Patent GB-481096-A (GB)
Title: A process of dyeing
Filed: 1936-06-30
Abstract: The sodium salt of complex chromic 5-sulphosalicylic acid is obtained by reaction of chromium acetate with 4-sulphosalicylic acid and neutralizing with soda.ALSO:Mordant dyes, dyeing with; cellulose esters or ethers dyeing.-Fast dyeings are obtained upon fibres, foils and like shaped materials made from an organic film-forming polymeric substance containing firmly fixed basic groups combined in residues present prior to the shaping operation by the action thereon, simultaneously or in any sequence, of a chromable dyestuff and a compound containing chromium in an anion.  The basic groups must be so firmly fixed as to be incapable of removal by a neutral saponaceous solution or by dilute acid.  When a pre-treatment with the compound containing chromium in an anion is employed, such compound may be reduced on the materials before applying the dyestuff.  Shaped materials containing basic groups which may be so dyed are basically substituted cellulose derivatives and cellulose esters or ethers or synthetic polymerization products containing components carrying basic groups or groups capable of receiving a basic character or increase of basic character by an after-treatment, e.g. the materials described in Specification 455,602.  As components carrying basic groups are specified (1) basically substituted phenol-formaldehyde resins such as those obtained by the action of (a) equivalent quantities of formaldehyde and amines, such as dimethyl-, diethyl- or dipropylamine, piperidine, morpholine, piperazine, diethanolamine or benzylamine on the products of condensation of formaldehyde and phenols in presence of hydrochloric acid, (b) halogen alkylamines on soluble phenol-formaldehyde condensation products, (2) products of the action of amines on basically substituted ethers of polyhydric alcohols such as those obtainable by reaction with epichlorhydrin, (3) condensation products of polyacrylic acid esters with polyamines, (4) products of reaction of polyglycide esters with organic bases, (5) products of reaction of polychlorinated paraffins with polyamines, (6) products of reaction of compounds containing more than one alkylating group on primary mono- or diamines, (7) basic thioureas from alkylene polyamines, (8) basic cellulose derivatives, e.g. acetyldiethylaminoethyl - cellulose (obtainable by acetylating the product of reaction of alkali cellulose with b -chlorethyldiethylamine).  As components capable of receiving a basic character or an increase of basic character by an after-treatment are specified (1) polyvinyl chloracetate, (2) polyglycide chloracetate, (3) soluble phenol-formaldehyde resins substituted by the chloracetylaminomethyl residue, (4) o -chlor-b -hydroxypropyl ethers of polyhydroxy compounds, which components (1) to (4) may be after-treated with an aminating agent such as di- or tri-methylamine, N-methylethyleneimine, pyridine, ethylenethiourea or N-cyclohexyl-N1-dimethyl thiourea, (5) interpolymerisates from maleic anhydride and vinyl compounds, which may be after-treated with polyamines such as ethylenediamine or 3-piperido-1-aminopropane, (6) cellulose isonicotinic acid ester (cf. Specification 347,451), (7) polymerized thioureas from polyamine resins and aliphatic mustard oils, which components (6) and (7) may be after-treated with an alkylating agent such as methyl iodide, toluenesulphonic acid methyl ester or benzyl chloride, (8) polymerizates containing carboxylic acid amide groups, which may be after-treated with formaldehyde and a secondary amine, (9) soluble nitroso compounds from amine resins, which may be treated with acid reducing agents. Alkylation of basic groups already present may be effected with alkyl halides, alkylene oxides, sulphides or imines, epichlorhydrin, 1-chloropropylene sulphide - 2 : 3, butadiene dioxide, 1 : 4-dibromobutane, 1 : 5-dibromopentane, 1 : 4-dichloroor dibromo-butene-2 : 3, 1 : 3-dichloracetone, tetra - g  - chloro - b  - hydroxypropylammonium chloride, the spirocyclic quaternary ammonium salt from N : N1-di-g -chloro-b -hydroxypropylpiperazine, N : N1-di-2 : 3-epoxypropyl-tetramethylethyleneammonium chloride, chloracetyl chloride or p-chloromethylbenzenesulphonic acid methyl ester. Components may also be incorporated having an acid character, e.g. such as are described in Specification 459,711 and the porosity of the shaped materials may be increased by incorporating substances such as fatty acids or their amides, soaps, glycerol or hygroscopic salts capable of being removed subsequently.  In some cases the capacity for absorption of dyestuffs may be increased by treatment with alkylating agents or agents effecting a partial saponification, e.g. alkylene oxides, alkylene imines, ammonia or amines.  The fastness to washing of the dyeings may be further improved by after-treatment with dodecylguanidine, dodecylbiguanide, o-tolylbiguanide, amines with long carbon chains and quaternary derivatives thereof, products of reaction of halogenated paraffins with ammonia or an amine or phenolformaldehyde resins containing substituted aminomethyl groups.  In examples, (1) acetate artificial silk containing 10 per cent of polyvinyl chloracetate and after-treated with pyridine (cf. Specification 455,849), is dyed in presence of wool in a bath at 95 DEG  C. containing Acid anthracene brown KE, Metachrome red G, Acid alizarine flavine R, Alizarine light grey BBLW or Fast mordant blue B, sodium sulphate and acetic acid, with addition after 1/2 hour of formic acid and after a further 1/2 hour of potassium bichromate, after-chroming being continued for 1/2 hour; (2) acetate artificial silk as in (1) is treated for 3/4 hour with a solution at 30-50 DEG  C. of potassium bichromate, suspended in air containing sulphur dioxide, rinsed and dyed in a bath at 30-75 DEG  C., containing Alizarine yellow GGW and acetic acid; (3) acetate artificial silk as in (1) is dyed by the metachrome process in a bath at 30-75 DEG  C. containing Alizarine yellow GGW or Alizarine direct green 5G, sodium sulphate, metachrome mordant and sulphite waste liquor; (4) fabric of acetate artificial silk as in (1) is treated with a solution at 30-75 DEG  C. containing potassium bichromate, lactic acid and glucose, reduction of the bichromate being completed by treatment with a cold solution of sodium bisulphite and glycine, and is dyed at 65-70 DEG  C. with Coerulein S; (5) fabric as in (4) is treated with a solution at 30-75 DEG  C. containing potassium bichromate, lactic acid and sulphuric acid, reduction of the bichromate being completed by treatment with a cold solution of sodium bisulphite and hydrolyzed glue, and dyed at 40-75 DEG  C., with Gallocyanine F, Coerulein S or Alizarine red S; (6) acetate artificial silk containing 7,5 per cent of polyacrylic acid o -diethylaminoethylamide is treated with a solution at 40-50 DEG  C. containing potassium bichromate and acetic acid, suspended in a sulphur chamber for reduction of the bichromate and dyed at 30-70 DEG C. with Coerulein S or Alizarine W in presence of acetic acid or with Alizarine V2a bluish in feebly alkaline solution; (7) acetate artificial silk as in (6) is heated for 12 hours in a moist atmosphere at 85 DEG  C. containing methyl iodide, dyed in a bath at 40-85 DEG  C. containing Fast mordant blue B, sodium sulphate and acetic acid, with later addition of formic acid, and after-treated with potassium bichromate; (8) acetate artificial silk containing 7,5 per cent of polyvinyl chloracetate and 5 per cent of the inter-polymerizate from vinyl methyl ether (1 mol.) and maleic anhydride (1 mol.) and after-treated with pyridine is dyed and after-chromed as in (1) or pre-chromed and dyed as in (2); (9) acetate artificial silk as in (8) with replacement of the pyridine by 3-dimethylamino-1-aminopropane is dyed in a bath at 50-85 DEG  C. containing Acid anthracene red 3BL, sodium sulphate and formic acid and after-chromed with potassium bichromate; (10) acetate artificial silk as in (8) with replacement of the maleic anhydride by vinyl acetate and of the pyridine by 3-piperido-1-aminopropane is dyed in a bath at 50-85 DEG  C. containing Diamond black P2B, formic acid and N-cyclohexyl-N1-dimethylthiourea with addition of potassium bichromate to the exhausted bath for after-chroming for 1/2 hour at 85-90 DEG  C.; (11) acetate artificial silk containing 10 per cent of the inter-polymerisate from vinyl methyl ether (1 mol.) and maleic anhydride (1 mol. and after-treated with ethylene diamine is treated for 12 hours with a moist atmosphere at 70 DEG  C. containing epichlorhydrin vapour, dyed at 50-90 DEG  C. with Alizarine direct green G and after-chromed with potassium bichromate; (12) an acetylcellulose film containing 15 per cent of the inter-polymerizate from vinyl methyl ether (1 mol.) and maleic anhydride (1 mol.) and after-treated with 1-dimethylamino-3-aminopropane is dyed at 50-70 DEG  C. with Chromaxane pure blue B with addition to the exhausted bath of formic acid and potassium bichromate for after-chroming at 85-90 DEG  C.; (13) acetate artificial silk containing 7,5 per cent of polyvinyl chloracetate and 5 per cent of the interpolymerizate from vinyl methyl ether (1 mol.) and maleic anhydride (1 mol.) is dyed in a bath at 40-80 DEG  C. containing Acid anthracene brown KE and N-cyclohexyl-N1-dimethylthiourea with addition to the exhausted bath of formic acid and potassium bichromate for after chroming at 85 DEG  C.; (14) acetate artificial silk containing 8 per cent of polyvinyl chloracetate and 7 per cent of N-cyclohexylN1-dimethylthiourea is dyed in a bath at 40-80 DEG  C. containing Diamond black P2B, sodium sulphate and acetic acid with later addition of formic acid and after-chroming with potassium bichromate; (15) acetate artificial silk containing 8 per cent of a reaction product from chlorinated paraffin and ethylenediamine and after-treated with ethylene imine vapour i