Patent GB-598475-A (GB)
Title: Hydrophilic colloid colour-formers and photographic elements containing the same
IPC: G03C7/327
Filed: 1945-03-23
Abstract: A colour-yielding element comprises a support bearing a light-sensitive silver halide emulsion layer and including a layer of a hydrophilic dye intermediate ether of a hydrolysed terminally unsaturated mono-olefine/vinyl ester interpolymer formed (a) by etherifying a hydrolysed mono-olefine/vinyl ester interpolymer with a dye intermediate containing a reactive hydroxyl group attached to an aliphatic hydrocarbon group; (b) by reacting such an interpolymer with a dye intermediate containing a reactive hydroxyl group attached to an aliphatic hydrocarbon group and with an aldehyde or a compound reacting as an aldehyde; (c) by reacting such an interpolymer with chloracetic acid and converting the carboxyl groups in the product to amide groups by reacting with dye intermediates containing amino groups; or (d) by reducing a nitrobenzyl ether of such an interpolymer and reacting the product with a dye intermediate which is an acid chloride or with diketene.  The interpolymer may contain a molecular ratio of 0.2 to 0.02 of ethylene to one of vinyl acetate and at least 25 hydroxyl groups for every 100 chain atoms, and the final colloid dye intermediate may contain 1 to 30 dye intermediate ether groups for each 200 chain atoms.  The original dye intermediate may be a phenol, naphthol, or aromatic amine having a coupling position o or p to the aromatic hydroxyl or amino group, or a methylene compound in which a -CH2- group is activated by two unsaturated groups of the formula >CO, >CS, <FORM:0598475/IV/1> , connected either directly or through a conjugated system, e.g. (i) b -ketoacylamides such as benzoylacetanilide p-nitrobenzoylacetanilide, p-nitroacetoacetanilide, naphthoylacetanilide, p-acetoacetamidobenzoic acid, 2,5-dichloroacetoacetanilide, and furoylacetanilide; (ii) pyrazolones such as 1-p-carboxy-phenyl-3-methyl-5-pyrazolone, 1 - p - chlorophenyl - 3 - methyl - 5 - pyrazolone, 1-phenyl-3-carboxy-5-pyrazolone, and 1-m-sulphophenyl-3-methyl-5-pyrazolone; (iii) benzyl cyanides, e.g. p-nitrobenzyl cyanide; (iv) indoxyl and thioindoxyl; (v) homophthalimides such as N-phenylhomophthalimide, N-b -naphthylhomophthalimide, and N - dodecyl - homophthalimide; (vi) 2 : 4-dihydroxyquinoline; (vii) diketohydrindene; (viii) malonamides such as N : N1-diphenylmalonamide and ethyl - N - phenylmalonomate; (ix) phenacylpyridinium halides; (x) hydroxypyridines; (xi) cyanacetanilide; (xii) benzoylaceto-nitrile; and (xiii) ethyl cyanoacetate.  A group or atom readily eliminated (e.g. a sulphonic or carboxylic acid group or a halogen atom) may be in the coupling reactive position. The hydrolysed interpolymer and a dye intermediate may be linked by condensation with formaldehyde or formaldehyde-yielding material either by adding formaldehyde or formaldehyde-yielding material to a solution or suspension of the two components in the presence of a catalyst or by first condensing the formaldehyde with either component to form a methylol derivative and condensing this derivative with the other component.  The change in water solubility and permeability produced by the introduction of the dye intermediate groups may be balanced by balancing the dye intermediate ether groups and the hydroxy groups in the correct ratio, by the selection of an inter-polymer having a higher or lower viscosity or more or less olefine groups, by the introduction into the interpolymer of groups having the appropriate solubilising or insolubilising effect (e.g. acetal groups from butyraldehyde, benzaldehyde, phthaldehydic acid, benzaldehyde-o-sulphonic acid, or glyoxylic acid, ester groups from butyric, benzoic, phthalic, or succinic acid, or ether groups from hydroxy acids such as glycollic acid), which groups may be introduced before or after condensation of the dye intermediate with the interpolymer, or by the introduction into the dye intermediate of solubilising groups such as sulphonic or carboxylic acid groups.  The colour-forming nuclei need not be attached directly to the methylene ether group, since the formaldehyde may react with noncolour-forming groups (e.g. amide, mercapto, or aliphatic amino or hydroxyl) in the dye intermediate to form the methylol derivative.  The dye intermediate nuclei may be joined to the polymer chain through other ether groups such as -OCH2COX, -OCH2CH2X, -OCHRX, -OCR2X, -OCH2CH2SX, -OCH2C6H4X, -OCH2OCH2COX, -OCH2 CHOHCH2OX, -OCH2OCH2X, -OCH2CH2 NHX, or -OCH2CHOHCH2NHX, wherein R is hydrogen or a lower alkyl radical and X is a dye intermediate group. Formaldehyde-releasing compounds such as trioxane, hexamethylenetetramine, or methylene diacetate, compounds capable of forming methylol derivatives, e.g. chloromethyl ether, or dimethylol derivatives of amides or ureas such as dimethylolurea, dimethyloladipamide, dimethyloloxamide, or bis-methoxymethyl urea may be used for linking the dye intermediate to the interpolymer chain. The ethers may be used as emulsion binders or may be incorporated in gelatino-silver halide emulsions, or ether layers may be coated adjacent to gelatino-silver halide emulsion layers. The support for the light-sensitive layer may be paper, metal, glass, a transparent cellulose derivative, or a synthetic resin such as polyvinyl acetal or a superpolyamide.  Sensitizers, antifogging agents, preservatives, or hardeners may be added to the emulsion.  In example 1, paper and cellulose acetate film are coated with an emulsion formed by precipitating silver bromide and iodide in a solution of the ether formed from o-hydroxybenzyl alcohol and completely hydroysed ethylene/vinyl acetate interpolymer (which solution also contains sodium dodecylsulphate and ammonia), cooling, adding acetone to precipitate the binder and silver halides, washing, adding more interpolymer solution, ethyl alcohol, and aqueous potassium bromide solution, and ripening.  The material may be colour developed.  In example 2, cellulose nitrate film is coated with an emulsion formed by adding ammoniacal silver nitrate solution and then silver nitrate solution to a solution of the ether formed from phenol, formaldehyde, and hydrolysed ethylene/vinyl acetate interpolymer, which solution also contains ammonium bromide and potassium iodide, cooling, adding sodium sulphate solution, washing the precipitate, adding more interpolymer, ethyl alcohol, and aqueous potassium bromide, and ripening.  Further examples employ the ethers formed from hydrolysed ethylene/vinyl acetate interpolymer and (a) 2-hydroxy-3-methyl-5-chlorobenzyl alcohol; (b) o-phenylphenol and formaldehyde; (c) a -naphthol, formaldehyde, and o-sulphobenzaldehyde; (d) 1-phenyl-3-methyl-5-pyrazolone, formaldehyde, and o-sulphobenzaldehyde; (e) o-chloroacetoacetanilide and formaldehyde; (f) sodium acetoacetanilide and methyl chloromethyl ether; (g) N-diphenylacetoacetanilide and formaldehyde, and (h) 1-N-b -hydroxyethylaminonaphthalene-6-sulphonic acid and formaldehyde and the ether prepared by reacting p-nitrobenzyl chloride and hydrolysed ethylene/vinyl acetate interpolymer, reducing with hydrogen in presence of platinum oxide catalyst, and reacting with diketene. Specifications 545,443, 545,444, [both in Group XX], 569,646 and 598,477 are referred to.