Patent GB-776043-A (GB)
Title: Improvements in colour photographic material
IPC: G03C7/29
Filed: 1952-05-06
Abstract: A soluble non-diffusing dye-forming compound for use in colour photography comprises a polymeric radical (-A-)n wherein A is an organic radical and n is greater than 2, carrying a plurality of -SO2Y groups, wherein Y is a radical selected from: <FORM:0776043/IV(a)/1> -NHR11 and -OR, wherein R is a radical having a dye-forming functional group, R1 is hydrogen, alkyl or aryl and R11 is an aromatic radical having an available coupling position.  The functional group in R may be phenolic, enolic or aromatic amine, e.g. derived from acetoacetic acid, pyrazolone, naphtholsulphonic acid, napthylamine, diazoaminobenzene and phenylhydrazine.  Preferred <FORM:0776043/IV(a)/2> radicals are derived from benzoylacet-(p-amino) anilide, 1 - (p - aminophenyl) - 3 - methylpyrazolone, 1,2,3,4 - tetrahydro - 2,4 - dioxo6 - aminoquinoline, m - aminophenol, m - diethylaminophenyl - b  - (p - aminophenoxy)-ethyl ether, m - diethylaminophenyl - b -(methylamino) - ethyl ether, 1,5 - aminonaphthol, 1 - p - aminobenzoylamino - 5-naphthol, 1 - methylamino - and 1 - phenylamino - 5 - naphthols, 3 - diethylaminoaniline, N - (aminobenzoyl) - H - acid, m - aminophenylcyanoacetyl urea, 6 - aminocoumaranone, (1-hydroxy - 2 - naphthoyl) - ethylenediamine.  The radical -R.OH may be derived from 1,5-dihydroxy - naphthalene and p - acetoacetamido phenol and -NHR11 may be derived from 1-naphthylamine. (-A-)n is exemplified by polystyrene, styrene-maleic anhydride interpolymer, polyvinylnaphthalene, polyvinylcarbazole, natural rubber and dicarboxylic acid-diamine condensation products.  The products are formed by reacting compounds: <FORM:0776043/IV(a)/3> with the dye-formers.  These compounds may be formed by chlorosulphonation or by sulphonation followed by chlorination. Examples are chlorosulphonated polystyrene, styrenepolysulphone sulphonated and after treated with phosphorus pentachloride, rubber sulphonic acid (German Specification 582,565) treated with phosphorus pentachloride, a methyl methacrylate-ethylene sulphonic acid interpolymer treated with phosphorus pentachloride (U.S.A. Specification 2,348,705), the chloride of a sulphonated anisole-formaldehyde condensation product (German Specification 503,923), benzyl chloride simultaneously polymerized and chlorosulphonated (U.S.A. Specification 2,445,569), the chloride of an ethylenediamine-sulphosuccinic acid condensate (U.S.A. Specification 2,252,401), chlorosulphonated dimethoxydinaphthylhydro-rubber, chlorosulphonated adipic acid-m-phenylenediamine condensate, the products obtained by treating the sodium sulphonate of a trimethylene bromide-1,1-hydroquinone condensate with phosphorus pentachloride, by treating a saponified styrene-ethyl vinylsulphonate copolymer with phosphorus pentachloride or with excess of chlorosulphonic acid or by treating the above copolymer with chlorosulphonic acid, reacting with an amine and saponifying. In examples: (1) polystyrene dissolved in ethylene chloride is treated with chlorosulphonic acid and the precipitated sulphochloride purified by dissolving in acetone and precipitating with benzene.  The sulphochloride of (1) is reacted in acetone with (2) N - (m - aminobenzenesulpho) - 1,5 - aminonaphthol or 1,5-aminonaphthol and pyridine and the products coupled with diazotized 4-nitro - 1 - naphthylamine - 6 - sulphonic acid yield azo dyes which are cyan above pH 7; (3) N,N - dimethyl - m - phenylenediamine and N,N - dimethyl - N1 - p - aminobenzoyl - m-phenylenediamine and coupled with diazotized 2 - nitraniline - 4 - sulphonic acid to yield azo dyes which are magenta at pH 8; (4) N-(m-aminophenyl) - 1,2,3,4 - tetrahydro - 2,4 - dioxoquinoline and coupled with diazotized 2-nitraniline - 4 - sulphonic acid to yield a yellow azo dye; (8) p-nitrophenol, the unreacted sulphochloride groups are hydrolysed and the product reduced with iron filings in acetic acid.  After diazotization it may be coupled with N-toluenesulpho-H-acid to form a magenta dye; or (9) it may be reacted with salicyl chloride which can be coupled with diazo compounds to form yellow dyes or with colour developers containing p-aminodiethylaniline to form cyan dyes; (10) free H-acid and cetyldimethylamine in methyl-isobutyl ketone to form a tan powder which, coupled with 4-nitro-2-sulphodiazobenzene yields a magenta dye and with 4-diazo-41-ethoxydiphenylamine yields a blue dye; (11) salicyl (m-aminoanilide) or 1-(p-aminophenyl)-5 - pyrazolone - 3 - carboxylic acid and pyridine in acetone which yields a cyan dye with p-aminodiethylaniline; (12) 1-naphthylamine, hydrolysed and coupled with 2-nitro-2-sulphodiazobenzene to form a dye which is purple in alkali and yellow in acid, or with the oxidation product of p-aminodiethylaniline to form a blue dye.  In Example (6) a styrene-diethylmaleate copolymer is chlorosulphonated as in (1) and reacted with 1 - (p - aminobenzoylamino - 5-naphthol, N,N - dimethyl - m - phenylenediamine, N,N - dimethyl - N1 - p - aminobenzoylm - phenylenediamine, m - diethylaminophenylb  - (p - aminophenoxy) ethyl ether or 1,2,3,4-tetrahydro - 2,2 - dioxo - 6 - aminoquinoline to form compounds which react with diazo compounds to form azo dyes; or with 1,5-aminonaphthol which may be coupled with diazo compounds as in (2). Specification 776,044 also is referred to.