Patent GB-585372-A (GB)
Title: Improvements in or relating to photographic materials
IPC: G03C1/83
Filed: 1944-09-05
Abstract: 585,372. Photographic materials. EDWARDS, H. D. Sept. 5, 1944, Nos. 16893/44 and 12176/45. [Class 98 (ii)] Photographic material comprises at least one light-sensitive layer and a layer comprising a dye which is either a salt formed between a dye base and a synthetic anion-active compound containing at least one acid group or a salt formed between an acid dye and a synthetic cation-active compound containing at least one basic group. The dye layer may be an antihalation or filter layer. The anionactive compound may be an anion-active wetting agent containing sulphonic or sulphuric acid groups, e.g. a long chain alkyl sulphonic acid, a sulphated higher fatty alcohol, e.g. a fatty alcohol sulphate in which the alkyl group contains at least 8 carbon atoms such as lauryl or oleyl hydrogen sulphate, a sulphated secondary alcohol containing at least 8 carbon atoms, an alkylated aromatic sulphonic acid such as an alkylbenzene, alkylnaphthalene, or an alkylated hydroxydiphenyl sulphonic acid, a long chain alkyl ester of sulphated succinic acid, or oleoylaminoethanesulphonic acid. Numerous commercial anion-active wetting agents are specified. The cation-active compound may be an alkyl-, aryl-, or aralkylsubstituted ammonium compound or a quaternary salt of a heterocyclic nitrogen compound such as dodecyl pyridinium sulphate, hexadecyl .pyridinium bromide, " Fixanol" (Registered Trade Mark), which is a quaternary ammonium compound, " Sapamine MS " (Registered Trade Mark), which is a diethyl aminoethyl long chain alkyl amide ester, or " Lissolamine A." The dyes may be obtained by reacting the dye bases with the free acids obtained by reacting the alkali metal or amine salts with strong acids, or mixing a dye salt (e.g. hydrochloride) with an anion-active salt. The dye bases may be prepared by treating solutions of the dye salts with alkali. An acid dye or salt thereof may be reacted with a cation-active agent, and the dye salt extracted with an organic solvent. The dyes may be used alone to form antihalation or filter layers, or a developer-permeable (gelatin) or developer-soluble (resins containing free acid or acid anhydride) colloid may be incorporated therein. The colloid may contain free carboxylic or sulphonic acid groups and may be a natural or synthetic resin or derivative thereof, e.g. glycerol-phthalic acid resins containing free carboxyl groups, the commercial resins "Paralac" and "Abralac" (Registered Trade Marks), polyvinyl phthalates containing free carboxyl groups, polymerized alkyl methacrylate resins containing free carboxyl groups as described in Specifications 573,917 and 575,512, natural resin derivatives such as the mixed resin acids derived from tall oil, as described in Specification 540,382, derivatives of Yellow Gum Accroides as described in Specification 548,411, cellulose derivatives containing free carboxyl groups, e.g. cellulose glycollic acid, and film-forming acids, e.g. polyglucuronic and polymannuronic acids. Colloids not containing free acid groups, e.g: gelatin, agar-agar, and synthetic and natural resins, may be used in addition. Dyes of the diphenyl and triphenylmethane classes, e.g. polyamino diphenyl and triphenyl dyes such as triaminoaminodiphenylmethanes (Auramine and its acyl derivatives) and diamino- and triamino-triphenyl methanes (Malachite Green, Magenta and Methyl Violet 10B) may be used as basic dyes, and Tartrazine, Acid Green G, Acid Magenta and dyes such as 1-p-sulphophenyl-3-methyl-4-cinnamylidene-5-pyrazolone as described in Specification 584,609. An organic solvent solution of the dye salt may be stirred into a solution of the colloid. The antihalation layer may be on the opposite side of the support to the emulsion layer, or may be disposed between the emulsion layer and the support. Coloured colloid layers between the emulsion layer and the support or between emulsion layers may be formed wholly or in part from alkali-insoluble colloids such as gelatin. In example 1, an acetone solution of the free acid from "Calsolene" oil (Registered Trade Mark) is mixed with an acetone solution of Malachite Green, silvestic acid is added, arid the composition is used as an antihalation coating on the opposite side of a transparent support to a panchromatic emulsion. The dye salt may also be formed by adding "Calsolene" oil (Registered Trade Mark) to an aqueous solution of Malachite Green (the oxalate). In example 2, an antihalation layer is formed from the dye salt obtained from " Teepol X" (Registered Trade Mark), Malachite Green base, and hydrochloric acid, and alkali - soluble partially hydrolysed methyl methacrylate polymer. In example 3, acid and neutral dye salts are formed from the free acid from Aresklene 375 and Malachite Green, and an antihalation coating composition is made using either of the dye salts with either the mixed resin acids from tall oil or partially hydrolysed methyl methacrylate polymer in a mixture of methyl alcohol and acetone. In example 4, basic and neutral dye salts are obtained by adding " Teepol X " (Registered Trade Mark) solution: to a solution of Magenta base in hydrochloric acid, and antihalation coating solutions are made using methyl methacrylate polymer as in example 3, or the mixed resin acids from tall oil as in example 1. In example 5, the dye salt obtained by reacting the sodium salt of 1-psulphophenyl - 3 - methyl - 4 - cinnamylidene - 5 - pyrazolone and cetyltrimethylammonium bromide in aqueous solution is made into an antihalation coating solution with a suitable binder. In examples 6 and 7, the dye salts obtained by reacting Tartrazine and Fixanol " (Registered Trade Mark) in aqueous solution and by reacting Acid Green G and cetyltrimethylammonium bromide in aqueous solution are similarly employed. Filter layers may be similarly made by dispersing the dye salts in alkali -permeable but not alkali-soluble colloids, e.g. gelatin or polyvinyl alcohol. Specifications 428,158, 517,559, 550,028 and 555,642 also are referred to.