Patent GB-613818-A (GB)
Title: Improvements in the treatment of textile and other materials having a basis of cellulose derivatives or synthetic resins
IPC: D06P5/22
Filed: 1945-06-07
Abstract: The dyeing affinities of hydrophobe cellulose derivative or p synthetic resin materials such as yarns or fabrics are modified by incorporating in the materials, from a liquid medium which has a swelling action on the materials, a polyamine containing at least three basic amino groups at least one of which is attached only to aliphatic carbon.  The swelling medium may be anhydrous ethyl alcohol, a mixture of ethyl alcohol and water, a mixture of ethyl acetate, ethanol, and water, or aqueous dioxane.  The amine may be present in the form of its salt with a weak acid.  A large number of polyamines is specified, including diethylene triamine, triethylene tetramine, 1.13-diamino-7-aza-tridecane, 1.16-diamino-7.10-diaza-hexadecane, 1.30-diamino-3.14.17.28-tetra-aza-triacontane, 4.41-bis-o -amino-methyl-diphenyl, c.c.c.-tri-g -aminopropylmethyl-amine, and 1.16-di-(benzylamino)-7.10-diazahexadecane.  The polyamines used may contain substituents other than hydrocarbon radicals, e.g. there may be used a crude product obtained by reacting excess of diethylene triamine or 1.16-diamino-7.10-diazahexadecane with one mole of a dicarboxylic acid or ester, e.g. ethyl oxalate.  There may be used a crude amine obtained by reacting 1 mole of ethylene dibromide with 2 moles of hexamethylene diamine, or 1 mole of 1.4-bis-o -bromo-methyl benzene or 4.41-bis-o -bromo-methyl diphenyl with 2 moles of ethylene diamine.  The polyamine is preferably of only limited solubility in water, and preferably of molecular weight less than 1,000.  The amount of polyamide incorporated in the materials may be such as to give a nitrogen content of at least 0.1 per cent and preferably 0.2 to 2 per cent. After application of the polyamine solution, the material may be dyed with acid dyes immediately or after rinsing or drying.  The fastness of the polyamine deposit on the materials may be improved by an aftertreatment with formaldehyde, glyoxal, ethyl oxalate, a poly-isocyanate or isothiocyanate, hexamethylene di-isocyanate, hexamethylene diphenyl-urethane, or the compound formed from 1 mole of hexamethylene di-isocyanate and 2 moles of acetoacetic ester.  After the treatment with formaldehyde, the materials may be subjected to a heat treatment.  The process may be applied to materials of vinyl chloride-vinyl acetate co-polymers, polyacrylonitrile, or nylon, e.g. a nylon from hexamethylene diamine and adipic acid.  Specifications 581,153, 586,549, 597,253, 610,311, 613,807, [Group IV (b)], and 613,817 are referred to.ALSO:Polyamines containing at least three basic amino groups, at least one of which is attached only to aliphatic carbon, used for treating synthetic resins and cellulose derivatives include the following: 1.16-di-(benzylamino)-7.10-diazahexadecane made by condensing 1.16-diamino-7.10-diazahexadecane with 3 moles. of benzaldehyde to give 1.3-bis-(61-benzylideneaminohexyl) -2-phenyltetrahydroimidazole, which is then reduced and hydrolysed with hydrochloric acid, 1.12-diamino-3.10-diazadodecane made by condensing 1.6-dibromohexane with a large excess of ethylene diamine, C.C.C.-tri-g -aminopropylmethylamine prepared by hydrogenation of tri-b -cyanoethylnitromethane and N.N1-bis-g -aminopropyl-p-phenylenediamine made by reacting p-phenylenediamine with 2 moles. of acrylonitrile and hydrogenating the product.  The polyamines may contain substituents other than hydrocarbon radicals, e.g. a crude product obtained by reacting excess of diethylenetriamine or 1.16-diamino-7.10-diazahexadecane with 1 mole. of a dicarboxylic acid or ester, e.g. ethyl oxalate.  Crude amines obtained by reacting 1 mole. of ethylenedibromide with 2 moles. of hexamethylenediamine and 1 mole. of 1.4-bis-o -bromomethylbenzene or 4.41-bis-o -bromomethyldiphenyl with 2 moles. of ethylenediamine are mentioned.  In examples, 1.20-diamino-7.14-diazaeicosane obtained by refluxing 2 moles. of hexamethylene diamine with 1 mole. of hexamethylene dibromide in presence of ethanol and a polyamine prepared by refluxing 1 mole. of hexamethylene diamine with 1 mole. of ethylene dibromide in ethanol are employed for treating cellulose acetate fabric. Specifications 581,153, 586,549, 597,253, 610,311, 613,807 and 613,817 are referred to.ALSO:The dyeing affinities of hydrophobe cellulose derivative or synthetic resin materials such as yarns or fabrics are modified by incorporating in the materials, from a liquid medium which has a swelling action on the materials, a polyamine containing at least three basic amino groups at least one of which is attached only to aliphatic carbon.  The treatment may be applied before or after dyeing.  When it is applied to already dyed materials, the colourations are more resistant to fading under the influence of burnt gas fumes.  The treatment may be applied to cellulose acetate materials to render them amenable to dyeing by water-soluble dyes containing acid groups, e.g. the acid wool dyes. The treatment may be applied to mixed materials such as mixtures of cellulose acetate with wool or cotton yarns.  The swelling medium may be anhydrous ethyl alcohol, a mixture of ethyl alcohol and water, a mixture of ethyl acetate, ethanol, and water, or aqueous dioxane. The amine may be present in the form of its salt with a weak acid.  A large number of polyamines is specified, including diethylene triamine, triethylene tetramine, 1.13 - diamino - 7 - aza - tridecane, 1.16 - diamino - 7.10 - diaza - hexadecane, 1.30 - diamino - 3.14.17.28 - tetra - aza - triacontane, 4.41 - bis - o  - amino - methyl - diphenyl, C.C.C.-tri - - - aminopropyl methyl-k-amine, and 1.16-di - (benzylamino) - 7.10 - diaza - hexadecane.  The polyamines used may contain substituents other than hydrocarbon radicals, e.g. there may be used a crude product obtained by reacting excess of diethylene triamine or 1.16-diamino - 7.10 - diaza - hexadecane with one mole of a dicarboxylic acid or ester, e.g. ethyl oxalate. There may be used a crude amine obtained by reacting 1 mole of ethylene dibromide with 2 moles of hexamethylene diamine, or 1 mole of 1.4-bis-o -bromo-methyl benzene or 4.41 - bis - o  - bromo - methyl diphenyl with 2 moles of ethylene diamine.  The polyamine is preferably of only limited solubility in water, and preferably of molecular weight less than 1,000.  The amount of polyamine incorporated in the materials may be such as to give a nitrogen content of at least 0.1 per cent and preferably 0.2 to 2 per cent. After application of the polyamine solution, the material may be dyed with acid dyes immediately or after rinsing or drying.  For heavy shades the treated material is not rinsed or scoured before dyeing. Dyeing with acid wool dyes may be effected by substantive absorption, the dye-bath being at a temperature not exceeding 90 DEG  C. Dispersed water-insoluble dyes commonly used for cellulose acetate may be applied by customary dyeing methods. Dyes may be applied by padding or printing methods.  Acid wool dyes may be applied from solutions in organic media, e.g. aqueous ethanol, having a swelling action on the materials.  The fastness of the polyamine deposit on the materials may be improved by an after-treatment with formaldehyde, glyoxal, ethyl oxalate, a poly-isocyanate or isothiocyanate, hexamethylene di-isocyanate, hexamethylene diphenyl-urethane, or the compound formed from 1 mole of hexamethylene di-isocyanate and 2 moles of acetoacetic ester.  After the treatment with formaldehyde, the materials may be subjected to a heat treatment.  In an example, cellulose acetate fabric is treated with an aqueous ethanol solution of 1.16-diamino-7.10-diaza-hexadecane.  It is squeezed and dried and baked and may then be dyed with acid wool dyestuffs.  Cellulose acetate yarn is run through a solution of diethylene triamine in a mixture of ethyl acetate, ethanol, and water.  The squeezed and dried fabric may then be dyed with acid wool dyestuffs. Cellulose acetate fabric is treated with an aqueous ethanol solution of 1.20-diamino-7.14-diazaeicosane.  This compound is obtained by refluxing 2 moles of hexamethylene diamine with 1 mole of hexamethylene dibromide in presence of ethanol.  The treated fabric after drying is dyed with 1.4-dimethylamino anthraquinone. In another example, 1 mole of hexamethylene diamine and 1 mole of ethylene dibromide in ethanol are heated under reflux to form a polyamine. Cellulose acetate fabric is treated with a solution of the product in aqueous ethanol.  The fabric is then squeezed and dried.  It may be dyed with Solway Ultra Blue BS. or 1.4-dimethylamino-anthraquinone. In another example cellulose acetate fabric is treated with alcoholic triethylene tetramine, dried and then exposed to formaldehyde gas. The fabric may be dyed with Lissamine Navy Blue, Carbolan Blue BS or Azo Geranine 2GS.  The process may be applied to materials of cellulose esters or ethers, vinyl chloride-vinyl acetate co-polymers, poly-acrylonitrile, or nylon, e.g. a nylon from hexamethylene diamine and adipic acid.  Specifications 581,153, 586,549, 597,253; 610,311, 613,807, [both in Group IV (b)], and 613,817 are referred to.