Patent GB-698039-A (GB)
Title: Process of dyeing and printing
IPC: D06P1/14
Filed: 1949-08-25
Abstract: Complex metal derivatives of 3-imino-isoindolenines containing in the 1-position an alkoxy, amino or substituted amino group are obtained as follows.  (1) o-Arylene dinitriles are treated with copper salts in organic solvents; (2) 1-amino-3-imino-isoindolenines are reacted with soluble heavy metal compounds and ammonia; (3) condensed 1-alkoxy-3-imino-isoindolenines are reacted with soluble heavy metal compounds, preferably in organic solvents, and the products precipitated; (4) metal phthalocyanines are treated with nitric acid or bromine in the presence of an organic solvent and the products decomposed with a basic substance; (5) metal phthalocyanines are reacted with nitrates of amino-imino-isoindolenines at elevated temperatures in inert solvents; (6) o-arylene dicarboxylic acids or their functional derivatives (especially nitriles) are heated with cuprous halides in the presence of urea and formamide.  In examples, (1) the copper derivative of 1-amino-3-imino-iso-indolenine is obtained from the isoindolenine, copper chloride and pyridine; the product may have 1, 2 or 4 mols. of isoindolenine per atom of copper according to the conditions of formation; (2) a copper derivative of a condensed imino-isoindolenine is prepared by treating copper phthalocyanine with methanol and bromine and removing halogen from the product by interaction with ammonia; (3) cobalt derivatives of condensed imino-iso-indolenines (2 forms) are obtained by treating cobalt phthalocyanine with nitric acid and nitrobenzene and adding caustic soda to the product; (4) a cobalt-containing polyiminoisoindolenine is prepared by reacting 1-amino-3-imino-isoindolenine with cobalt chloride in nitrobenzene. The preparation of the metal-free isoindolenines is described in Specifications 698,049 and 698,070, but further examples are given here:-(1) a dimolecular methoxy-imino-isoindolenine is obtained by reacting phthalonitrile with sodium methoxide in benzene; (2) the acetate of 1-amino-3-imino-isoindolenine is prepared by adding acetic acid to a methanolic solution of the base.ALSO:Compounds of the formula (1) or (2) below are applied to the fibre and subjected to a heat treatment, preferably in the presence of a reducing agent, whereby phthalocyanines are formed; heavy metal compounds may be present or the isoindolenines may be used in the form of their N-(heavy metal) derivatives: <FORM:0698039/IV (c)/1> <FORM:0698039/IV (c)/2> R1, R2 and R3 are hydrogen or alkyl, aryl, aralkyl or cycloalkyl (which may be substituted) or R2 and R3 together form an alkylene group; A is a substituted or unsubstituted o-arylene or o-cycloalkylene radical; n is 1 to about 6; X is hydrogen or a substituent that does not inhibit phthalocyanine formation; Z is hydrogen; Y is alkoxy, mercapto or -NR2R3; one carbon atom in the carbocyclic ring of (2) may be replaced by nitrogen.  The invention also includes compositions of the above compounds with a water-miscible organic solvent for the compound, water and a compound of a heavy metal capable of forming phthalocyanines; the latter may be omitted if the isoindolenine has a heavy metal attached to its nitrogen atom. Instead of heavy metal compounds the isoindolenines may be applied in the form of their alkali or alkaline earth metal derivatives or as salts with acids.  Particular isoindolenines that may be used are those described in Specifications 698,049 and 698,070, [Group IV (b)].  Thus the groups attached to the nitrogen atoms may be methyl, ethyl, propyl, butyl, pentyl, cyclohexyl, phenyl, naphthyl, anthraquinonyl, oxyethyl, cyclohexyloxypropyl, methoxyphenyl, chlorophenyl, nitrophenyl, carbethoxyphenyl, sulphonamidophenyl, aminophenyl or hydroxyphenyl.  The isoindolenine ring may have condensed aromatic or heterocyclic nuclei and may be substituted with methyl, ethyl, propyl, butyl, cyclohexyl, substituted cyclohexyl, phenyl, naphthyl, pyridyl, bromine, chlorine, sulphonic acid, carboxyl, methoxy, ethoxy, butoxy, cyclohexoxy, phenoxy, methylthio, ethylthio, phenylthio or arylsulphonyl.  The compounds may exist in different tautomeric forms, and may contain an additional molecule of alkanol.  Reducing agents are preferably included when the compounds are applied to the fibre; these may be any compounds capable of yielding two equivalents of hydrogen, e.g. mono- and polyhydric alcohols, sugars, formic acid and derivatives, hydroxyacids and their esters, sulphinic acids, aminohydroxy compounds, inorganic compounds with a metal in a lower valency state, hydrosulphites, bisulphites, aldehydes and ketones and their bisulphite compounds, inorganic sulphides, hydrazine, semicarbazide and hydroxylamine.  Suitable compounds are mentioned.  When metal salts (preferably halides or carboxylates) are used separately they may be applied to the fibre before, with, or after the isoindolenines.  When a metal derivative of the isoindolenine is used this may be formed in situ from an o-arylene dinitrile.  Suitable metals are copper, cobalt, nickel, iron, magnesium, zinc, tin, lead, aluminium, chromium and titanium.  Suitable organic solvents for the isoindolenines are formamide, dimethylformamide, pyridine, glycerol and glycol. Fixation is aided by the presence of ammonia or an amine, especially an alkanolamine.  Development is brought about by heat, e.g. steaming with or without acidic vapours.  The materials may be applied by dyeing, padding or printing, in the last-named case with the usual thickeners; fibres that may be treated are cotton, wool, silk, regenerated cellulose, cellulose acetate, polyamides and other synthetic fibres and paper.  In some cases the shade is developed by means of dilute acids before soaping. Other dyestuffs may be present, particularly those also developed on the fibre, to give multi-colour shades.  Resist effects may be obtained by means of strong acids or alkalis or strong organic bases.  Examples show (1) printing (in conjunction with metallic salts) with methoxyimino - isoindolenine, ethoxy - imino - isoindolenine, oxyethylamino - oxyethylimino - isoindolenine, bimolecular methoxy - imino - isoindolenine, amino - imino - isoindolenine, amino - imino - phenylisoindolenine, copper compounds of amino - imino - isoindolenine (1 : 1, 1 : 2, 1 : 4 and 1 : 6), copper compounds of polymeric amino-imino-isoindolenines, amino-imino-azaisoindolenine, amino-imino-methylisoindolenine, amino - imino - n - butylisoindolenine, amino - imino - dichloroisoindolenine, amino - imino - phenylsulphonylisoindolenine, amino - imino - methoxyisoindolenine, amino - imino - ethoxyisoindolenine, amino - imino - phenoxyisoindolenine, amino - imino - benzisoindolenine, amino - imino - diphenylisoindolenine, imino - amino - tetrahydroisoindolenine and cobalt compounds of polymeric imino-isoindolenines; (2) dyeing with a solution of amino-imino-isoindolenine and copper chloride; (3) padding with amino-imino-isoindolenine (and various of its substitution products as above) and copper salts; white resists may be applied before development of the colour; (4) printing with the copper derivatives of amino-imino-isoindolenine and alkoxy-imino-isoindolenine and the nickel derivative of amino-imino-isoindolenine formed in situ from phthalonitrile; (5) printing with an amino-imino-isoindolenine and the leuco sulphuric ester of dibromanthanthrone (oxyamine salt); (6) printing with an amino-imino-isoindolenine, 2 : 3-oxynaphthoic o-anisidide and the diazoamino compound from diazotized 2 : 5-dichloraniline and 2-methylamino - 5 - sulphobenzoic acid; (7) printing with an amino-imino-isoindolenine, the dyestuff from oxalyl chloride and 1-amino-5-benzoylamino-anthraquinone, and a reducing agent, and after-treating with acid bichromate; (8) printing with an amino-imino-isoindolenine, N : N1 - bisacetoacetyl - o - tolidine and the diazoamino compound from 2-methoxy-5-chloraniline and sarcosine. It is also stated that phthalocyanines may be obtained from the isoindolenines in substance.  The Provisional Specification contains further examples of printing pastes and their application.