Patent GB-1375395-A (GB)
IPC: B41M5/136
Filed: 1971-10-21
Abstract: 1375395 Metallosiloxanes; metallosiloxanepolyphenol reaction products PILOT MANNEN-HITSU KK 21 Oct 1971 [24 Oct 1970 9 Feb 1971 30 June 1971 13 Sept 1971 (2) 20 Oct 1971] 48960/71 Headings C3T and C3S [Also in Divisions D2 and C4] A colourant for a recording ink is obtained by reaction of (I) a metallosiloxane or (R 3 SiO) p-x XR<SP>2</SP> x  wherein X represents a trivalent metal atom or metalloxy radical #M=O from a pentavalent metal, or a tetravalent metal atom or metalloxy radical # M = O from a hexavalent metal, R and R<SP>1</SP> represent an alkyl or aryl radical, OH or O 1/2  (or R<SP>1</SP> may be an acetylacetonate radical when X is a tetravalent metal), R<SP>2</SP> represents a monovalent anion or ligand or O 1/2 , m and n are 1-30, p is the valency of X, and x is 0, 1 or 2 with (II) a polyphenol which (E) is a 1 : 2-dihydroxybenzene optionally bearing in the 3-position a group R<SP>3</SP> which is an OH, alkyl, aryl or acyl radical, and/or elsewhere one or two groups R<SP>4</SP> which are each an alkyl, aryl, acyl, sulphonamide, amine sulphate, carbamide, amine carbonate, -SO 3 M, -COOY, -CH 2 Z, -NAB, or -NHCOX radical (M being Ca 1/2 , Ba 1/2 , Sr 1/2  or organo-ammonium; Y being H, alkyl, aryl, or organo-ammonium; Z being an N-morpholinyl, -pyridyl or -pyrrolyl radical; and A and B being H or alkyl or aryl radicals), or (F) is a 1 : 2- or 2 : 3-dihydroxynaphthalene optionally bearing in the remaining 1- or 3-position a group R<SP>3</SP> as above and/or in the 4-position and/or once or twice on the other ring a group R<SP>4</SP> as above, or (G) contains two dihydroxybenzene residues as in (E), but wherein R<SP>4</SP> may also be -CHO or -NO 2 , linked by the 3-positions by a group R<SP>5</SP> which is -O-, -SO 2 -, -N = N-, -(CH 2 ) x - (x is 1-10), or (X is H, alkyl or aryl), or (H) contains two dihydroxy-naphthalene residues as in (F), but wherein R<SP>4</SP> may also be -CHO or -NO 2 , linked via the remaining 1- or 3-positions by a group R<SP>5</SP> as above. There is preferably also present (III) an alkyl amine, a basic heterocyclic nitrogen compound, or an alkylene carbonate. For recording purposes the components (I) and (II) are dissolved separately in an "oily" medium and applied to separate surfaces, or one or both may be micro-encapsulated, and both may then be applied to a single surface; on contacting the two compositions and applying pressure, the coloured reaction product appears. In Examples 1-21 metallosiloxanes are prepared by condensation or cohydrolysis of BiCl 3 , FeCl 3 , iron alum, diphenyl dibutyl titanate, ammonium or sodium vanadate, VOCl 3 , V 2 O 5 , V(NEt 2 ) 4 , ammonium molybdate or sodium tungstate with chlorosilanes, silanols, Na silanolates, acetoxysilanes or a disiloxane; in these and later examples they are caused to react with a variety of polyphenols. Typically, in Example 2, polyvinyl alcohol microcapsules of a solution of a vanadosiloxane of unit formula -Ph 2 SiO-VO 1À5 -O-, with a UV absorber, trioctylamine and a polyisocyanate in dibutyl phthalate are applied in an aqueous mixture of a carboxy-SB rubber, gelatine, methylcellulose and H 3 PO 4  to a sheet; a second sheet is coated with a mixture of tricaprylammonium protocatechuate, citric acid, phthalic acid, thiourea, silica and ethoxycellulose; on contacting the two surfaces and applying pressure black markings are obtained.