Patent GB-565317-A (GB)
Title: Improvements in or relating to colour photography
IPC: G03C7/30
Filed: 1943-10-29
Abstract: In a colour photographic process a dyeintermediate which is to be converted to an image in a quinone-imine or azo dye is a compound of the formula <FORM:0565317/IV/1> (the hydroxy group being alternatively in the 5 or 8 position) wherein R1 and R2 are the same or different and represent H, alkyl, cycloalkyl, or substituted alkyl groups, or together form part of a heterocyclic nucleus, or one of them together with the group X forms part of a monocyclic heterocyclic nucleus, wherein X is a hydrocarbon radical, a hydrocarbon radical containing an ether linkage or any other group which substantially prevents coupling in the 2-position, or is linked to one of R1 and R2, and wherein Y is H or a reactive or replaceable atom or radical which permits azo coupling in the 4-position.  The groups R1 and R2 may be methyl, ethyl, dodecyl, cyclohexyl, or benzyl groups, which may contain substituents, e.g. halogen atoms or ether, thioether, amide or sulphone groups.  Preferably, at least one of R1 and R2 contains more than 5 carbon atoms or is a recurring unit of a polymeric chain.  R1 and R2 must be selected so that the amino residue is still basic, and neither must be an acyl group.  X may be methyl, ethyl, methoxy, ethoxy, phenoxy, ethoxyethyl, carboxyl (and esters thereof), carbonamide, sulphonamide, nitro, chloro, chloromethyl, or b -hydroxyethyl.  Y may be H, Cl, Br, or a free sulphonic or carboxylic acid group. Preferably, there is a sulphonic or carboxylic acid group substituted in the radicals R1, R2, or X, or in the naphthalene nucleus, and preferably the compound has a molecular weight of at least 300.  A substituted alkyl group may be introduced into 1-amino-2-methyl-5-naphthol or its 6-sulphonic acid. Groups referred to are derivatives of stearic acid, phthalic acid, octadecylsulphonic acid, polyacrylic acid, and maleic anhydridevinyl compound heteropolymer.  With compounds in which the amino group contains at least one H atom, the amino group may be directly alkylated with a high molecular weight alkyl or substituted alkyl chloride or bromide of 8 to 18 carbon atoms, or an aliphatic haloacid or acetal, e.g. chloracetic acid or chloropropionaldehyde diethyl acetal, may be condensed therewith to form (1) a naphthylamino acid which can be condensed with a high molecular weight amine or (2) an acetal which can be converted by acetal interchange into a polyvinyl acetal by the method of Specification 535,341.  A 1 - acetamino - 2 - substituted - 5 - naphthol - acetate - 6 - sulphonic acid may be treated with chlorosulphonic acid or phosphorus pentachloride to produce the sulphonyl chloride which is then condensed with a high molecular weight or polyfunctional amine, and the acetate groups hydrolysed.  A 1-nitro-2-substituted-5-(or 8-) naphthol-acetate-3- (or 6- or 7-) carboxylic acid or 1-nitro-2-carboxy-5- (or 8-) naphthol acetate may be treated with PCI5 and the acid chloride formed reacted with a high molecular weight amine or polyamine, e.g. octylamine, octadecylamine, cyclohexylamine, or aminocellulose, and the nitro group reduced. The a -amino group may be alkylated.  Other groups that may be in the intermediate are halogen atoms and alkoxy, aryl, amide, sulphone and nitro groups.  Compounds that may be used in preparing the intermediates are 1 : 2 : 3 : 4-tetrahydro-7- (or 10-) hydroxy-7 : 8-benzoquinazoline, 1 : 2 : 3 : 4-tetrahydro-7 : 8-benzoquinoline-3 : 7- (or 10-) diol, 1 : 2-dihydro-5- (or 8-) hydroxy-b -naphthothiazole, 1 : 2-dihydro-7- (or 10-) hydroxy-4-naphth-(1 : 2-a )-m-oxazine, 1 : 2 : 3 : 4 : 8 : 9 : 10 : 11-octahydro-7- (or 12-) hydroxy-7 : 8-b -naphthoquinoline, 2 : 3-dihydro-7- (or 10-) hydroxy-4 : 1-a -naphthisoxazine, and 2 : 3-dihydro-6- (or 9-) hydroxy-a -naphthazole and in example 1, 1 : 2 : 3 : 4-tetrahydro - 7 : 8 - benzoquinoline - 3 : 7 - diol is reacted with ethylene-maleic anhydride heteropolymer, and the compound obtained is dissolved in sodium carbonate solution and added to gelatin solution and coated on a subbed cellulose acetate film base. A silver bromide emulsion is coated above the gelatin layer, and after exposure may be colour developed to produce a bright blue imate.  Dyes are also produced in the coating on treatment with diazotized 4-nitro-2-chloroaniline, diazotized 4-nitroaniline-2-sulphonic acid, and diazotized 2 : 4-dinitroaniline. In example 2, 1-amino-2-methyl-5-naphthol is reacted with p-acetamino phenoxyethyl bromide, followed by hydrolysis, sulphonation, and condensation with a styrenemaleic anhydride heteropolymer.  In example 3, an ethyl alcohol solution of 1 : 2 : 3 : 4 : 8 : 9 : 10 : 11 - octahydro - 7 - hydroxy-1 : 8-b -naphthoquinoline is added to a gelatino silver chlorobromide emulsion, which is then coated on a subbed cellulose acetate support.  The material may be colour developed, or processed to give an azo dye image.  In example 4, a colour developer for an exposed silver idobromide image comprises p-aminodiethylaniline hydrochloride, sodium carbonate, sodium sulphite and 1 : 2 : 3 : 4-tetrahydro-7 : 8-benzoquinoline-3 : 7-diol.  The silver salt images may also be developed with aromatic hydrazines to produce azo dye images.  Other organic colloids of use in preparing the materials comprise albumen, agar-agar, Irish moss, cellulose derivatives and synthetic resins (e.g. polyvinal acetals). The dye intermediates may be incorporated in a separate gelatin or other water-permeable colloid layer superimposed on a light-sensitive layer or spaced therefrom by means of a thin water-permeable colloid layer, or may be used in a colloid layer in materials free from light-sensitive layers or containing light-sensitive layers not in operative contact with the colloid layer.  The materials may have reducible silver salt images, e.g. silver chloride, bromide and chlorobromide (including latent images) and silver ferrocyanide, silver copper chloride, silver chromium chloride, and silver chromate images.  The dye intermediates may also be used in the production of coloured images in exposed bichromated gelatin. Specifications 2562/13, [Class 98 (ii)], 436,587; 458,400, 465,823, 478,345 and 479,838, [all in Group XX], 484,698, 487,769, [Group XX], 489,093, 491,958, 497,698, 512,542, 520,528, [Group XX], 539,494, 541,649, 545,443, [Group XX], 552,009, 554,302, 556,768, 546,858, [Group XX], 562,092, 569,646, and 14656/39 and 11153/43 as open to inspection under Sect. 91 of the Acts, also are referred to.  1,2-Dihydro - 7 - (or 10-) hydroxy - 4 - naphth-(1 : 2 : a )-m-oxazine is prepared by reacting 1-amino-5- (or 8-) naphthol with excess 1 : 1-dichlorodimethylether.  1 : 2 : 3 : 4 : 8 : 9 : 10 : 11-Octahydro-7- (or 12-) hydroxy-7 : 8 : b -naphthoquinoline is prepared by sulphonating 1 : 2 : 3 : 4 : 8 : 9 : 10 : 11-octahydro-7 : 8 : b -naphthoquinoline, separating the 7- and 12-sulphonic acid and fusing with alkate.  2 : 3 - Dihydro - 7 - (or 10-) hydroxy - 4 : 1 : a -naphthisoxazine is prepared by reducing 1 : 5-(or 1 : 8-) dinitro-2-b -chlorethoxynaphthalene diazotizing and hydrolysing.  2 : 3 - Dihydro - 6 - (or 9-) hydroxy - a  - naph - thazole is prepared by reacting 1-amino-5- (or 8-) naphthol with excess ethylene dibromide to give 1-b -bromoethylamino-5- (or 8-) naphthol, heating in n-butanol to effect ring closure and treating with sodium carbonate.  The Specification as open to inspection under Sect. 91 refers also to the use of compounds which are 1-amino-5- (or 8-) naphthols containing a substituent in the 2-position which is capable of p  substantially preventing azo coupling in the 2-position and in which the 4-position is available for azo-coupling and to the use of the compounds 4- (or 1-) hydroxy-7 : 8 : 9 : 10-tetrahydrobenzo - (g) - cyclopent - (b) - indole and 1 : 2-dihydro-5- (or 8-) hydroxy-b -naphthoxazole.  This subject-matter does not appear in the Specification as accepted.