 200 parts of a 60% urea-formaldehyde precondensate, 30 parts of sodium bicarbonate, 62 parts of the condensation product of ethylene bisdicyandiamide and diethylene triarnine hydrochloride, 5 parts of a 50% aqueous dispersion of methylol stearamide and 1 part of the condensation product of cetyl alcohol with 17 moles of ethylene oxide. It is then dried in warm air at 70 C. and baked for 3 minutes at sulphonate.
  • the fabric is then dried to a dark blue shade, which is fast to washing, and is resistant to creasing.
  • Example 34 100 parts of bleached mercerised botton poplin are padded with a solution containing 28 parts of the 1:2-chromium complex and 12 parts of the 1:2-cobalt complex of 1 (4'chloro-6-amino-s-triazine-2'-ylarnino)- 2 (5"- nitro -2- bydroxyphenylazo) 8 naphthol 3,6- disulpnonic acid, 5 parts of sodium triisopropyl naphthalene sulphonate and 10 parts of sodium bicarbonate in 100-!) parts of water, squeezed to 100% expression, maintained in a moist condition for 45 minutes at atmospheric temperature and dried.
  • the fabric is then padded through a solution containing parts of a 40% aqueous solution of l,3-dimethylol-5-fi-hydroxyethylhexahydrotriazin- Z-one, 6.5 parts of magnesium chloride hexahydrate, 2 parts of tartaric acid, 5 parts of a 50% aqueous dispersion of methylolstearamide, 1 part of the product obtained by condensing cetyl alcohol with 17 moles of ethylene oxide and 20 parts of the condensate of dicyandiamide, formaldehyde and ammonium chloride obtained as described in Recipe 1 of United Kingdom specification No. 651,139.
  • Example 35 A viscose rayon fabric is padded at expression with a solution containing, per 1000 parts, 10 parts of 4- [5"-(dichloro-s-triazinylamino)-3"-sulphophenylazo] 1- (4'-sulph-ophenyl)-3-carboxypyrazolone, 10 parts of so dium bicarbonate and 5 parts of sodium triisopropyl naphthalene sulphonate, and dried at 70 C.
  • the dried fabric is then subjected to the treatment described in the second paragraph of Example 1. It is dyed a reddish yellow shade having good fastness to mild washing treatments and is resistant to creasing.
  • the fabric is then subjected to the treatment described in the second paragraph of Example 1. It is dyed a greenish blue shade fast to mild washing treatments and is resistant to creasing.
  • Example 37 100 parts of a mercerised cotton poplin fabric are padded at 100% expression with a solution containing 10 parts of la-mino 4-(3-dichloro-s-triazinyl-aminoanilino) anthraquinone-2,4-disulphonic :acid, 10 par-ts of sodium bicarbonate and 5 parts of sodium triisopropylnaphthalene It is .then dried at 70 C. and baked for 3 minutes at C.
  • the fabric is then subjected to the treatment described in the second paragraph of Example 28. It is dyed a reddish-blue shade which is fast to severe Washing treatments and resistant to creasing.
  • the fabric is thereafter maintained in a moist condition at atmospheric temperature for a period of time of from 15 minutes to 24 hours and is then dried,
  • the material is treated with the liquor containing the resin-finish ing agent and said cationic dye fixing agent, and
  • the fabric is thereafter maintained in a moist condition at atmospheric temperature for a period of time of from minutes to 24 hours and is then dried,
  • the material is treated with the liquor containing the resin-finis ing agent and said cationic dye fixing agent, and
  • the material is treated with the liquor containing the resinfini-shing agent and cationic dye fixing agent, and
  • the material is treated with the liquor containing the resinfinishing agent and cationic dye fixing agent, and
  • the mate 12 rial is treated with the liquor containing the resinfinishing agent and cationic dye fixing agent, and
  • the fabric is thereafter maintained in .a moist condition at atmospheric temperature for a period of time 'of from 15 minutes to 24 hours and is then dried,
  • the material is treated with the liquor containing the resinfinishing agent and cationic dye fixing agent, and
  • Process according to claim 1 characterised in that the textile material after treatment is then subjected to a Washing step to remove unpolymerised resin-formin g agent and residual acid, and is dried.
  • Process according to claim 1 characterised in that a linen textile material treated, and thereafiter it is subjected to a mercerisation step and washed to remove alkali and is dried.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Coloring (AREA)

Description

United States Patent 3,193,595 STEP-WISE PRUCESS FOR CQLGRING AND FEN- ISHHNG CELLULQSE MATEREALS WHEREHN A (ZATIONIC DYE-FDHNG AGENT IS EMPLGYED WITH THE RESTN FTNL SHENG AGENT Jack Frauhland Mawson, Ian Durham Rattee, and Erwin Seltzer, Manchester, England, assignors to Imperial Chemical Industries Limited, London, England, a corporation of Great Britain No Drawing. Filed May 3, 1962, Ser. No. 192,063 Claims priority, application Great Britain, May It}, 1961, 17 ,titlti/ 61 9 (Ilaims. (Cl. 8-48} This invention relates to a new colouration process. More particularly, the invention relates to a process for the finishing of cellulose textile fabrics coloured with reactive dyestuffs whereby a very high level of fixation of: dyestufi" on the fibre is combined with excellent quality of dyeing.
It is well known to dye or print cellulose textile fabrics with reactive dyestufis, and thereafter to submit the fabric to a conventional finishing treatment to obtain a creaseresistant or dimensionally stabilised coloured fabric. It has now been found that in such a process, a valuable eifect may be obtained by adding a cationic dye-fixing agent to the liquor from which the resin-finishing agent is applied. This procedure prevents unfixed dyestutr" from dissolving in the resin-finishing bath, and assists fixation so that the expensive and time-consuming washing process normally required when dyeing with reactive dyestuffs can be dispensed with between the dyeing and finishing steps, and is considerably shortened and frequently may be dispensed with entirely after the resin-curing step.
By a cationic dye-fixing agent, we mean an organic compound free from anionic water-solubilising groups such as sulphonic acid groups, but containing one or more ammonium groups, and frequently, but not always, an aliphatic chain of 6 or more carbon atoms. As examples of such compounds there may be mentioned the following classes:
(a) Compounds having an ammonium group and at least one aliphatic or cycloaliphatic residue having at least carbon atoms. Such substances are named in United Kingdom specifications Nos. 339,962, 366,918, 441,767, 443,588, 646,921 and 496,611. These substances may be applied in conjunction with a copper salt as described in United Kingdom specification No. 535,582.
(b) The condensation products of formaldehyde with dicyandiamide, or mixtures of urea and dicyandiamide in the presence of amine or ammonium salts. Such products are described in United Kingdom specifications Nos. 19783/38, 576,562 and 651,139. These products may also be applied in conjunction with a copper salt.
(c) The condensation products of aldehydes with hydroxyalkyl derivatives of amino and imino compounds, in the presence of salts of nitrogen containing inorganic or organic bases. Such products are described in United Kingdom specification No. 611,235.
(d) The water-soluble condensation products of nitrogen-containing complex copper compounds with compounds containing at least once the grouping:
and with aldehydes of low molecular Weight. Such prod nets are described and claimed in United Kingdom specification No. 736,792. 7
(e) The acid salts of the condensates of cyanamide, di-
cyandiamide N-substituted dicyandiamides, guanidine and Patented Aug. .3, 1965 N-substituted guanidines, with polyalkyleneimines. Such products are described and claimed in United Kingdom specifications Nos. 522,539, 657,753, 755,478 and 755,519.
(f) Arylene and alkylene biguanides such as those described and claimed in United Kingdom specification No. 705,833 and their polymers.
('3) The quaternary salts of polyaminoethylacrylates and other polymerised ethylenically unsaturated compounds containing primary, secondary or tertiary amino groups.
Thus according to the present invention there is provided the improvement in the process of colouring textile materials consisting wholly or partly of fibrous cellulose by application of a reactive dyestuff, thereafter applying a resin-finishing agent and thereafter baking the treated material to cure the resin, which improvement consists of adding to the aqueous liquor containing the resinfinishing agent, a cationic dye fixing agent as hereinbeiore defined.
By a reactive dyestuft we mean a water-soluble dyestun which contains a reactive halogen atom or other substituent capable of reacting with the resin or fibre so that the remainder of the dyestuff becomes attached to the resin or fibre through a covalent bond. As examples of such dyestuffs, there may be mentioned, for example, dyestufis containing s-triazinyl or pyrimidyl radicals carrying labile atoms or groups directly attached to the ring, and dyestuffs containing a beta-halogenopropionyl, betahalogenoethylsulphonyl, beta halogenoethylsulphamyl, beta-sulphatoethylsulphonyl, beta hydroxyethylsulphonyl, chloro-acetylamino, beta-(chloromethyl)-beta-sulphatoethylsulphamyl, acryloylamino, beta-(alkyland aryl-sulphonyloxy) alkyl sulphonyl, beta-acyloxyalkylsulphonyl, vinylsulphonyl, alkyl phosphite or sulphon fluoride radical.
By a labile atom or group, We means an atom or group which is bound by a covalent bond to a carbon atom of the pyrinn'dine or triazine nucleus but which readily dissociates under the influence of heat or alkalis, especially in the presence of moisture, to form an ion or an uncharged molecule. As examples of such atoms or groups, there may be mentioned, for example, bromine, or, preferably, chlorine atoms, sulphonic acid groups, thiocyano groups, negatively substituted aryloxy and arylthio groups, such as sulphophenoxy, sulphophenylthio, nitrosulphophenoxy, disulphophenoxy and sulphonaphthoxy groups, quaternary ammonium groups, groups of the formula:
Y r I wherein Y represents the group of atoms necessary to form a 5- or 6-membered heterocyclic ring which may carry substituents or form part of a fused ring system;
groups of the formula:
wherein R and R each represents the same or different aikyl, cycloalkyl, aryl or aralkyl groups, or R and R together form, together with the nitrogen atom, a 5- or 6-membered heterocyclic ring; and groups of the formula:
contain metal in complex formation. Specific examples of suitable dyestuffs are described in United Kingdom specification No. 209,723 in Examples 1 and 2, United Kingdom specification No. 298,494 in Example 1, in United Kingdom specifications Nos. 460,224, 733,471, 740,533, 775,308, 772,030, 774,925, 780,591, 781,930, 785,120, 785,222, 802,198, 805,562, 826,689 and 852,604, and 937,182 and 924,990.
There may also be used dyestuffs containing hydroxyl, amino, hydroxyalkylamino, guanyl hydrazide, semicarbazide r thiosemicarbazide groups linked to a triazine nucleus or hydroxyalkylamino groups linked to a pyrimidine nucleus or to the alkyl radical of an alkylsulphonyl, alkylsulphamyl, alkylcarbonyl or alkylcarbonamide group. Dyestuffs of these types have been described, for example in United Kingdom specification No. 209,723 in Example 1, in United States Patent No. 2,768,158 and United Kingdom specifications 904,227,
929,425 and 927,404, and the use of dyestuffs of these types has been described, for example in French Patents Nos. 1,206,833 and 1,208,532.
The dyestuif is applied to the textile material by immersion of the material in an aqueous solution of the dyestulf preferably by padding or by application of a printing paste containing .the dyestuif. The printing paste may be applied by any of the usual methods, such as by roller, block, screen or stencil. The dyestuff solution may contain other additions commonly used in the .art of dyeing with reactive dyestuffs, for example, urea,
wetting agents, such as alkali metal alkylated naphthalene sulphonates and condensates of ethylene oxide with alkylated phenols, fatty alcohols or fatty amines, migration inhibitor such as sodium chloride, sodium sulphate or sodium alginate and, usually, an acid binding agent to aid reaction with the fabric. The acid-binding agent is only necessary to achieve reaction with the fabric, and where the dyestuff is capable of reaction with the resin, there is no need to use an acid-binding agent. It is preferred to use a mild alkali, such as sodium carbonate or bicarbonate, as the acid-binding agent to minimise neutralisation of any acid or acid salt which may be used as curing catalyst in the subsequent processing.
After application of the dyestulf solution, the fabric is preferably dried at atmospheric temperature, but may also be dried at elevated temperatures for example by .treating with hot air at a temperature of between 50 to 150 C. or by treatment with steam in a steamer at a temperature of 100 to 105 C. for about 2 to 20 minutes. Before drying, fabric which has been dyed, particularly when containing viscose rayon, is advantageously allowed to stand in a moist condition for a period of time, which may be from minutes to 24 hours, preferably from 30 minutes to 2 hours, the treatment leading to improved fixation and diffusion of the dyestuif into the fibres, and hence to improved quality and appearance of dyeing.
The printing pastes containing the dyestulf may also contain the additives usually used with reactive dyestuffs such as urea, sodium, m-nitro-benzene sulphonate, wetting agents of the types indicated above and thickening agents such as sodium alginate, ethyl cellulose, starch, locust bean gum, and, preferably, oil-in-water emulsions and water-in-oil emulsions.
After application of the printing paste, the fabric is preferably dried, for example by passage over heated rollers, and may, if desired, then be baked or steamed for, for example, from 2 to minutes.
The dried textile fabric is then treated with the resinfinishing agent, for example by padding the material through an aqueous solution or suspension of the agent. The solution or suspension may contain other commonly-used additives for example curing-catalysts for for about 1 minute.
4: the resin-finishing agent, which may be acidic or alkaline as necessary, anionic and nonionic surface active agents, lubricating agents, softening agents, water repellentsand stiffening or bodying agents, as well as the cationic dyefixing agents.
As examples of resin-finishing agents which may be used, there may be mentioned acetal cellulose reactants (as defined in the Textile Research. Journal for 1959 at page 74) and, more particularly, mixtures comprising the methylol derivatives or lower alkyl ethers of methylol derivatives of monomeric or polymeric compounds containing a plurality of amino or mono substituted amino groups, said compounds being known from the art or used in practice for the formation of resins by condensation with formaldehyde. Suitable compounds include, for example monomeric nitrogen compounds such as urea, thiourea, substituted ureas and thioureas, dicyandiamide, dicyandiarnidine, biguanides, amides, carbamates, allophanates and heterocyclic compounds such as aminotriazines, urons, ureins, ureides, imidazolidones, triazones and hydantoins or mixtures of such compounds, and polymeric nitrogen compounds such as the polymeric amides made by the reaction of dibasic acids with diamines. The lower alkyl ethers of the methylol derivatives of these compounds include for example the methyl, ethyl, propyl and butyl ethers. Other resin-finishing agents which may be used are condensation products of ketones with aldehydes, in particular, CI-I O.
As examples of acid catalysts which may be used there may be mentioned salts formed from weakbases and mineral acids such as zinc chloride, ammonium sulphate and ammonium chloride, mineral acid salts of organic amines, weak acids, for example organic acids such as oxalic acids and substantially neutral substances which develop acidity on heating or steaming, such as magnesiumchloride and ammonium thiocyanate; mixtures of such catalysts may be used.
As examples of alkaline catalyst which may be used there may be mentioned sodium bicarbonate and sodium carbonate.
The aqueous solution used for application of the resinforming composition may contain between 3% and 40% and preferably between 5% and 30% of the resin-forming compositionsand between 0.1% and 5% and preferably between 0.5% and 3.0% of acid or alkali catalyst.
As examples of lubricating and softening agents which may be used, there may be mentioned, for example dispersions of natural or synthetic waxes, methylol stearamide and the quaternary ammonium salts of United Kingdom specification No. 808,265 (which in low concentration act as lubricants rather than as cationic dye-fixing agents). The amount of dye-fixing agent used can vary within wide limits, in some cases as little as 0.005 gram per litre of padding liquor being effective whilst in other cases as much as 1.5 grams per litre is required. These amounts are those at which a reasonable effect is shown and the use of higher quantities up to to grams per litre will give improved results.
The baking stage may be carried out at a wide range of temperatures, provided the temperature is sufficiently high to cure the resin. The timesof baking will depend upon the temperature used, a short period of heating, for example, about 10 seconds, being suificient at temperatures of the order of 200 C. whilst a period of about 1 to 5, usually 3, minutes is required at a temperature of about 155 C. The baking temperatures are preferably maintained at between C. and 200 C. adjusting the time to minimise thermal degradation of the cellulose.
If desired, the textile material can be given a short washing treatment, for example, a treatment in a weakly alkaline aqueous solution of soap or detergent at the 'boil This washing treatment serves the purpose of removing small amounts of unpolymerised resin-forming agent and the residual acidity caused by the acid catalyst or the decomposition products thereof.
The invention is illustrated but not limited by the following examples in which parts and percentages are by weight:
Example 1 100 parts of viscose rayon fabric are padded with a solution containing parts of the copper complex of 2- (5' sulpho-2'-hydroxyphenylazo)-6-(2",4"-dichloro-6"- s-triazinylamino)1-naphthol-3,S-disulphonic acid, 10 parts of sodium bicarbonate and 5 parts of sodium triisopropyl naphthalene sulphonate in 975 parts of Water, squeezed, maintained in a moist condition at atmospheric temperature for 1 hour and dried at 70 C. in a hot air drier.
The fabric is then padded through 1000 parts of a solution containing 400 parts of a 60% aqueous solution of a urea-formaldehyde precondensate (obtained by stirring a mixture of 1 mole of urea and 1.6 moles of formaldehyde at pH 8.5 and 20 C. for 4 /2 hours), parts of ammonium dihydrogen phosphate, parts of the condensate of dicyandiamide, formaldehyde and ammonium chloride obtained as described in Recipe 1 of United United Kingdom specification No. 808,265. The fabric 1 is then squeezed, dried on a pin stenter at 100 C. and baked at 150 C. for 3 minutes. The fabric is dyed a bluish-red shade having good fastness to severe Washing treatments and is resistant to creasing.
The following table sumrnc rises further examples of the new process, following the procedure of Example 1 above, but substituting the dyestufi' named in the first column for that used in the first padding solution and using the resinfinishing agent, acid catalyst and cationic dye-fixing agents named in the second, third and fourth columns for the urea-formaldehyde precondensate, the ammonium dihydrogen phosphate and the dicyandiamide/formaldehyde/ ammonium chloride condensation product, respectively.
In each case a fabric is obtained-having excellent fastness to creasing and coloured in the shade described in the fifth column; the dyeing has good fastness to severe washing:
Dyestufi Resin-finishing agent Acid catalyst Cationic dyte-fixing Shade agen 2. Disodium i-amino t-(3--sulphatoethylsulphonylaniline) an- As in Example 1- As in Example 1 As in Example 1. Bright redthraquinone-2-sulphonate, 5 parts. dish-blue.
3. The dyestufi having the formula: do ..do d0 Bright-red,
SI 0 H H g 503E (1)11 l IIHC\ N N N=N- C1 H0 38 s 0 3H 10 parts 7 4. 1-(2,5-dichloro-4-sulphophenyl)-3-methyl-4-(5-diehloro-s- 70% aqueous solu- Dicthanolamine 1,4-phenylene bigua- Greenishtriazinylamino-2-sulphophenylazo)-5-pyrazolone, parts. tion of1,3-d1- hydrochloride mde hydroyellow.
methylol-2- 10 parts. chloride, 10 parts. imidazolidone, 80 parts.
5. 6-(N-dichloro-s-triazinyl-N-methyl)amjno-1-hydroxy-2,2- As in Example 4- Magnesium chlo- 1,6-hexamethylene Orange.
azonaphthalene-l,3,5-trisulphonic acid, 10 parts. ride, 12 parts. higuazrde p501 mer, par s.
6. l-(dichloro-s-triazinyl) amino-7-phenylazo-8-naphthol-3,6- 50% aqueous solu- Magnesium chlo- Cetyl pyricliuium Bluish-red.
disulphonic acid, 5 parts. tion of hexamethride, 15 parts. bromide, 20 parts.
oxymethylmelamine, 70 parts. 7 7. l-amino-t[-(dichlorostriazinyl) amino anilinolanthraquinone- 50% aqueous solu- Ammonium dihy- The polymer of the Greem'sh. 2,3,5-trisulphonic acid, 10 parts. tion of 4,5-d1hydrogen phosphate, dimethyl sulphate blue.
droxy-LBJneth- 10 parts. quaternary amylo1-2-imidazmonium salt of oliclone, 70 parts. diethylaminoethyl methacrylate, 10 parts.
8. The copper complex of 6-(dichloros-triazinyl)tuninO-Z-W- 45% aqueous solu- Magnesium chlo- Saturated aqueous Da b1 (2,5-disulphophenylazo)-5-mcthyl-2-hydroxyphenylazo]- tion of trimethride, 6 parts; solution or chloro- 1-naphthol-3,5-disulphonic acid, 20 parts. ylol urea, 60 tartaric acid, 1.4 hexidine hydroparts. parts. chloride, parts.
9, 1-amino-4-[4"-(dichloros-triazinyl)amino-2,2-disulphostilben- 60% aqueous solu- Diethanolam ne 1,6-l1examethylene Gr 4-y1amino]anthraquinone-2,5-disulphonic acid, 10 parts. tion of a 1:1.6f hydrochloride, 10 biguamde po1yurea/formaldeparts. mar, 25 parts. hyde condensate, 300 parts. p
10. The 1:2-chromium complex of G-(dichloro-s-triazinyl)amino- 50% aqueous solu- Ammonium dihy- 1,4-phenylene bigua- Reddish. 2- (2'-carboxyphenylazo)-1-naphthol-3-sulphonic acid, 10 parts. tion of hexamethdrogen phosphate, nide polymer, b
oxy-methyl mel- 15 parts. 20 parts. amine 70 parts.
11. The copper complex of 8-(2-amiuo-4-chloro-s-triazinyl)aminoaque us S Z1110 trate, 10 As in Example 1-.-- Royal blue.
1,1 dihydro1;y-2,2-azo-naphthaoene-3,-6,8-tetrasulphonic tion of tnparts. acid, 10 parts. :grgethyllol urea,
par s.
12. The copper complex of 8-(2-m-sulphoanilinoy-chloros-triaqueous solu- Magnesium chlo- Cetyl pyridinium Purple.
azinyl)amin0-2-(3-chloro-5-sulpho-2-hydroxyphenylazo)- tion of 4,5-d1hyride, 12 parts. bromide. 1-naphth0l-3,6-disulphonic acid, 15 parts. droxy-1,3-d1- methylol-Z-imldazolidone, 80 parts. 13. 1-(2-chlor0-6-methyl-4-sulphophenyl)-3-methyl i-(2-methoxy- 70% aqueous solu- Zinc nitrate, 10 The condensate of Greenish- 5',8-sulphatocthylsulphonylpheuylazo)-5-pyrazolone, 10 parts. tion ,3-d 1- parts; tartaric ethylene bis-diye110w methylol-2-1m1dacid, 1 part. cyandiamide with azolidone, 80 diethanolamine parts. hydrochloride,
parts.
14. The copper complex of 1-(4-sulphophenyl)-3-methyl-4-(2'- 50% aqueous solu- Diethanolemine Saturated aqueous Rcddishhydroxy-5-B-sulphatocthylsulphonylphenylazo)5-pyrazolone, tion of hexahydrochloride, solution of chloroyellow. 15 parts. methoxymethyl- 7 parts; ammohexidme hydromelamine, nium nitrate, chloride, 30 parts. parts. 3 parts.
Dyestuft Resin-finishing agent Acid catalyst Cationic dyte-fixing Shade agen 15. 2-(2-methoxy-5-fi-sulphatocthylsulphonylphenylazo)-1- As in Example 1 Zinc nitrate, 10 As in Example 1 Red.
naphthol-S-sulphonic acid, 10 parts. parts. 16. The copper complex of S-acetylamin-2-(2-hydroxy-5-;3- 45% aqueous solu- Ammonium di- 1,6-hexamethylcne Violet.
sulphatoethylsulphonylphcnylazo)-1-naphthol-3,G-disulphonic tion 0 trihydrogen phosbiguanide polyacid parts. methylol urea, 40 photo, parts. nier, parts.
parts; 50% aqueous solution of hexamethoxy mcthylrnclamine, 40 parts.
Example 17 In this example, the procedure followed is that of Example 1, with the exception that the sodium bicarbonate is omitted from the first padding solution.
The coloured fabric so obtained has a lower fastness to severe Washing treatments, but has a commercially satisfactory standard of fastness to the mild washing treatments normally recommended for viscose rayon fabrics.
The following table lists dyestuffs which can be used in the above procedure in place of these named in Example 1. The second padding liquor can be formulated in accordance with any of those described in Examples 1 to 16 inclusive.
Example Dycstutf Shade 18 The product obtained by condensing copper Turquoise. phthaloeyaniue tetra- (3')- sulphonchloride with 1.5 moles of B-chloroethylaminc in the presence of ammonia.
The product. obtained by condensing copper phthalocyanine tri- (3)- sulphonchloride mouosulphonic acid with 1.5 moles of 5 ehloroethylamin e.
The product obtained by condensing copper phthalocyanine tri- (3)- sulphonchloridc monosulplionic acid with one mole of pphenylene diamine sulphonic acid in the presence of ammonia and reacting with 1 mole of 2,4,6-trichloropyrimidine.
The 1:2-chroniium complex of 6- -1nethoxy-4- chlor0-s-triazinylamino)-2-(2-carb0xypl1enylazo)-1-naphthol-8snlphonic acid.
A mixture of 1 part of the lz2-cobalt and 3 parts of the l:2-chromium complex of 6- "1Ini110- 4-chloro-s-triazinylamino)-0-nitro-1,2-dihydreary-2,1 ,-azonaphthalcne-SA -di s l p h o n i c act The copper complex of 6-(2 -m-sulphoanilino- 4,-ch1oros-triazinylamino) 2-[4-(2,5-d is u l phophenylazo)-5"-mcthyl-2"-hydroxyphenylazo}1-3,fi-disulphonic acid.
The product obtained by condensing copper phthalocyanine tri- (3 -snlphonchloride monosulphonio acid with 1 mole oi2-a1nino 4-ehloro-6-(4-amino-3-sulphaoanilino)-s-triacme.
8- [2, 4,-di (hydroxynicthylamino)-s-triazin-6- ylamino]-2- (2- sulphophenylazo) -1-naphthol3,5-disulphonic acid.
S-[2, 4'-di (pcntahydroxyn-hexylamino)stri azin-G-ylami11o]-2- (2 -sulphophc11ylar.0)-lnaphthol 3,G-disulphonic acid.
Reddishbrown.
22 Dark grey.
23 Dark blue.
24 Turquoise.
Grecnishyellow.
Bright red.
Example 28 chloride obtained as described in Recipe 1 of United King-- dom specification No. 651139, 1.15 parts of aqueous ammonia of specific gravity 0.88, 5 parts of a 50% aqueous dispersion of methylol stearamide, 1 part of the product obtained by condensing cetyl alcohol with 17 moles of The fabric is then squeezed, dried on a stenter at C.
and baked at 150 C. for 5 minutes.
The fabric is then washed at 100 C. for 1 minute with a solution contining 3 parts of sodium carbonate and 1 part of the reaction product of octyl phenol with 8 moles of ethylene oxide per 1000 parts water, rinsed and dried. The fabric is dyed a greenish-blue shade which is fast to severe washing treatments and resistant to creasing.
if in the above example the'dyestuff is replaced by 10 parts of the product obtained by condensing 1 mole of tetrachloropyrimidine with 3-rnethyl-1-(2,5-dichloro-4'- sulphophenyl) 4 (5"-amino-2-sulphophenylazo)-5- pyrazolone, the fabric is dyed a fast greenish-yellow shade and is resistant to creasing.
Example 29 A printing paste containing:
Parts Dyestuff of Example 1 of specification No. 846,949 2 later 32 Oil-in-water emulsion thickening 55 Sodium alginate thickening (4% sodium alginate) 9 Sodium m-nitrobenaenesulphonate 1 Sodium bicarbonate 1 is printed on mercerised cotton fabric and the fabric is dried at 70 C. and then treated for 5 minutes with steam at atmospheric pressure.
The printed fabric is then padded in the resin pad liquor described in Example 28, dried and heat baked for 3 minutes at 150 C. The fabric is then washed as described in Example 28 and finally dried.
A bluish-red print is obtained on the cotton which possesses good fastness to' light and washing and which is resistant to creasing.
The emulsion thickening used in the above example may be obtained by adding 80 parts of white spirit to a rapidly stirred mixture of 5 parts of a 26.5% aqueous solution of the condensate of octyl phenol with 8 moles of ethylene oxide, 7 /2 parts of a 20% aqueous solution of the condensate of cetyl alcohol with 17 moles of ehtylene oxide, and 7 /2 parts of water.
Example 30 In place of the dyestuif used in Example 29 there are used 2 parts of the dyestuif of Example 2 of specification No. 83 8,335 and the resultant printing paste is printed on viscose rayon. The fabric is dried at 70 C. and then heat treated for 3 minutes at C.
The printed fabric is then padded in the resin pad liquor described in Example 1 and heat treated for 3 minutes at C. The fabric is then washed as described in Example 28, rinsed in water and finally dried.
A bright reddish-blue print is obtained on the viscose fabric possessing good fastness to light and washing and which is similar in strength to an unsoaped print produced by the same method.
Example 31 100 parts of a mercerised cotton poplin fabric are padded with a solution containing 5 parts of the copper complex of the compound of the formula:
10 parts of sodium bicarbonate and 5 parts of sodium triisopropyl naphthalene sulphonate in 980 parts of water, squeezed, dried at 70 C. in a hot air drier and baked for 3 minutes at 150 C. The fabric is then padded through an aqueous solution containing 80 parts of a 40% aqueous solution of 1,3-dimethylol-5-beta-hydroxyethyl-hexahydro-triazin-Z-one, 10 parts of zinc nitrate hexahydrate, 10 parts of hexarnethyleue biguanide polymer, 5 parts of a 50% aqueous dispersion of methylol stearamide, 1 part of the product obtained by condensing cetyl alcohol with 17 moles of ethylene oxide and 1 part 05 acetic acid in each 1000 parts. Thefabric is then squeezed, dried on a stenter at 100 C. and baked at 150 C. for 5 minutes. The fabric is then washed at 80 C. for 1 minute with a solution containing 3 parts of sodium carbonate and 1 part of the reaction product of octyl phenol with 3 moles of ethylene oxide per 1000 parts of Water, rinsed and dried. The fabric is dyed a purple shade which is fast to severe washing treatments and the fabric is resistant to creasing.
If the dyestuff used in the above example is replaced by 10 parts of the dyestuif of the formula:
SIOQH II I I son II I N O NH SOaH the material is dyed a fast blue shade and is resistant to creasing.
Example 32 Example 33 100 parts of bleached mercerised plain weave cotton fabric are padded, at 100% expression, with a solution containing, per 1000 parts, 10 parts of the copper complex of 6-(dichloro-s-triazinylamino)-2-[4'-(2",5"- disulphophenylazo) methyl 2' hydroxyphenylazo1- l-naphthol-3,5-disulphonic acid, parts of sodium bicarbonate, 5 parts of sodium triisopropyl naphthalene sulphonate and is then dried in warm air at 70 C. The fabric is then padded, at 100% expression, through a solution containing, per 1000 parts, 200 parts of a 60% urea-formaldehyde precondensate, 30 parts of sodium bicarbonate, 62 parts of the condensation product of ethylene bisdicyandiamide and diethylene triarnine hydrochloride, 5 parts of a 50% aqueous dispersion of methylol stearamide and 1 part of the condensation product of cetyl alcohol with 17 moles of ethylene oxide. It is then dried in warm air at 70 C. and baked for 3 minutes at sulphonate.
. 10 160 C. The fabric is then washed off as described in Exarnple 28.
The fabric is then dried to a dark blue shade, which is fast to washing, and is resistant to creasing.
Example 34 100 parts of bleached mercerised botton poplin are padded with a solution containing 28 parts of the 1:2-chromium complex and 12 parts of the 1:2-cobalt complex of 1 (4'chloro-6-amino-s-triazine-2'-ylarnino)- 2 (5"- nitro -2- bydroxyphenylazo) 8 naphthol 3,6- disulpnonic acid, 5 parts of sodium triisopropyl naphthalene sulphonate and 10 parts of sodium bicarbonate in 100-!) parts of water, squeezed to 100% expression, maintained in a moist condition for 45 minutes at atmospheric temperature and dried. The fabric is then padded through a solution containing parts of a 40% aqueous solution of l,3-dimethylol-5-fi-hydroxyethylhexahydrotriazin- Z-one, 6.5 parts of magnesium chloride hexahydrate, 2 parts of tartaric acid, 5 parts of a 50% aqueous dispersion of methylolstearamide, 1 part of the product obtained by condensing cetyl alcohol with 17 moles of ethylene oxide and 20 parts of the condensate of dicyandiamide, formaldehyde and ammonium chloride obtained as described in Recipe 1 of United Kingdom specification No. 651,139.
Example 35 A viscose rayon fabric is padded at expression with a solution containing, per 1000 parts, 10 parts of 4- [5"-(dichloro-s-triazinylamino)-3"-sulphophenylazo] 1- (4'-sulph-ophenyl)-3-carboxypyrazolone, 10 parts of so dium bicarbonate and 5 parts of sodium triisopropyl naphthalene sulphonate, and dried at 70 C.
The dried fabric is then subjected to the treatment described in the second paragraph of Example 1. It is dyed a reddish yellow shade having good fastness to mild washing treatments and is resistant to creasing.
Example 36 A viscose rayon fabric is padded at 100% expression with a solution containing, per 1000 puts, 10 parts of 1- =amino-4- [4'-dichloro-s triazinyla-minoanilino]anthraquinone-2,3',5-trisulphonic acid and 5 parts of sodium butyl naphthalene sulphon-ate, and is then dried at 70 C.
The fabric is then subjected to the treatment described in the second paragraph of Example 1. It is dyed a greenish blue shade fast to mild washing treatments and is resistant to creasing.
Example 37 100 parts of a mercerised cotton poplin fabric are padded at 100% expression with a solution containing 10 parts of la-mino 4-(3-dichloro-s-triazinyl-aminoanilino) anthraquinone-2,4-disulphonic :acid, 10 par-ts of sodium bicarbonate and 5 parts of sodium triisopropylnaphthalene It is .then dried at 70 C. and baked for 3 minutes at C.
The fabric is then subjected to the treatment described in the second paragraph of Example 28. It is dyed a reddish-blue shade which is fast to severe Washing treatments and resistant to creasing.
What We claim is:
1. In the process of colouring cellulose materials comprising treatment with a reactive dye-stuff, thereafter applying a resin-finishing agent and thereafter baking the treated material to cure the resin, the improvement which consists in adding to the aqueous liquor containing the resin-finishing agent, an organic cationic dye-fixing agent free from anionic solubilizing groups and having at least one ammonium group.
2. Process according to claim 1 consisting essentially in the following sequence of steps:
(a) the textile material is immersed in an aqueous solution of the dyestutf containing an acid-binding agent,
(b) the fabric is thereafter maintained in a moist condition at atmospheric temperature for a period of time of from 15 minutes to 24 hours and is then dried,
() without any intermediate washing step, the material is treated with the liquor containing the resin-finish ing agent and said cationic dye fixing agent, and
(d) the material is thereafter baked to cure the resin.
3. Process according to claim 1 consisting essentially in the following steps:
(a) the textile material is immersed in an aqueous solution of the dyestuff which is free from acidbinding agent,
(b) the fabric is thereafter maintained in a moist condition at atmospheric temperature for a period of time of from minutes to 24 hours and is then dried,
(c) without any intermediate washing step, the material is treated with the liquor containing the resin-finis ing agent and said cationic dye fixing agent, and
(d) the material is thereafter baked to cure the resin.
4. Process =accordingto claim 1 consisting essentially in the following sequence of steps:
(a) the textile material is immersed in an aqueous solution of the dyestuif containing an acid-binding agent,
(b) the material is dried,
(c) without any intermediate washing step, the material is treated with the liquor containing the resinfini-shing agent and cationic dye fixing agent, and
(d) the material is thereafter baked to cure the resin.
5. Process according to claim 1 consisting essentially in the following steps:
(a) the textile material is immersed in an aqueous solution of the dyestuff which is free from acid-binding agent,
(b) the material is dried,
(0) without any intermediate washing step, the material is treated with the liquor containing the resinfinishing agent and cationic dye fixing agent, and
(d) the material is thereafter baked to cure the resin.
6. Process according to claim 1 consisting essentially in the following sequence of steps:
(a) the textile material is immersed in an aqueous solution of the dyestuif containing an acid-binding agent,
(b) the material is dried and subjected to a baking step,
(c) without any intermediate Washing step, the mate 12 rial is treated with the liquor containing the resinfinishing agent and cationic dye fixing agent, and
(d) the material is thereafter baked to cure the resin.
7. Process according to claim 1 consisting essentially in the following sequence of steps:
(a) the textile material is immersed in an aqueous solution of the dyestuff containing an acid-binding agent,
(b) the fabric is thereafter maintained in .a moist condition at atmospheric temperature for a period of time 'of from 15 minutes to 24 hours and is then dried,
(c) the textile material is then subjected to a baking step,
(d) without any intermediate washing step, the material is treated with the liquor containing the resinfinishing agent and cationic dye fixing agent, and
(e) the material is thereafter baked to cure the resin.
8. Process according to claim 1 characterised in that the textile material after treatment is then subjected to a Washing step to remove unpolymerised resin-formin g agent and residual acid, and is dried.
9. Process according to claim 1 characterised in that a linen textile material treated, and thereafiter it is subjected to a mercerisation step and washed to remove alkali and is dried.
References Cited by the Examiner UNITED STATES PATENTS 2,768,158 10/56 Strobel et a1. 81.2 3,116,103 12/63 Gamlen et a1. 8-18 FOREIGN PATENTS 209,723 3/25 Great Britain.
496,611 12/38 Great Britain.
535,592 4/41 Great Britain.
611,235 10/ 48 Great Britain.
651,139 3/51 Great Britain.
705,838 3/54 Great Britain.
755,519 3/54 Great Britain.
736,792 9/55 Great Britain.
775,308 5/57 Great Britain.
785,222 10/57 Great Britain.
826,689 1/60 Great Britain.
846,505 8/60 Great Britain.
NORMAN G. TORCHIN, Primary Examiner.
ABRAHAM H. WINKELSTEIN, Examiner.

Claims (1)

1. IN THE PROCESS OF COLOURING CELLULOSE MATERIALS COMPRISING TREATMENT WITH A REACTIVE DYE-STUFF, THEREAFTER APPLYING A RESIN-FINISHING AGENT AND THEREAFTER BAKING THE TREATED MATERIAL TO CURE THE RESIN, THE IMPROVEMENT WHICH CONSISTS IN ADDING TO THE AQUEOUS LIQUOR CONTAINING THE RESIN-FINISHING AGENT, AN ORGANIC CATIONIC DYE-FIXING AGENT FREE FROM ANIONIC SOLUBILIZING GROUPS AND HAVING AT LEAST ONE AMMONIUM GROUP.
US3198595D Step-wise process for coloring anb fin- ishing cellulose materials wherein a cationic dye-fixing agent is employed with the resin finishing agent Expired - Lifetime US3198595A (en)

Publications (1)

Publication Number Publication Date
US3198595A true US3198595A (en) 1965-08-03

Family

ID=3457595

Family Applications (1)

Application Number Title Priority Date Filing Date
US3198595D Expired - Lifetime US3198595A (en) Step-wise process for coloring anb fin- ishing cellulose materials wherein a cationic dye-fixing agent is employed with the resin finishing agent

Country Status (1)

Country Link
US (1) US3198595A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3416875A (en) * 1964-07-17 1968-12-17 Acna Process for dyeing cellulose textile materials with quaternized reactive dyestuffs
US3490860A (en) * 1967-09-05 1970-01-20 Geigy Ag J R Process for aftertreatment of freshly colored polyamide fibers
US3490859A (en) * 1967-09-05 1970-01-20 Geigy Ag J R Process for aftertreatment of colored polyamide fibers
US3871817A (en) * 1973-09-07 1975-03-18 Us Agriculture Simultaneous dyeing and crosslinking of cellulosic fabrics
US3983588A (en) * 1970-12-23 1976-10-05 Ciba-Geigy Ag Process for the dyeing or printing and simultaneous finishing of cellulose materials
US3988108A (en) * 1973-04-09 1976-10-26 Kanebo, Ltd. Process for coloring fibrous structures
US4304567A (en) * 1979-05-09 1981-12-08 Hoechst Aktiengesellschaft Process for the pad-dyeing of textile webs of cellulose fibers
US4629470A (en) * 1985-10-18 1986-12-16 The United States Of America As Represented By The Secretary Of Agriculture Process for dyeing smooth-dry cellulosic fabric

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB209723A (en) * 1923-01-09 1925-03-23 Chem Ind Basel Manufacture of new azo-dyestuffs
GB496611A (en) * 1936-10-23 1938-12-02 Chemical Works Formerly Sandoz Basic derivatives of fatty acids and a process for their manufacture
GB535592A (en) * 1938-10-13 1941-04-15 Monsanto Chemicals Improvements in or relating to rubber composition and method of preserving rubber
GB611235A (en) * 1946-02-25 1948-10-27 Sandoz Ltd Process for the manufacture of new condensation products
GB651139A (en) * 1948-04-05 1951-03-14 James Albert Moyse Improvements in or relating to the manufacture of coloured paper
GB705838A (en) * 1951-02-05 1954-03-17 Ici Ltd New bactericidal substances
GB736792A (en) * 1951-05-10 1955-09-14 Bayer Ag Condensation products of complex copper compounds with nitrogen-containing compounds and aldehydes
GB755519A (en) * 1953-08-14 1956-08-22 Ici Ltd Water-soluble organic nitrogen compounds
US2768158A (en) * 1953-03-30 1956-10-23 Gen Aniline & Film Corp Triazine dyes
GB775308A (en) * 1953-08-10 1957-05-22 Ciba Ltd New monoazo-dyestuffs and process for making them
GB785222A (en) * 1954-11-29 1957-10-23 Ici Ltd New monoazo dyestuffs derived from cyanuric chloride
GB826689A (en) * 1956-12-14 1960-01-20 Ici Ltd New phthalocyanine dyestuffs
GB846505A (en) * 1957-11-22 1960-08-31 Ici Ltd New colouration process for textile materials
US3116103A (en) * 1959-09-24 1963-12-31 Ici Ltd Textile colouration process

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB209723A (en) * 1923-01-09 1925-03-23 Chem Ind Basel Manufacture of new azo-dyestuffs
GB496611A (en) * 1936-10-23 1938-12-02 Chemical Works Formerly Sandoz Basic derivatives of fatty acids and a process for their manufacture
GB535592A (en) * 1938-10-13 1941-04-15 Monsanto Chemicals Improvements in or relating to rubber composition and method of preserving rubber
GB611235A (en) * 1946-02-25 1948-10-27 Sandoz Ltd Process for the manufacture of new condensation products
GB651139A (en) * 1948-04-05 1951-03-14 James Albert Moyse Improvements in or relating to the manufacture of coloured paper
GB705838A (en) * 1951-02-05 1954-03-17 Ici Ltd New bactericidal substances
GB736792A (en) * 1951-05-10 1955-09-14 Bayer Ag Condensation products of complex copper compounds with nitrogen-containing compounds and aldehydes
US2768158A (en) * 1953-03-30 1956-10-23 Gen Aniline & Film Corp Triazine dyes
GB775308A (en) * 1953-08-10 1957-05-22 Ciba Ltd New monoazo-dyestuffs and process for making them
GB755519A (en) * 1953-08-14 1956-08-22 Ici Ltd Water-soluble organic nitrogen compounds
GB785222A (en) * 1954-11-29 1957-10-23 Ici Ltd New monoazo dyestuffs derived from cyanuric chloride
GB826689A (en) * 1956-12-14 1960-01-20 Ici Ltd New phthalocyanine dyestuffs
GB846505A (en) * 1957-11-22 1960-08-31 Ici Ltd New colouration process for textile materials
US3116103A (en) * 1959-09-24 1963-12-31 Ici Ltd Textile colouration process

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3416875A (en) * 1964-07-17 1968-12-17 Acna Process for dyeing cellulose textile materials with quaternized reactive dyestuffs
US3490860A (en) * 1967-09-05 1970-01-20 Geigy Ag J R Process for aftertreatment of freshly colored polyamide fibers
US3490859A (en) * 1967-09-05 1970-01-20 Geigy Ag J R Process for aftertreatment of colored polyamide fibers
US3983588A (en) * 1970-12-23 1976-10-05 Ciba-Geigy Ag Process for the dyeing or printing and simultaneous finishing of cellulose materials
US3988108A (en) * 1973-04-09 1976-10-26 Kanebo, Ltd. Process for coloring fibrous structures
US3871817A (en) * 1973-09-07 1975-03-18 Us Agriculture Simultaneous dyeing and crosslinking of cellulosic fabrics
US4304567A (en) * 1979-05-09 1981-12-08 Hoechst Aktiengesellschaft Process for the pad-dyeing of textile webs of cellulose fibers
US4629470A (en) * 1985-10-18 1986-12-16 The United States Of America As Represented By The Secretary Of Agriculture Process for dyeing smooth-dry cellulosic fabric

Similar Documents

Publication Publication Date Title
US3116103A (en) Textile colouration process
US3066005A (en) Process for the treatment of hydroxyl group-containing textile materials
TW211595B (en)
GB2154615A (en) Dyeing assistants
US3198595A (en) Step-wise process for coloring anb fin- ishing cellulose materials wherein a cationic dye-fixing agent is employed with the resin finishing agent
US3088790A (en) Dyeings and prints possessing fastness to wet processing and their manufacture on cellulose material
US2416884A (en) Methylated methylolmelamine as a fixing agent for dyed cotton textiles
EP0151370B1 (en) Dyeing and printing fibres
US4297101A (en) Process for the dyeing of synthetic polyamide fibers with reactive dyes according to the batchwise exhaustion method
AU610932B2 (en) Process for dyeing or printing of fibre material from natural or synthetic polyamides with reactive dyes
US5851240A (en) Process for dyeing cellulosic textile fibre materials
US3177214A (en) Resinous triazinylamevo amhua- quinone dyestuffs
US4009000A (en) Process for the dyeing or printing and simultaneous finishing of cellulose materials
US3072454A (en) Reactive dyes containing methylolamide triazine groups
US3501259A (en) Process for simultaneous coloration and finishing of cellulose fibers and reactive dyes therefor
US6350872B1 (en) Salt free dyeing of cellulosic fibers with anionic dyes
US3220793A (en) Coloration process
US3125403A (en) New colouration process
US3086832A (en) Process for finishing dyeings
US4139344A (en) Process for the continuous dyeing of wool
US3411860A (en) Method of dyeing cellulose fibers
US3248379A (en) Fiber reactive dyestuffs and process for their preparation
US3054699A (en) Water-soluble latent curing catalysts for textile treatment resins
US2902472A (en) Production of dicyandiamide triethylene tetramine formaldehyde condensate
US3511590A (en) Process for dyeing or printing fibrous materials