DE725872C - Process for the production of halogen silver emulsion layers for single or multi-layer color photographic material - Google Patents

Description

Process for the production of halogen silver emulsion layers for color photographic single- or multilayer material It is known to use photographic emulsion layers for the production of colored images which contain dye formers which are developed with the oxidation products. certain developers give dye images. Farbstoftbildner which are suitable for this process are called in German Patents a53 335 and 257 16o. If photographic layers which contain these dye components are developed with developers which have a free amino group, for example p-phenylenediamine, p-dimethylaminoaniline, ethoxyp-dimethylaminoaniline, a dye image is obtained. When using multilayer film for the production of multicolor images, the problem arises that dye formers of one layer diffuse into other layers either when further layers are applied or when the multilayer material is developed. For the production of perfect multi-color images, however, it is absolutely necessary to fix the individual color components in their respective layers and to prevent any diffusion into adjacent layers. The substances known up to now do not sufficiently meet this requirement. It has now been found that the diffusion of the dye formers can be largely reduced or even completely suppressed if compounds are used as dye formers for the production of the photographic halogen silver emulsion layers which have an aliphatic carbon chain in the molecule with at least six, suitably significantly more than six, carbon atoms own. The carbon chains can themselves be substituted as desired, they can also be derived from aliphatic unsaturated hydrocarbons.

As a dye-forming agent, which can be found in soda or caustic solutions react with the oxidation products of the developer, for example: Phen oils, naphthols, aminonaphthols, anilines, naphthylamines. For example may be mentioned: resorcinol, in aminophenol, aminocresol, chloraminocresol, salicylic acid i-0, -3, 5-dicarboxylic acid, m-Nylenolcarbonsiiure, 2 Aininol> lienol-4-sulfonic acid, 2-Amino-6-methoxyplienol, i, 5-Dioxynaplithaliii, i-8-Dioxynaplitlialin, i, 2-Aminonaplitliol. 1, 5-aminonaphtliol, .1-Clilor-5-amino-a-naplithol, 2-oxynaplithoic acid, .1-chloro-i-oxy-2-naphthoic acid, 6-amino-i-oxy-2-nalilitlioic acid, 6-methoxy-i-oxy-2-naphtholioic acid, 2-amino-.l-sulfonic acid-a.-naphthol, 5-Amino-q.-sulpho acid-a-naphthiol, 2 - oxy - ¢ - aminodiphenylmethane, 6 - oxycinnamic acid. Furthermore, all bodies that have a reactive methylene group, e.g. E. acetoacetic ester, Cyanoacetate, Ben7ovIessigester, Benzoylacetonitrile, Hydrindenes, Pyrazolone, Cuinaranone, Oxythionaphthene and the like an aliphatic carbon chain with six or more carbon atoms takes place in a well-known `, 'ice. For example, an acid amide-like bond be prepared by converting the remainder into an amino group of the dye former an aliphatic acid with six or more carbon atoms introduces or by one acid group of the dye former with an aliphatic amine finite six and connects more carbon atoms. An O.xy group of the dye former can also be used Acvate with aliphatic acid chlorides with six or more carbon atoms. Or one svntlietisiert the dye formers by means of starting products that already contain an aliphatic chain with six or more carbon atoms.

The dye formers obtained in this way are added to the photographic emulsions at any point in time during their preparation. These substances adhere very firmly to the emulsion layers cast from them, and the more carbon atoms the aliphatic chain contains, the more the diffusivity of the compound is reduced. If a sufficiently large aliphatic radical is chosen, for example the stearic acid radical, any diffusion of the dye components when further layers are applied or when the finished multilayer photographic material is being developed can be completely prevented. Only with the aid of the present emulsion layers is it possible to completely prevent the diffusion of the dye formers, so that with the aid of these layers perfectly flawless multicolored photographic images can be obtained. Example ri Mo1. i- (p-Aniinoplienyl) -3-inetliyl-5-pyrazolone, either free or as the hydrochloride, is dissolved in dry pyridine and mixed with i mol. Stearic acid chloride added. To one hour warming on the water bath becomes the reaction product by pouring isolated in water. : 1 g i- (p-stearoylaniino- phenyl) - 3 - methyl - 5 - pyrazolone are used in 3 ccni 20% sodium hydroxide solution and about 50 ccni Dissolved in water and iooo g of a photographic added halogen silver emulsion. Example e i mol. i - (m-aminophenyl) - 3 - methyl - 5 - Pyrazolone is dissolved in dry pyridine and finitely 1 mol. Oleic acid chloride added. To one hour warming on the water bath the reaction product is obtained by inputting: 'le, i isolated in water. dg i- (ni-oleoylaniino- phenyl) -3-methyl-5-pyrazolone are in 3 ccni 20 per cent sodium hydroxide solution and 50 cc water solved and iooo g of a photographic Halosilver emulsion added. Example 3 i Mol. Decvlamin is in dry Pvr- i-dissolved and with i-mole. chloride added. After one hour of heating in the water bath, the reaction product isolated by pouring it in water. d. g decyl-i-oxy-2-naphthoylamine are in 5 ccin 20 per cent sodium hydroxide solution and about 50 ccni Dissolved methanol and iooo g of a photographic phischen halosilver inhalation added. Example .l i Mol. 5-Ainino-i-naplithol is in dry Dissolved pyridine and added to this solution i mol. of capryls; iureclilorid added. To one hour heating on your water bath the product is poured into water failed. .1 g of the 5-Cal rylamino- i-naphtliols "-erden in 5 ccm 20 ° / ,, i-, er \ atron- Lye dissolved in 5o ccin methanol and added 100 g of a halogen silver emulsion added. example p-Aniinobenzoylacetanilid is 1111t Lauryl- chloride to p-laurylaminobenzoylacetanilide implemented. 5 g of p-laurylaminobenzoylacetanilide will be in 2 cc. 50% sodium hydroxide solution in 5o cc Dissolved in methanol and the solution grams of a halogen silver emulsion added. Photographic layers cast with it give after development with p-diethyl amitioaniline a yellow color picture. Example 6 ni aniinobenzovlacetanilide-p'-carbonsätire finite stearic acid chloride becomes in-stearyl aminobenzoylacetanilide-p'-carboxylic acid unige- puts. 5 g of m-stearylaminobenzoylacetanilide-p'-carboxylic acid are dissolved in 5 ccm of 20% sodium hydroxide solution in 50 cc of methanol and added to one kilogram of a silver halide emulsion. Photographic layers cast therewith give a yellow color image after development with p-diethylaminoaniline.

Example ? One mole of phenylhydryzine-3-sulfonic acid is treated with one mole of p-nitrobenzoyl acetic ester condensed to 1- (3'-sulfophenyl) -3 - (4 "nitrophenyl) -5-pyrazolone and this according to a known method to i -. (3'-sulfophenyl) -3- (q. "- aminophenyl) -5-pyrazolone reduced. Furthermore, a stearic acid residue becomes in the amino group of this compound introduced.

io g i- (3'-sulfophenyl) -3- (4 "-stearylaminophenyl) -5-pyrazolone sodium salt are dissolved in 5o ccm of water and added to one kilogram of a silver halide emulsion. Photographic layers cast therewith give after development with p-diethylaminoaniline a bluish-tinted red color image.

Example 8 i - (m - Stearylaminophenyl) - 3 - methyl - 5 -pyrazolone from Example 3 are sulfurized in concentrated sulfuric acid with 15 % oleum. The sulfo group is probably meta to the acylamino group.

iog 1- (5'-sulfo-3'-stearylaminophenyl) -3-methyl-5-pyrazolone sodium salt .are dissolved in 5o cc of water and one kilogram of a silver halide emulsion added. Photographic layers cast with it are part of the development p-Diethylaminoaniline a yellow-tinged red color image.

Example g 1/10 mol. Monostearylphenylenediamine (F. P. 104 °) is used in. Pyridine with% o mol. I-oxynaphthoic acid chloride to i-N-stearinoyl-4-N- (i'-oxy-2'-naphthoyl) -phenylenediamine implemented. This reaction product is dissolved in concentrated sulfuric acid and sulfurized with oleum.

5 g of i-N-stearyl-4-N- (i'-oxy-2'-naphthoyl) -phenylenediaminesulfonic acid Sodium are dissolved in 5o cc of water and one kilogram of a silver halide emulsion added. Layers cast with this emulsion can be coated with dimethylaminoaniline develop into a blue picture.

Example io -. I 1 mole, 4'-aminophenyl-3-methyl-5-pyrazolone was dissolved in dry toluene and treated with i mol Cetyljodid and 5 hours it cooks.. The toluene is driven off with steam and the 4'-cetylamino-i-phenyl-3-methyl-5-pyrazolone is obtained from the residue by cooling and neutralizing in soda.

4 g of the substance obtained are mixed with 5 ccm of 20% strength sodium hydroxide solution dissolved in 50 cc of methanol and added to 100 g of a silver halide emulsion.

Example ii 'i mol. Dodecylaniline is dissolved in dry xylene and i mole of benzoyl acetic ester is added dropwise at the boiling point of xylene to the extent that how liberated alcohol is distilled off. When one mole of alcohol has been distilled off, the residue is freed from xylene with steam and the benzoyl acetic dodecyl anilide won.

4 g of the substance obtained are mixed with 5 ccm of 20% sodium hydroxide solution dissolved in 50 cc of methanol and added to 100 g of a silver halide emulsion.

For example, a multilayer film is made as follows: First, a silver halide emulsion layer is applied to a substrate, which is panchromatically sensitized and 10 g decyl-i-oxy-2-naphthoylamine on 1 kg of emulsion contains.

This is immediately followed by an emulsion layer, which is orthochromatic is sensitized and on i kg of emulsion io g i- (m-stearylaminophenyl) -3-methyl-5-pyrazolone contains.

Then follows an intermediate layer that has a yellow washable or Contains bleachable dye.

Finally, an unsensitized emulsion layer is applied, which contains 10 g of decanoylaminobenzoyl acetic acid epanisidide per 1 kg of emulsion.

The emulsion layers can also be arranged in other ways. Further filter layers can also be used.

Protection is not sought after for the manufacture of the dye formers.

Claims (1)

PATENT CLAIMS: i. Process for the preparation of halogen silver emulsion layers for color photographic single or multi-layer material, - characterized by that dye formers are added to the emulsion at any point in time, which has a non-ionically bonded aliphatic, optionally unsaturated carbon chain, which can be substituted with at least six, suitably much more than contain six carbon atoms. z. `` experienced according to claim i, characterized in that the emulsion in any. Time of dye former added «earth whose amino group has an aliphatic acid residue with at least contains six, suitably substantially more than six, carbon atoms. 3. Procedure according to claim r, characterized in that the emulsion at any time Color formers are added, the acid group of which has an aliphatic amino radical contains at least six, suitably significantly more than six carbon atoms.