Patent GB-471979-A (GB)
Title: Process for the manufacture and use of liquid self-hardening glazes derived from synthetic resins
IPC: F24D17/00
Filed: 1936-03-16
Abstract: Non-discolouring self-hardening glazes are prepared by mixing solutions of hardenable synthetic resins with solutions of hardening agents and with hydroxylamine or hydrazine or their organic derivatives, or organic nitriles, isonitriles, cyanides, or dicyanides.  The hardening agents may be those known per se, e.g. alkyl sulphates or acid chlorides, and/or hydroxylamine organic or inorganic salts, halogenated ethers such as CHCl2.CHCl.O.C2H5 and CH2Cl.CHCl.O.C2H5, di-and tri-halogenated aromatic hydrocarbons or dinitro-compounds, or aromatic di- and tri-nitro-compounds.  The hardening agent and additional substances may be added to an otherwise ready glaze at the time of use, in quantity not exceeding 5 per cent.  There may also be added phthalates; acid-, chlorine-, and light-fast dyes such as Sudan brown, pure blue, fast spirit blue; or acid- and alkali-fast pigments.  The glazes may be applied to woods, papers, and the like, bricks, plaster, or undercoatings of chlorinated rubber, alkali-stable polyacrylic or polyvinyl esters, e.g. polymethyl acrylate, the undercoatings being, e.g. on metal, porcelain, glass, and lime-containing surfaces.  They may also be employed for impregnation, e.g. of wood, paper, porous stone, to give hard objects, e.g. relief maps by hot-pressing.  In examples a solution in butanol, butyl acetate, and ethanol or ethyl acetoacetate is prepared of a waterclear phenol-formaldehyde resin, blown castor oil, diamylphthalate, benzonitrile and hydrazine or benzylhydrazine. At the time of use there is further added (1) alcoholic dimethyl sulphate, diethyl sulphate or an arylsulphate, e.g. benzene sulphoxide; (2) alcoholic hydroxylamine hydrochloride, nitrate, or sulphate or hydrazine chloride, nitrate, or sulphate and a nitrile, e.g. ethylene cyanhydrin, ethylene cyanide (NC.CH2.CH2.CN) or an aryl cyanide such as benzyl cyanide; (3) a halogenated ether, e.g. trichloroether (CHCl2.CHCl.O.C2H5), benzotrichloride, and benzonitrile with or without hydroxylamine or hydrazine.  The Specification as open to inspection under Sect. 91 specifies also: urea-aldehyde resins for preparing the glazes; as hardening agents aniline sulphate and hydrochloride, aryl sulphohalides such as C6H5.SO2Cl and CH3.C6H5.SO2Cl, esters or heavy metal salts of halogenated organic acids, e.g. trichloracetic acid ester or Zn salt, halogenated hydrocarbons, di- or tri-nitro-acid esters such as ethyl dinitrobenzoate or picrate, and aryl sulphates; and as additional substances hydrazobenzene, carbazide, urethanes as such or condensed with dibasic acid, e.g. oxalic, carbonic esters, e.g. CO(OC2H5)2, and "Amidoxime (Type R.C. <FORM:0471979/IV/1> "  It also includes examples in which a solution is prepared as in the above examples but with the substitution for benzonitrile of (4) alcoholic dimethyl or diethyl sulphate; (5) benzyl sulphochloride and benzyl or an aliphatic, e.g. acetyl or butyryl, chloride; (6) chlordinitrobenzene. The solution of example 4 is allowed to stand for 2 or 3 days, diluted with ethyl acetate or with acetone and cyclohexanone, and homogenized in a colloid mill; to that of example 5 is added a carbylamine boiling above 150 DEG  C. and hydrazo-benzene or -toluene with or without a carbonic ester (e.g. amyl) and hydrazine; to that of example (6) is added hydroxylamine sulphate solution with or without a nitrile and a carbonic acid ester.  This subject-matter does not appear in the Specification as accepted.ALSO:Non-discolouring self-hardening glazes are prepared by mixing solutions of hardenable synthetic resins with solutions of hardening agents and with hydroxylamine or hydrazine or their organic derivatives, or organic nitriles, isonitriles, cyanides, or dicyanides.  The glazes may be applied to undercoatings (e.g. on metal, porcelain, glass, or lime-containing surfaces) of chlorinated rubber.