Patent GB-491314-A (GB)
Title: A process of improving animal fibres or similar natural or artificial fibrous or film-like materials
IPC: D06P1/00
Filed: 1937-01-26
Abstract: Animal fibres or other natural or artificial fibrous or film-like materials consisting of or containing protein substances, or containing basic amino or imino groups attached to residues, not removable by rinsing with water, are treated with one or more substances adapted to react under the treatment conditions with amino or imino groups to form a substituted amidine.  Such treatment modifies the affinity of the materials for various agents, e.g. acid or basic dyestuffs and their components, mordants, tanning and loading agents or agents for combating pests and may be effected before, during or after a dyeing operation.  Specified materials treated are wool, chromed or chlorinated wool, wool pre-treated with alkali, potassium thiocyanate or hydrogen peroxide, loaded or non-loaded silk, artificial silk of fibroin or casein, feathers, bristles pelts, felts, horn, tanned or non-tanned hides and cellulose derivatives containing basic ester, ether or amide groups or containing basic resins.  The treatment may be applied locally to obtain printing, including reserve printing effects.  Specified amidine-forming reagents are cyanogen, cyanogen halides and their polymerides, cyanamide and its dialkyl derivatives and tautomerides, N-cyanosarcosine, N-cyanomethyltaurine, 3-cyanamidobenzoic acid, 2-dimethylaminophenylcyanamide barium succinocyanamidate, acetimino-ethyl and -thioethyl ethers, terephthalic acid diiminoethyl ether, isourea and isothiourea ethers, S-methylisothiourea methosulphate, N-o - dimethylaminophenyl - N1 - allylmethylisothiourea methosulphate, the addition product from g -chloro-b -hydroxypropanesulphonic acid and N - diethylaminoethyl - N1 - allylthiourea, the addition product from sodium chloracetate and methyl thiocarbaminylmethyltaurine, 2 - hydroxymethylthiazole, benzothiazole - 2 - sulphonic acid, halogenpyridinesulphonic acids, 2-methoxypyridinemethiodide, 4 : 6 - dichloro - N - methylpyridinium - 2 - sulphonic acid, dichloropyridazine, cyanuric dichloride monoamide, the condensation product from equimolecular proportions of malonitrile, formaldehyde and dimethylamine and its methiodide, disulphides carrying the group <FORM:0491314/IV/1> , amidines carrying easily exchanged amino or imino groups and other agents referred to in the examples below.  When the amidine-forming reagent is a strong base it may be used in the form of a salt and the reaction may be effected in presence of an acid-binding or buffering agent, such as sodium acetate, borax, disodium phosphate or an alkali salt of a dialkylaminoacetic acid. The materials may be made more reactive by a preliminary treatment, e.g. with chlorine, a thiocyanate solution, hydrogen peroxide or a swelling agent, such as urea, thiourea, formamide, resorcinol, glycol, mannite or an alkali salicylate.  The amidine-forming reagent may also contain additional residues having a solubilizing or an affinity-modifying effect or a specific protective effect against pests or capable of further reaction or containing a chromophoric group.  When a bleaching effect is desired, the treatment may be effected in presence of an oxidizing or reducing agent.  A softening effect is produced when the treatment introduces a residue carrying a chain of more than 8 carbon atoms. Amidine formation may be effected by reaction of several substances in presence of the material, e.g. wool may be treated with an alkylthiourea and a desulphurizing agent such as zinc oxide or a basic zinc salt or with thiourea and a reactive halogen compound. Alternatively the material may be treated successively with several reagents, e.g. wool, impregnated with an alkylthiourea, may be after-treated with sodium chloracetate, ethyl bromide, methyl ethanesulphonate or toluenesulphonate or mono- or dichlorhydrin.  The amidine groups may be further modified by simultaneous or subsequent treatment with reagents such as formaldehyde, chloral, chloracetaldehyde, heptyl, or dodecyl aldehyde, glyoxal, diacetyl, benzoin, acetylacetone, ethyl acetoacetate, dimethylaminomethanol, dimethylolurea and methylol derivatives of cyanuric acid or amino-1 : 3 : 5-triazine, in presence, if desired, of urea, thiourea, dicyandiamide, toluenesulphonamide or phenol.  The materials may also be treated before, during or after the amidine-forming treatment with an alkylating or aralkylating agent such as ethyl bromide or iodide, methyl p-toluenesulphonate, benzyl chloride, xylylene chlorides, methyl chloracetoacetate, vinyl chloracetate, chloracetone, 1 : 3-dichloracetone, diazoparaffins, ethylene or propylene oxide, propylene sulphide, epichlorhydrin, tetra (g -chloro-b -hydroxypropyl) ammonium chloride, piperidopropenoxide, oxidopropyltrimethylammonium chloride, butylethylene imine, diethylethyleneiminium chloride, the quaternary salt from piperazine (1 mol.) and epichlorhydrin (2 mols.) and aromatic compounds carrying reactive nuclear halogen. In examples: (1) a zephyr yarn is impregnated with an aqueous solution of S-hydroxyethyl-m -mercaptodihydroglyoxaline hydrochloride, centrifuged and suspended in a moist atmosphere at 50-60 DEG  C., the product has increased affinity for acid dyes such as Alizarine direct blue A and Thiazine red R; (2) a mixed fabric of wool and acetate artificial silk is impregnated with an aqueous methanol solution of 2-amino-5-chloromethyloxazoline-2 : 3, squeezed and stored in a moist atmosphere at 50 DEG  C.; the wool has increased affinity for acid dyes; (3) wool is impregnated with an aqueous solution of the product obtained by reaction of ethylene chlorhydrin with the reaction product from 3-diethylaminopropylamine and allyl isothiocyanate, centrifuged and subjected to a moist atmosphere at 60 DEG  C.; the product is dyed darker than non-treated wool with Alizarine direct blue A; (4) wool is treated with a moist atmosphere at 80 DEG  C. containing acetiminoethyl ether; the product is dyed more deeply than untreated wool with Amidonaphthol red 2B or Alizarine direct blue A; (5) wool is impregnated with a hot solution of ethylenethiourea and treated with a moist atmosphere at 60 DEG  C. containing ethyl bromide; (6) wool is padded with a solution containing equimolecular proportions of ethylenethiourea and b -chlorethyldiethylamine hydrochloride, squeezed and stored in a moist atmosphere at 75 DEG C.; (7) wool is padded with the isothiourea ether salt from 1 : 3-dibromopropane and p  ethylenethiourea and subjected to a moist atmosphere at 60 DEG  C.; (8) natural silk is treated as in (2); (9) wool is treated with a boiling methanol solution of malonitrile in presence of potassium acetate; (10) viscose artificial silk which has been treated with ethylene imine is further treated as in (2); (11) films of cellulose methyl-p-nitrobenzyl ether are subjected to a reduction of the nitro groups and suspended in a moist atmosphere containing benziminomethyl ether; (12) wool, dyed with Amidonaphthol red BB, is impregnated with a solution of S-hydroxyethyl-m -mercaptodihydroglyoxaline hydrochloride, centrifuged and stored in a moist atmosphere containing propylene oxide; (13) dry wool is treated in a closed vessel with a solution at 60 DEG  C. of cyanuryl chloride in acetone with or without a simultaneous alkylation with butadiene dioxide or epichlorhydrin, squeezed, and treated with hot air; (14) artificial silk of cellulose ethyl-p-nitrobenzyl ether is subjected to a reduction of the nitro groups and dyed in a neutral bath at 60-85 DEG  C. containing Alizarine direct blue A and benziminomethyl ether dispersed with oleylpolyglycol, acetic acid being added towards the end of the dyeing.  N - cyanosarcosine, N - cyanomethyltaurine and 3 - cyanamidobenzoic acid are obtained by reaction of a cyanogen halide with sarcosine, methyltaurine and 3-amidobenzoic acid respectively.  2 - Dimethylaminophenylcyanamide is obtained by desulphurizing with zinc oxide, a basic zinc salt or lead oxide the product of reaction of as.-dimethyl-o-phenylenediamine hydrochloride with an alkali thiocyanate.  Barium succinocyanamidate is obtained by neutralizing with barium hydroxide the product of reaction of succinic anhydride with cyanamide.  Terephthalic acid di-iminoethyl ether is obtained by treating terephthalic acid nitrile with alcohol and hydrochloric acid.  S - methylisothiourea methosulphate is obtained by reaction of dimethyl sulphate with thiourea.  N - o - dimethylaminophenyl - N1 - allylmethylisothiourea methosulphate is obtained by alkylating with dimethyl sulphate the reaction product from as.-dimethyl-o-phenylenediamine and allyl isothiocyanate.  N - diethylaminoethyl - N1 - allylthiourea is obtained by reacting diethylaminoethylamine with allyl isothiocyanate.  4 : 6 : Dichloro - N - methylpyridinium - 2 - sulphonic acid is obtained by the action of sodium sulphate on the reaction product from 2 : 4 : 6-trichloropyridine and dimethyl sulphate.  Dichloropyridazine is obtained by reaction of maleic acid azine with phosphorus pentachloride.  S - hydroxyethyl - m  - mercaptodihydroglyoxaline is obtained by reaction of ethylenethio urea with b -chlorethyl alcohol. Cellulose - methyl - p - nitrobenzyl ether is obtained by reaction of a lowly methylated cellulose with p-nitrobenzyl chloride or p-nitrobenzylphenyldimethylammonium hydroxide in presence of alkali. Cellulose - ethyl - p - nitrobenzyl ether is similarly obtained by reaction of a lowly ethylated cellulose with p-nitrobenzyl chloride. The Specification as open to inspection under Sect. 91 comprises also the use, as amidine-forming reagent, of glutaric acid di-iminoethyl ether.  This subject-matter does not appear in the Specification as accepted.