Patent GB-427089-A (GB)
Title: Improvements in and relating to the dyeing of textiles
IPC: C09B44/02
Filed: 1933-07-12
Abstract: Substantive and mordant dyes, dyeing with; two or more specified types of dyes in one bath, dyeing with; regenerated celluloses, dyeing; azo dyes.--Dyeings fast to washing are obtained upon natural or artificial cellulose by forming on the fibre a water-insoluble salt of a substantive quaternary ammonium compound, having at least two quaternary ammonium groups in the molecule with a substantive or non-substantive organic compound of acid character containing more than ten carbon atoms, at least one of the two components having dyestuff properties, the dyeing being effected by treating the materials with aqueous solutions of the two components successively, the component employed first being of a substantive character.  The dyed materials may be subsequently treated with lake-forming metal salts.  The acid component may derive its acidity from carboxylic, sulphonic or other acid hydroxyl groups, e.g. phenolic groups.  In one form of the process, the materials are first dyed with a substantive dyestuff in the usual manner and then, with or without rinsing, are treated with the solution of a salt of the quaternary ammonium base, which may also be a dyestuff.  This treatment may in some cases, be effected by adding the solution to the exhausted dyebath.  Mordant drawing substantive dyes may be used, in which case the treatment with the mordanting metal salt and with the quaternary ammonium compound may be effected in a single bath. Alternatively the treatment with the quaternary ammonium salt may precede the dyeing, in which case the dyestuff used as second component need not be substantive, e.g. it may be an acid wool dyestuff.  If the quaternary ammonium salt used as first component is a dyestuff, the second component need have no dyeing properties but may be, for example, a suitable substituted or unsubstituted carboxylic or sulphonic acid of the aliphatic, alicyclic, aromatic or fatty aromatic series, and if soap-forming acids, sulphonated fats or oils, or ester salts of polyvalent inorganic acids with high molecular alcohols of the aliphatic, alicyclic or fatty-aromatic series, such as sulphuric ester salts of high molecular fatty alcohols, are used, a softening and, in the case of artificial silk, a matting effect is obtained. Natural or artificial tanning materials, either alone or together with acid dyestuffs, may be used as second components.  Specified natural tanning materials are those of the pyrogallol and ellagene classes and specified artificial tanning materials are sulphurized phenols such as those known under the Registered Trade Mark "Katanol," which, having a substantive character, are also applicable as first components.  The following examples are specified.  (1) Cotton is dyed with Congo red, rinsed, wrung out, treated for \ba1/2\be hour in a bath at 90--100 DEG  C. containing the methyl sulphuric acid salt obtainable by addition of methyl sulphate to a nitrobenzene solution of the azo dyestuff, benzidine \sQ dimethylaniline (2 mols.), rinsing and drying, the dyeing is of outstanding fastness to washing with soap solution at 90--100 DEG  C. (2) Cotton is treated for 1 hour in an aqueous bath at 85 DEG  C. containing sodium sulphate, sodium carbonate and sodium 1 : 5 - di(cinnamylamino)naphthalene - 3 : 7 - disulphonate and the treated material is rinsed and treated for \ba1/2\be hour in a warm aqueous bath containing sodium chloride, acetic acid and the dyestuff benzidine \sQ 2 - oxynaphthyl - 7 - trimethylammonium chloride (2 mols.).  Specification 173,313, [Class 15 (ii)], is referred to. Sodium 1 : 5 - di(cinnamylamino)naphthalene - 3 : 7 - disulphonate is obtained by treating sodium 1 : 5 - diaminonaphthalene - 3 : 7 - disulphonate with cinnamyl chloride in presence of a substance binding acid.  The Specification as open to inspection under Sect. 91 comprises also the following subject-matter:--(a) the use of the colourless quaternary ammonium compounds with soap-forming acids &c. as above to produce a softening and, in the case of artificial silk, a matting effect, without dyeing; (b) an example in which cotton, dyed with Direct deep black EW, is introduced into a bath at about 40 DEG  C. containing the dyestuff, trimethyl - m - aminophenylammonium chloride --> (acid) a  - naphthol (alkaline) \sM tolusafranine, the temperature is raised to 95--100 DEG  C. and so maintained for 25--30 minutes and the material is rinsed and dried to obtain a black dyeing fast to washing; (c) an example in which cotton is dyed with Benzo light blue FR from a neutral salt bath, a solution of the dyestuff, tolusafranine (2 mols.) \sQ a -naphthol, is added to the exhausted bath which is then boiled until the second dyestuff is absorbed, and the material is rinsed and dried to obtain a black-blue dyeing fast to washing and light; (d) an example in which cotton or viscose artificial silk is treated for 45 minutes in a bath at 85--100 DEG C. containing 1 - (4<1> - cinnamylaminobenzoylamino) - 4 - trimethylammoniummethosulphate (obtainable by condensing p-nitrobenzoyl chloride with p-aminodimethylaniline in pyridine, treating the product with dimethyl sulphate, reducing the nitro group and condensing with cinnamic acid chloride) or the amide obtainable by condensing 1 mol. of terephthaloyl chloride with 2 mols. of the 4<1>-trimethylammoniummethosulphate of 4-aminobenzoylaniline, acetic acid and sodium chloride, rinsed cold and introduced moist into a bath at 60 DEG  C. containing Orange II and sodium chloride; (e) an example in which cotton or viscose artificial silk is treated for 1 hour in a bath at 90--100 DEG  C. containing the azo dyestuff, the m-trimethylammonium chloride of aniline (2 mols.) \sQ the benzidide of 2 : 3 - oxynaphthoic acid, acetic acid and sodium chloride and after rinsing is treated for \ba1/2\be hour in a boiling bath containing Congo red, rinsed and dried; (f) an example in which cotton or viscose artificial silk is dyed with the azo dyestuff, dianisidine \sQ 2-oxynaphthyl - 7 - trimethylammonium chloride (2 mols.) together with a substantive ammonium base as in (d) above and softened by subsequent treatment in a hot bath containing sodium lauryl, cetyl-or octadecyl-sulphonate, turkey red oil, oleyltaurine, or the sulphuric ester salts of dodecyl, tetradecyl, cetyl- or octadecyl-alcohols; (g) an example in which cotton is dyed with diamine brown M, further treated as in (c) above and finally treated for 25 minutes in a bath at 80--100 DEG  C. containing acetic acid, potassium bichromate and copper sulphate; (h) an example in which a cotton fabric is treated for 1 hour in a bath at 85 DEG  C. containing a pyrogallol or ellagene tanning extract, squeezed out and treated in a bath at 80--100 DEG  C. containing the substantive disazo ammonium base of (1) above with addition to the exhausted bath of sodium bichromate and copper sulphate; (i) an example in which cotton is dyed by treatment for \ba3/4\be hour in a boiling bath containing the azo dyestuff, tolusafranine (2 mols.) \sQ a -naphthol, acetic acid and sodium chloride, the bath being then cooled to 40 DEG C. with addition of a natural tanning extract and then boiled for \ba1/2\be hour and the dyeing being developed by treatment for 25--30 minutes in a bath at 80--100 DEG  C. containing acetic acid, potassium bichromate and copper sulphate.  This subject-matter does not appear in the Specification as accepted.