Patent GB-462290-A (GB)
Title: A process for improving cellulosic materials
IPC: D06M13/256
Filed: 1935-07-25
Abstract: Cellulosic materials are improved, especially as regards their dyeing properties, by treating them, preferably in an aqueous medium, with substantially colourless organic compounds containing (a) at least one group rendering the compounds substantive, such group comprising at least one aromatic nucleus; (b) at least one aliphatic, cycloaliphatic, aliphatic-aromatic or heterocyclic radicle with at least 7 carbon atoms directly attached to one another; and (c) at least one quaternary ammonium or phosphonium or ternary sulphonium group not directly attached to an aromatic nucleus.  Specified groups rendering the compounds substantive are the residues of benzidine and its derivatives, of hydroxynaphthoic acids, of acetoacetic acid naphthylamides, of 4 : 4<1>-diaminodiphenylurea and its derivatives, of 4 : 4<1>-diaminostilbene, of 4 : 4<1>- or 5 : 5<1>-diaminocarbazole, of benzidinesulphone, of 1 : p 4-phenylenediamine and of 1 : 5-naphthylenediamine and residues of aminobenzoic or aminocinnamic acids linked together in an amide-like manner.  Specified types of the compounds are inter alia those of the general formul  <FORM:0462290/IV/1> <FORM:0462290/IV/2> <FORM:0462290/IV/3> <FORM:0462290/IV/4> in which R1, R2 and R3 are aliphatic, cycloaliphatic or aliphatic-aromatic radicles, e.g. methyl, ethyl, amyl, dodecyl, octodecyl, cyclohexyl, benzyl or naphthylmethyl or in which the N atom is in the heterocyclic ring of a quaternary ammonium chloride derived from pyridine, quinoline or like heterocyclic base.  The treatment improves the depth of subsequent dyeings with indigo and other vat dyes, enables dyeing to be effected with acid wool dyes and when the compound used contains an aliphatic radicle of at least 8 carbon atoms, decreases the sensitivity of the fibres to moisture and improves their feel and improves also the fastness to water and washing of subsequent dyeings with substantive dyes.  The following examples are specified: (1) viscose artificial silk cut fibre is treated for 1 hour in a boiling bath containing a compound as in I above in which R1 and R3 are methyl and R2 is dodecyl, hexadecyl or the alkyl radicle of the alcohol obtainable by reduction of the fatty acids in palm kernel oil and is hydroextracted and dried without rinsing; it may then be dyed with acid dyestuffs; alternatively, the corresponding compounds in which the <FORM:0462290/IV/5> groups are replaced by <FORM:0462290/IV/6> , in which R1, R2 and R3 are benzyl, or by <FORM:0462290/IV/7> , in which R1 is methyl and R2 is dodecyl, may be employed; (2) the fibre treated as in (1) is worked up with loose wool into yarn or fabric which is then dyed uniformly with Orange II in a bath containing Glauber salt and acetic and sulphuric acids; (3) a fabric of viscose artificial silk and wool is treated for 1 hour in a boiling bath containing the benzidide of oxamic acid-a -propylamide - g  - benzyldimethylammonium chloride and dried without rinsing; it is then dyed uniformly with Wool fast red 3B in a bath containing Glauber salt and acetic and sulphuric acids; the benzidine derivative may be replaced by the corresponding 1 : 5-naphthylenediamine derivative; (4) a yarn or fabric of artificial silk cut fibre and wool is treated for 1 hour in a boiling bath containing a compound as in III above in which R1 and R3 are methyl and R2 is benzyl and is rinsed and dyed uniformly with Alizarine direct blue AGG; (5) cotton piece goods, dyed with Sirius red 4B are treated for 20 minutes in a bath at 30 DEG  C. containing 1-naphthylmethyldimethyl-g -2<1> : 3<1> - oxynaphthoylaminopropylammonium chloride and are dried without rinsing; the fastness of the dyeing to water is improved; (6) viscose artificial silk skein goods are treated for 15 minutes in a bath at room temperature containing a compound as in IV above in which R1, R2 and R3 are methyl and are hydroextracted and dried without rinsing; the goods acquire a soft, smooth touch and their wetability is reduced.  Specification 427,089 is referred to.  Dialkyl-di-(2 : 3-oxynaphthoyl-g -aminopropyl)-ammonium chlorides and like compounds of type II above are obtained by reaction of 2 : 3-oxynaphthoic acid chloride (2 mols.) with dipropylenetriamine (1 mol.), introduction of the radicle R1 by means of an alkylating or like agent and further treatment to convert the tertiary amine into the quaternary ammonium chloride.  Benzidine derivatives of example (1) are obtained by reaction of benzidine with chloracetyl chloride in benzene, in presence of an equimolecular amount of pyridine, and treatment of the product in alcoholic solution with dimethyldodecylamine, dimethylhexadecylamine, tribenzylphosphine, methyldodecylsulphide, &c.  Dimethyldodecylamine and dimethylhexadecylamine are obtained by treating dodecyl and hexadecyl bromides respectively with an alcoholic solution of dimethylamine under pressure.  Methyldodecyl sulphide is obtained by reaction of dodecyl bromide with the sodium salt of methyl mercaptan.  The benzidide of oxamic acid-a -propylamide-g -benzyldimethylammonium chloride is obtained by reaction of benzidine-di-(oxamic acid ester) with g  - dimethylamino - a  - aminopropane and treatment of the product with benzyl chloride.  Benzidine-di-(oxamic acid ester) is obtained by treating benzidine (1 mol.) with oxalic acid diethyl ester (20 mols.).  g -Dimethylamino-a -aminopropane is obtained by hydrogenating the addition product from dimethylamine and acrylic acid nitrile.  The 4 : 4<1>-diaminodiphenylurea derivative of example 4 is obtained by treating with dimethylbenzylamine the condensation product from 4 : 4<1>-diaminodiphenylurea and chloracetic acid.  1 - Naphthylmethyl - dimethyl - g  - 2<1> : 3<1> - oxynaphthoylaminopropyl - ammonium chloride is obtained by treating with 1-naphthylmethyl chloride the amide derived from 2 : 3-oxynaphthoic acid and g -dimethylamino-a -aminopropane.  The trimethylammonium chloride derived from 1 - stearylamino - 4 - aminoacetylaminobenzene of example 6 is obtained by treating with trimethylamine the condensation product from 1 : 4-diaminobenzene (1 mol.), stearic acid chloride (1 mol.) and chloracetyl chloride (1 mol.).  Reference has been directed by the Comptroller to Specification 438,508.