DE1772945A1 - Rapid stabilization process for color photographic materials - Google Patents

Description

PATENT ANWXLTE

DR. E. WIEGAND DIPL-ING. W. NIEAAANN DR. M. KOHLER DIPL-ING. C. GERNHARDT

MDNCHEN HAMBURG

TELEPHONE: 55547 «8000 MONCH EN 15, 25. July 1968

TELEGRAMS: KARPATENT NUSSBAUMSTRASSE 10

W. 13 790/68 13 / Never

Fuji Shashin Film Kabushiki Kaisha Kanagawa (Japan)

Rapid stabilization process for color photographic

materials

The invention relates to a rapid stabilization method for color photographic materials.

Recently there has been a demand for photographic mining Recordings increased in short access time. Rapid processing of black and white silver halide photographic materials have been thoroughly studied and used extensively. However, this is not a rapid treatment method for

the

Hmlogen silver emulsions with incorporated coupler for / recording of colors other than Polacolor (registered trademark of Internationa ^ Polaroid Co.) was put into practice.

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BATH ORIGINAL

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The use of halide silver emulsions with incorporated coupler is advantageous in recording the visual Original exposure spectrum. However, the current processing systems for color photographic printing require Materials in several stages including development of the exposed halogen silver, discontinuation of development, Bleaching the developed silver, removing the undeveloped halogen silver and washing to remove any remaining treatment chemicals to remove.

A process has now been found for the stabilization treatment of color emulsions containing couplers, which has an improved treatment speed and does not require a washing operation.

A stabilization method for color photographic materials is described in U.S. Patent 3,335,004. According to this procedure, a color photographic material comprising variously sensitized gelatin-halosilver emulsions which contain color formers which are capable of reacting with the oxidation product of a primary aromatic Amine developers capable of forming a dye are exposed to light in a primary aromatic amine developed as a developer containing developer bath, the development by passing the material through a

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Interrupt bath is stopped; then the material is bleach stabilized with a bath which is an inorganic alkaline Containing ferricyanide, an inorganic alkaline thiocyanate and an inorganic alkaline bichromate, and then it is combined with one containing an inorganic alkaline thiosulfate and an inorganic alkaline disulfite Bath stabilized. "

However, the treatment method described above has the following disadvantages.

(1) Since an inorganic alkaline perricyanide is a strong oxidizing agent, it decomposes the solvent for the silver halide, for example an inorganic alkaline thiocyanate, which increases the durability and the useful life the bleach-stabilization solution can be significantly reduced.

(2) After described in US Pat. No. 3,335,004 i These processes require a further stabilization step after the bleach stabilization treatment, whereby the Number of treatment levels is increased.

(j3) As an inorganic alkaline thiocyanate as Solvent (stabilizer) for silver halide used in a light stabilization bath is shown light-resistant silver thiocyanate complex in the stabilized ' Copy effortlessly to a photosensitive silver thiocyanate

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Salt decomposes in contact with water and therefore through active radiation contaminates.

There has now been improved photographic technology Stabilization process found in which the Adhering disadvantages to the method described above can be avoided.

It is an object of the invention to provide an improved high speed process for color photographic materials. Another object of the invention is to provide an improved stabilization method for color photographic printing Materials, the service life of the treatment bath and the durability / treated copies are good.

According to the invention there is provided a rapid stabilization process for silver halide color photographic materials created, whereby nan an exposed color photographic material, the differently sensitized gelatin-halogen ■ Includes silver emulsions containing color formers with the oxidation product of a developer from a primary aromatic amine can react into one developing bath containing this developer and then in a bath containing an anion of Elsen (III) mono hydrogenäthylendiamln-Ν, Ν, Ν ¹ , N'-tetraacetate and ammonium

contains bleach thiosulphate, stabilized.

The developer bath used according to the invention contains a primary aromatic amine as the developer

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p-phenylenediamine type in which two hydrogen atoms on an amine group are substituted by lower alkyl groups. For example, N-ethyl-N-β-hydroxyethyl-p-phenylenediamine, N, N-diethyl-2-methyl-p-phenylenediamine and N-ethyl-N- (methanesulfonamidoethyl) -3-diethyl-4-aminoaniline can be used. The developer bath can contain hydroxylamine as an antioxidant. The developer solution may contain ammonium carbonate * (or an alkali metal carbonate, eg sodium carbonate) and ammonium iodide (or an alkali metal iodide, eg potassium iodide).

If desired, or if beneficial results are expected, an interrupter bath, usually is used in ordinary photographic processing in the method according to the invention for Application. The interrupt bath generally contains acetic acid and an alkali acetate. An alkali bisulfite can can also be used in the bathroom.

The bleaching stabilization bath can oxidize developed silver and converts the oxidized silver and undeveloped halogenated silver into a light-stable silver complex and at the same time converts the leuco dye (the intermediate product of the coupling reaction of color developing agent and color former) into the colored form. The lead stabilization bath contains an anion of iron (III) / monohydrofen-ethylenediaminetetraacetate as an oxidizing agent

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for the developed silver. An alkali salt of monohydrogenethylenediamine tetraacetate or a combination of ferric chloride and sodium ethylenediamine tetraacetate can form the above-mentioned anion in the solution. The amount of oxidizing agent in the solution is preferably 1 to 50 g per liter, it being noted that large concentrations of the oxidizing agent can contaminate the copies. ^A ls stabilizing agent is used an ammonium thiosulfate. The bleach stabilization bath can contain an alkali tosulfate as an accelerator for stabilization. The concentration of the stabilizing agent depends mainly on the amount of halogen silver that is applied to the carrier, it being preferably from 100 to 500 g / age. The bleach stabilization bath preferably has a pH value between 4 and 8. The thiosulfate is decomposed in the bleach stabilization bath at a pH value lower than 4. A bath with a pH higher than 8 produces fog and the copies formed in this way are then contaminated. A suitable combination of alkali hydrogen phosphate, alkali carbonate, alkali hydrogen sulfite and boric acid is used so that the bath has a buffering effect in the pH range given above. In addition to the components specified above, the bath can contain 0.3 to 10 g / liter

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of thiourea and potassium iodide as oxidative accelerators for the developed silver to be admitted.

Since in the method according to the invention an anion of iron (IIl) monohydrogenäthylendiamintetraacetat as Oxidizer for the developed silver in the bleach stabilization bath is used, the anion can stably together with a solvent for the silver halide be present and therefore the shelf life or useful life of the bleach stabilizing bath is essential longer than that of the bath, in which potassium ferricyanide is added as an oxidizing agent. The oxidizing power of iron (III) monohydrogenethylenediamine tetraacetate is weaker than that of potassium ferricyanide, but can be achieved through the use of a suitable oxidation accelerator the ability to oxidize can be maintained to the extent necessary.

When using the stabilizing bath according to the invention no further treatment is required, which is a special feature of the invention, moreover is used in the method according to the invention as a stabilizing agent ammonium thiosulfate, which as Fixing agent for conventional light-sensitive silver halide photographic materials is known. Ammonium thiosulfate can form a »silver complex, the opposite

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Dilution is stable and does not turn into a photosensitive silver salt on contact with water.

The rapid stabilization method according to the invention can not only improve the disadvantages inherent in the above-described known method achieve, but also gives copies with a better shelf life by rinsing or washing out the stabilized Copy for a short period of time due to the stability of the silver complex to dilution.

The invention is explained in more detail below with the aid of examples.

example 1

A blue-sensitive silver iodobromide emulsion which contained 3,5-dicarboxy-2- (4-stearoylamidbenzoyl) acetanilide as a yellow color former, a thoroughly sensitive silver chlorobromide emulsion which was used as a magenta color former 1- (J-SuIfo-4-phenoxyphenyl) -3- was applied to photographic baryta paper. stearoyl-5-pyrazolone contained *, and a red-sensitive chlorobromosilver emulsion which contained Nn-octadecyl-1-hydroxy-4-sulfo-2-naphthamide as a cyan color former, applied in the order given. This layer was coated with a gelatin coating. In preparing the above emulsions, each of the color formers was added to the corresponding emulsion in an alkaline aqueous solution.

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The thus prepared color photographic photosensitive copying paper was image-wise through a negative color film exposed and then developed for 60 seconds in a developer bath with the following composition at 40 ° C:

Solution A;

Ethylenediaminetetraacetic acid-2Na 2g Ä

Sodium carbonate (anhydrous) 84 g

Potassium bromide 1 g

Sodium sulfite 1 g

Water 600 ml

Solution B;

Hydroxylamine hydrochloride 2 &

N-ethyl-N-ß-hydroxyethyl-p-phenylenediamine-

sulfate 4.5 g

Water 100 ml

Immediately before use, the solution A with the solution B were mixed and the mixture was diluted with water to 1 liter like.

Thereafter, the thus developed color copying paper for 50 seconds was. Immersed in a stop bath having the following composition at 4O ⁰ G.

Glacial acetic acid 10 ml

Sodium acetate (anhydrous) 20 g

Water rest to 1 liter

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The color copier was then placed in a bleach stabilization bath Treated with the composition given below for 20 seconds at 40 ° C.

Sodium salt of ^ isene (III) -inonohydrogenethylenediamine tetraacetate 10 g

Sodium carbonate monohydrate 10 g

Boric acid 45 g

Ammonium thiosulfate 69.9 # -ig 358 ml

Thiourea 5 g

Water rest to 1 liter

The stabilized copy thus obtained was free from any residual silver image and was excellent Color image. The copy showed stability to actinic (active) radiation.

Example 2

A light-sensitive color copier paper was produced as described in Example 1 and was developed as in Example 1 and subjected to an interruption treatment and then ^{treated for 60 seconds at 40 °} C. in a bleach stabilization bath with the following composition:

Sodium salt of iron (III) monohydrogenethylenediamine tetraacetate 25 g

Ammonium thiosulphate 69.9 #ig I72 ml

Sodium thiosulfate 5 g

Potassium dihydrogen phosphate I5 g

Sodium sulfite 2 g

Potassium iodide 1 g

Water 009839/1703 rest to 1 liter

The stabilized copy thus obtained was excellent Color image and cleanly showed actinic radiation Persistence.

Example 3

A color copier paper prepared as in Example 1 was developed and subjected to breaker treatment, as described in Example 1, and then for 40 seconds at 35 ° C in a bleach-stabilizing bath with the treated with the following composition: Sodium salt of EisenClIlJ -monohydrogenäthylen-

diamine tetraacetate Rest on 2 g Ammonium thiosulfate 69.9 #ig 570 ml Sodium carbonate monohydrate 10 g Sodium bisulfite 45 g Thiourea -9 g water 1 liter

The stabilized copy thus obtained also showed excellent results as in Example 1.

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Claims (3)

Claims 1. Rapid stabilization process for color photographic materials, in which an exposed color photographic material contains differently sensitized gelatine-halogen ions, which contain color formers which can react with the oxidizing product of the developer, ^ in Ci) MvHi frin primary aromatic amine is developed as Entwicttlermittel containing color developer and the Entu'icklunr is unterbroclien by passing the developed material through (■ Ir stopped, characterized in that (i;:; ^ rr.in developed and the interrupter treatment u \: \ ■ ( \: - \; v .: ϊΊ ^: ίλ: j! lotx ^ grapliisclie Materiel r: t a bleaching act j lieic; '-,: n _f -; sb; id b-ehandelt, das eir: Anlor. "on iron ( IIl) -i "(. T; ohydr. \ · -.C: κ; ■ 1-y lonai ami nK, J-, 1» ', N ¹ -tx-tri-.aut> ^: .- ,,, , ",,. J ,,, .. ■! J.-j ₍ ,,:.;] F _a *, contains, ur.d -las material, ohr.e further Fiehrmdliinr dries. ™ 2nd ancestor; ·, nnrh claim. 1, thereby rekenr.2eich1.et, ar. ir, from :: v- phote _t; raphische material having a Bleichstabilis3erur. _t r - i :: ui that the ^ i.ior. of iron (III) -monohydronei: ätl: ylenediaminetetraacetate ir. a concentration. Contains 1 to Xc g / liter. 3. The method according to claim 1 or 2, characterized in that dai the iron (III) monohydrogenethyleridiamine tetraacetate anion before. an alkali salt of iron (III) monohydrogenäthylendianiiMetraacetut is derived or from a combination. "trichloride and sodium ethylenediamine tetraacetate 0Q9839 / 1703 is formed in the reading. BATH ORIGINAL