Patent GB-1086331-A (GB)
Title: Method of hardening photographic layers
Inventor: BURNESS DONALD MACARTHUR
IPC: C08G59/28
Filed: 1962-12-12
Abstract: Compositions suitable for providing hardened coatings on substrates comprise an aqueous solution of a film-forming linear polymer or polymer salt having in the molecule extralinear amino and/or carboxyl groups and, as a hardening agent, a quaternary ammonium salt having one or more quaternary ammonium groups and at least two glycidyl groups, each of which is bonded to a quaternary ammonium nitrogen atom.  Hardening of the polymer coating occurs gradually at room temperature; the process can be accelerated by heating.  The quaternary salt may be aliphatic, cycloaliphatic or aromatic and may be polymeric; the quaternary ammonium nitrogen atom can form part of a ring. Preferred quaternary ammonium salts have a perchlorate or sulphonate anion but other anions such as chloride, sulphate and phosphate are also suitable.  Various film-forming polymers are disclosed, the examples illustrating the hardening of gelatin, ethyl acrylate-acrylic acid copolymer, and a salt of a carboxy esterlactone of a maleic acid/vinyl carboxylate copolymer (of the type described in Specification 942,188); in some cases the polymer is incorporated in a photographic-type silver halide emulsion.  The preparation is described of the polymeric quaternary ammonium salt having the formula <FORM:1086331/C3/1> wherein 1,4 - bis - (methanesulphonoxy) - 2 - butyne and 1,4-bis-(2,3-epoxypropyl) piperazine are reacted in acetonitrile, firstly at 25-30 DEG  C. and then under reflux.ALSO:Quaternary salts having one or two quaternary ammonium groups and at least two glycidyl groups each of which is attached to a quaternary ammonium nitrogen atom are prepared by the various methods outlined below.  The salts are used for hardening water-soluble polymers (see Division C3).  Bis (2,3-epoxypropyl) methyl n-propyl ammonium p-toluenesulphonate is prepared by reacting epichlorohydrin with n-propylamine in the presence of water, treating the product with aqueous sodium hydroxide and then reacting the tertiary amine obtained with methyl p-toluenesulphonate.  Similar preparations are carried out wherein the propylamine reactant is replaced by (i) methylamine, (ii) piperazine and (iii) ethylamine; where methylamine is used the sulphonate salt is further treated with sodium perchlorate to produce the corresponding quaternary ammonium perchlorate salt.  Pentamethylene-bis (2,3-epoxypropyl diethyl ammonium methane sulphonate) is prepared by reacting 3-diethylamino-1,2-epoxypropane with 1,5-dimethanesulphonoxy pentane in benzene. Similarly reaction between 1,4 - dimethanesulphonoxy-2-butyne and 3-dimethylamino-1,2-epoxypropane and a subsequent treatment with sodium perchlorate produces 2-butynylene-1,4-bis(2,3-epoxypropyl dimethyl ammonium perchlorate). N,N - bis (2,3 - epoxypropyl) - N - (p-methoxyphenyl)-N-methyl ammonium p-toluenesulphonate is prepared by converting N,N-bis (3 chloro-2-hydroxypropyl)-p-anisidine to N,N-bis (2,3-epoxypropyl)-p-anisidine by treatment with KOH under reflux in ether, and then reacting the epoxy product with methyl p-toluenesulphonate.  2 - Butynylene - bis - [N,N - bis (2,3 - epoxypropyl)-N-methyl ammonium methane sulphonate] is prepared by reacting 1,4-bis (methanesulphonoxy)-2-butyne with N,N-bis (2,3-epoxypropyl) methyl amine in acetonitrile.  p - Xylylene - bis [N,N - bis (2,3 - epoxypropyl)-N-methyl ammonium perchlorate] is prepared by reacting p-xylylene dibromide with N,N-bis (2,3-epoxypropyl) methyl amine in acetonitrile and treating the product with sodium perchlorate.  Example 6 also describes the reaction of bis (2,3-epoxypropyl) ether methyl ammonium p-toluenesulphonate with sodium tetraphenyl boride in the presence of water, thereby converting the quaternary ammonium toluenesulphonate salt to the corresponding tetraphenyl boride salt.