DE1291624B - Process for producing color photographs using the reversal process - Google Patents

Description

1 2

The invention relates to a method for silver halide in the blue-sensitive emulsion position of color photographs after the reverse layer has been developed. Such an auxiliary developer solution, • Process in which a multi-layer color photo is such that it does not result in a stronger one graphic material with silver halide emulsion obscuring the undeveloped silver layers, the opposite of the various halides in the middle (purple) layer Rich in the spectrum are sensitized, reversal is caused, leads the development of the topmost however, layer usually does not finish when exposed and developed with color developing solutions that contain color couplers. not all of the silver halide grains develop there-

Color films for the reversal process have to be made possible by appropriately strong cozy at least three silver halide emulsion exposure to blue light during the reversal layers, which take place in relation to the various stages before the development of the yellow image across the spectrum are sensitized. In the can. Due to insufficient protection of the In most cases the top layer is sensitive to blue, the middle layer through the yellow filter layer is the layer below is sensitive to green, although often not possible, the top layer rend to completely expose the layer 15 closest to the wearer to blue light without is sensitive to red. After being exposed to one of them also some of the silver halide crystals colored object, the films will usually expose middle layer. This results initially in a black and white developer solution, the following disadvantages arise: For example, if the developed, with negative silver images in the emul reverse exposure of the blue-sensitive layer sion layers arise. Then the red-20 is not enough to fully expose it, sensitive emulsion layer is reversely exposed and this leads to the formation of magenta dyes in a color developer which has one in this layer, or it will be if sufficient a cyan dye-forming coupler exposes crystals of the middle emulsion layer and a silver halide developer of the type exposed, and results in color development of p-phenylenediamine, the oxidation of which there is a yellow dye. After all, often it is product with couplers forming a blue- difficult to find the right composition for one green image is able to react. Then find a developer who creates a yellow image, the blue-sensitive emulsion layer is reversed - which completely develops the top layer, exposed and developed in a color developer without causing undue fogging the yellow dye forming coupler 30 in the middle green sensitive emulsion layer contains, which leads to a yellow image in the layer. But it becomes a slight obfuscation forms is. Then the middle green sensitive induction yellow dye developer is used, Emulsion layer reversely exposed and with a so must for complete development of the top A color developer solution is developed that has one layer, often a black and white auxiliary developer Contains magenta dye forming coupler. The 35 are also used, with the same as the previous one Reverse exposure of the green-sensitive emul- called disadvantage occurs.

sion layer does not need to take place. Rather, the object of the invention is to provide a reversal process

Instead of this exposure, a veil can be developed using one of the reversal exposures Purple color developer can be used, which is omitted and the blue-sensitive layer completely The purple color is developed on the green-sensitive emulsion layer without the red image lying underneath generated. a yellow haze arises on the layer.

It is also known to have undeveloped silver halide. The subject invention proceeds from one

by treatment with so-called nucleating agents, processes for the production of color photographs for photographic developer solutions, the reverse process develops, in which an exposed bar to make in this way a reversal 45 photographic material that is opposite to exposure to avoid. Different areas of the visible spectrum are suitable as nucleating agents US Pat. No. 2,984,567 discloses silver halide emulsion metal borohydrides sensitized differently from alkali and in the Belgian patent layers, in a black and white developer writing 634 229 amine boranes, polyamine boranes, Phos- developed, then reverse exposure at least once, phinborane, arsine borane, stibine borane and borazole 5 ° with at least one color coupler containing described. In the known processes, developer baths are color-developed and, after the reversal, reversal films of the type described after exposure and color development with an aqueous one treatment of the blue-green image and the yellow solution containing a borohydride, Image treated with the nucleating agents and is characterized in that the material Reverse exposure of the green sensitive layer 55 after the reverse exposure and color development to avoid before color development. treated with a solution other than

When developing reversal color films in borohydride in addition in alkaline solutions as described above, it is difficult to dissolve hydroquinone containing a side chain with preventing color images of undesirable colors from having at least 4 carbon atoms, are formed in the emulsion layers. If, according to the method of the invention, for example, the exposure of the silver halide after the color development of the blue-sensitive emulsion layer does not take place correctly and before the color development, a magenta dye can subsequently form with the blue-sensitive emulsion layer in the layer, which actually only a yellow adjacent emulsion layer, such as image should form. As a result, it has been customary overall ⁶ 5 a middle green-sensitive emulsion layer with which to treat after the yellow image development of a conventional color film, treating the material with a black and white Hilfsent- a boron compound and a Hydrochinonverbinwickler which is still present dung containing solution. This solution

thus consists of an alkaline solution of a reverse bath with a hydroquinone derivative as Developer aid compound and a boron compound which is a nucleating agent for the silver halide. In the process of the present invention, it becomes a hydroquinone compound when developing the color film and the solution containing a borohydride after color development of the blue-sensitive ones Emulsion layer and applied before the last color development stage, the remaining, undeveloped silver halide generates nuclei in the blue-sensitive emulsion layer and reducing the silver halide to silver without developing the silver in the adjacent one green-sensitive emulsion layer takes place. However, by treating the films in the solution you can nuclei can also be generated in the silver halide of the green-sensitive emulsion layer without the To develop silver halide of the layer with the result that subsequently a common fogging or a non-fogging color developer containing a magenta dye forming coupler can be used. Accordingly, it is in the reverse exposure of the blue-sensitive emulsion layer not necessary to fully expose the silver halide, with the risk of exposure the neighboring green-sensitive layer, which is sensitive to blue light, is avoided.

Suitable borohydrides are, for example, boranes and borazines, such as alkali metal borohydrides, e.g. B. Potassium or sodium borohydrides, or aminoboranes of the following formula

ZBH ₃

wherein Z represents: ammonia, an amine, for example an aliphatic amine such as methylamine, Dimethylamine, trimethylamine, ethylamine, ethanolamine, diethylamine, triethylamine, diethanolamine, Propylamine, 3-hydroxypropylamine, dipropylamine, tripropylamine, primary butylamine, secondary Butylamine, tertiary butylamine, primary amylamine, secondary amylamine, and tertiary amylamine; also a polyamine, for example ethylenediamine, 2-aminoethylamine or an aromatic one Amine, for example aniline, a cyclic amine, for example pyridine, 2,6 - lutidine, 3,4 - lutidine, 2,4 - lutidine, 2 - ethylpyridine, 2,4 - diethylpyridine, 2,6 - diethylpyridine, 2,4 - diethylpyridine, 2 - propylpyridine, 4-propyl pyridine and 3-propyl pyridine.

Also suitable are boranes which are bound to a hydrazine or to a phosphine, e.g. B. an alkylphosphine, such as methylphosphine, dimethylphosphine, trimethylphosphine, ethylphosphine, diethylphosphine, Triethylphosphine, propylphosphine, dipropylphosphine, tripropylphosphine, primary butylphosphine, secondary butylphosphine; an arylphosphine, e.g. phenylphosphine; an arsine, for example an alkylarsine, such as methylarsine, dimethylarsine, Trimethylarsine, propylarsine, primary butylarsine, secondary butylarsine, amylarsine; a Arylarsine such as phenylarsine; a stibine, such as an alkylstibine, e.g. methylstibine, Dimethylstibine, trimethylstibine, ethylstibine, diethylstibine, Triethylstibine, propylstibine, primary butylstibine, secondary butylstibine, tertiary butylstibine; an arylstibine, for example a "phenylstibine.

Suitable borazines have the formula
R.

Η —Β
R "-N

TT

NO'

wherein R, R 'and R "each represent a hydrogen atom, a halogen atom, an alkyl group, preferably a lower alkyl group, or an alkoxy group, preferably a lower alkoxy group.
The following boron hydrides are preferred:

Alkali metal borohydrides

Potassium borohydride
Sodium borohydride

Amine boranes

Trimethylamine borane

Diethylamine borane

Triethylamine borane

Tert-butylamine borane

Pyridine borane
2,6-lutidine borane

Polyamine boranes

Ethylenediamine diborane
Hydrazine diborane

Phosphine borane
Dimethylphosphine borane

Arsine borane

Dimethylarsine borane
Stibine borane

Dimethylstibine borane
Borazine

Borazine

N, N ', N "-trimethylborazine
N, N ', N "-trimethoxyborazine

The preparation of these compounds is known. The production of aliphatic amine boranes is for example in the chemical reports, Vol. 93, pp. 928 to 938 and 1078 to 1083 (1960) described.

Phosphine boranes, arsine boranes and stibine boranes are described, for example, in US Pat. No. 2,999,864.
The borazines can be produced by condensation of diborane with the corresponding nitrogen compounds. For example, borazine can be produced by condensing diborane with ammonia. N, N ', N "-Trialkylborazines can be prepared by condensation of diborane with corresponding N-alkylamines. Finally, N, N'-dialkylborazines can be prepared by condensation of diborane with a mixture of ammonia and an N-alkylamine.

The hydroquinones required for the process according to the invention, which are in alkaline solution soluble and contain a chain with at least 4 carbon atoms, consist of the alkali-soluble Alkyl hydroquinones with preferably up to 20 carbon atoms in the alkyl group. Will higher molecular weight hydroquinones are used, it is useful if these solubilizing groups, such as, for example, sulfo and / or carboxyl groups, which have their solubility in alkaline solution raise. The suitable hydroquinones also include those which have a cyclic side chain Contain group, such as with the group

9. Sodium salt of 2- (sec-octadecyl) -5- (sulfot-butyl) -hydroquinone dihydrate,

OH

NaO ₃ SC ₄ H ₈

C ₁₈ H ₃₇ -SeC.

OH

10. Disodium salt of 2- [4- (3,5-disulfobenzamido)] phenethylhydroquinone dihydrate

CH ₇ CH, -

15 SO ₃ Na

OH

which occur in compounds 10 and 11, which are described in more detail below.

2,5-Dihydroxyacylophenones with 8 to 10 carbon atoms in the acyl group are particularly suitable, such as compounds 5, 6 and 7 given below. Suitable hydroquinones are for example:

1. t-butyl hydroquinone

2. n-Hexylhydroquinone

3. n-Octylhydroquinone

, 4. n-Nonylhydroquinone

5. 2,5-dihydroxy-n-octanophenone
OH

CONH

S 0, Na

OH

11.

Disodium salt of 5- [4- (3,5-disulfobenzamido)] - phenethyl-2-methylhydroquinone

SO ₃ Na

OH

C ₂ H ₄

SO, well

OH

(A-CO-C ₇ H ₁₅

OH

6. 2,5-dihydroxy-n-nonanophenone

OH

J-CO-C ₈ H ₁₇

OH

7. 2,5-dihydroxy-n-decanophenone

OH

CO - C ₉ H ₁₉

OH

8. Sodium salt of 2-n-octylhydroquinone-5-sulfonic acid

OH

NaO, S.

C ₈ H ₁₇

OH

The compounds mentioned by way of example have very good solubility in alkaline Solution and have the desired ability to, through photographic emulsion layers, such as gelatin-silver halide emulsion layers to diffuse. As a result the compounds cause the reduction of the silver halide to silver on a single emulsion layer is restricted, e.g. B. on the outer blue-sensitive emulsion layer of a conventional multilayer Color film.

While 1,4-dihydroxybenzenes are generally used for carrying out the process of the invention suitable, which have a side chain with at least 4 carbon atoms, are for example hydroquinones, like n-propylhydroquinone, not suitable,

because they tend to develop the green-sensitive emulsion layer when the remaining blue-sensitive silver halide of the blue-sensitive Layer is developed. Furthermore, they are not suitable for carrying out the method of the invention such hydroquinones as 2,5-di-t-butyl hydroquinone, η - decyl hydroquinone, lauryl hydroquinone, cyclohexyl hydroquinone and 2,5-dicyclohexylhydroquinone because they have too low a solubility. While 2,5-dihydroxyacylohydroquinones, such as the compounds 6, 7 and 8 described, e.g. B. 2,5-dihydroxynonanophenone, represent very suitable compounds, the homologous compound 2,5-dihydroxydodecanophenone is suitable not to carry out the method of the invention.

If the solutions used according to the invention are prepared, the phenones become the hydroquinones obviously reduced to the corresponding alcohols by the borohydride compounds.

For example, the groups —COCsHn, —COC ₇ Hi ₅ and —COCoHi _{9 of} these compounds ”become the groups

-CHC ₈ H ₁₇ ,

OH

- CHC ₇ Hi ₅
OH

IO

- CHC ₉ Hi «

OH

reduced.

The solutions containing a hydroquinone and a boron compound should be strongly alkaline and have a pH of at least 10. 0.05 to 10 g of the boron compound can be used per liter of solution and 0.05 to 5.0 g of the hydroquinone can be used. The processing time of the photographic Material with the alkaline solutions takes about 15 to 120 seconds. The alkaline Component of the solution used according to the invention can consist of a strongly alkaline organic or inorganic compound exist, such as an alkali metal hydroxide or a quaternary ammonium hydroxide. The solutions which are customary in photographic developer solutions can also be added used additives are incorporated.

The method of the invention is useful for processing photographic material with at least two silver halide emulsion layers, preferably gelatin silver halide emulsion layers, which are sensitive to different areas of the spectrum. Particularly suitable the method of the invention for developing a photographic material having a blue-sensitive emulsion layer, a green and a red sensitive emulsion layer. The solutions containing a borohydride and a hydroquinone can also be used in cases where a red- or green-sensitive emulsion layer the outermost layer forms the nucleation and reduction of the remaining silver halide to limit. Usually the nucleating and developing activity is the one Borohydride and a hydroquinone containing solutions on the outer silver halide emulsion layer limited, although germs are also present in an emulsion layer below the outer layer Action of the boron compound can be generated.

The method of the invention is particularly useful for photographic processing Material containing gelatin-silver halide emulsions which can be developed.

The following examples are intended to further illustrate the process of the invention.

example 1

A multilayer paint film was used, which consisted of a cellulose ester support, which in the following order red-, green- and blue-sensitive gelatin-silver bromoiodide emulsion layers with a yellow filter layer between the blue- and green-sensitive emulsion layers was arranged. After exposure, the film was in a black and white developer solution the following composition:

Sodium sulfite (anhydrous) 80.0 g

N-methyl-p-aminophenol sulfate .... 5.0 g

Hydroquinone 2.0 g

Sodium carbonate (monohydrate) ... 25.0 g

Sodium bromide 2.0 g

Potassium iodide (0.1% solution) 2.0 cc

Isopropylamine 6.0 g

Topped up with water to 11

pH 10.3

After rinsing the film, the red-sensitive emulsion layer of the film was subjected to a reverse exposure exposed to red light through the carrier, whereupon the film in a cyan developer the following composition was developed:

Sodium sulfite (anhydrous) 5.0 g

Color developer *) 0.55 g

Sodium carbonate (monohydrate) ... 15.00 g

Potassium bromide 0.25 g

Potassium iodide (0.1% solution) 2.00 cc

Color coupler **) 0.55 g

Sodium hydroxide 0.4 g

Topped up with water to 11

pH 10.0

*) 4-Amino-3-methyl-N, N-diethylaniline hydrochloride. **) 2,4-Dichloro-5- (p-toluenesulfonamido) -l-naphthol.

This development resulted in a subtractively colored cyan image in the red sensitive Emulsion layer generated.

After rinsing the film, the outer, blue-sensitive emulsion layer became incomplete exposed to blue light so that the underlying green-sensitive emulsion layer is not exposed became. This was followed by yellow development using a color developing solution of the above mentioned composition with the exception that ω-Benzoylacetanilid used as a coupler whereby a subtractively colored yellow image was produced in the layer.

The film was then placed in a 27 ° C bath of the following composition for 30 seconds treated, whereby the remaining silver halide of the blue-sensitive emulsion layer with seeds was provided and developed and wherein the silver halide of the green-sensitive emulsion layer germinated.

Water 800 ml

NaOH 3.0 g

KBH ₄ 0.10 g

Na ₂ SO ₃ 5.0 g

2,5-dihydroxy-n-nonanophenone .. 0.7 g made up to 11th with water

After washing the film, the film was developed in a color developing solution similar to the above with the exception that, as the magenta dye, F forming coupler 1 - ρ - nitrophenyl - 3 - methyl-5-pyrazolone was used.

The film was then first washed for 5 minutes to remove the silver

909 513/1951

Claims (1)

9 10 and then are sensitive to red or green in a silver layer for 2 minutes, Bleaching bath of the following composition, where a borohydride and a acts: hydroquinone-containing bath before the last dye . . .. <, "stage of development is applied. Natnumferricyamd 160 g _{5 The when carrying out the} method of the invention Natnumbromid Jt. G _d initially applied black and white developer Made up to II with water _{normally consists of a} rapid developer, The film was then immersed in a hydroquinone and p-N-methylaminophenol for 2 minutes contains a fixing bath of the following composition or a 3-pyrazolidone, treats: io The to carry out the method of the invention _XT . , . _{Ci 10r} . Suitable color developers are known. That Natnumhyposulnt 180 g method of the invention is not limited to the use Sodium sulfate y, ug _{d of a particular} color developer. Made up to 11 with water. Particularly suitable color developing agents Finally, the film was made of a primary aromatic amine for 5 minutes wash and then dried. with an additional substituent, d. H. additional In this way, positive cyan, Hch became the primary amino group that Purple and yellow images in the red, green and optionally substituted, amino group or obtained blue-sensitive emulsion layers. It can consist of a hydroxyl group. To the- it was found that the use of a borohydride 20-like color developer included the phenylene and a bath containing hydroquinone, the diamines and substituted derivatives of the phenylene winding of the purple dye in the blue diamine, the at least one primary amino group sensitive emulsion layer and the developer, such as the color developer development of the yellow dye in the green-sensitive compounds in the US patents Emulsion layer was effectively prevented. 25 2 548 574 and 2 566 271. Particularly are suitable color developing agents Example 2 also contains the aminophenols which contain at least one amino group. The color developer was repeated, but this time 0.5 g of 2,5-di-baths can contain the usual additives, hydroxy-n-nonanophenone and 0.2 g of tertiary butyl-30 _D. . _o .... amine borane used instead of KBH ₄ . There claims, equally good results were obtained, the first process for the production of true color dyes in the blue and green perceptions by the reverse process, in which the borrowed emulsion layer were produced. an exposed photographic material that 35 towards different areas of the visual Example 3 differently sensitized SiI- The procedure described in Example 1 was containing berhalide emulsion layers in one with the exception that 0.5 g of 2.5-Di black and white developer develops, then min- hydroxy-n-nonanophenone and 0.2 g dimethyl at least once reverse exposure, with at least amineborane were used in place of KBHi. 40 a developer bath containing a color coupler Equally good results were obtained, with color developed and after the reverse exposure the right dyes in the blue and green and color developing with an aqueous solution sensitive emulsion layers were developed. containing a borohydride is treated thereby marked that the Ma- B e i s ρ i e 1 4 45 material after reverse exposure and color development treated with a solution that In addition to the borohydride, the process described in Example 1 was also alkaline repeated with the exception that 0.5 g of 2,5-di solutions soluble hydroquinone, which has a side has hydroxy-n-nonanophenone and 0.2 g trimethyl chain with at least 4 carbon atoms, amineborane were used in place of KBHi. 5 ° contains. Equally good results were obtained, wherein 2. The method according to claim 1, thereby gedie correct dyes in the blue and green denotes that a color photographic three-sensitive Emulsion layers were formed. Layer material with the usual layer arrangement is used and after color development If the blue-sensitive layer contains the material with 1 5 55 the alkaline solution containing the borohydride and The procedure described in Example 1 was treated containing hydroquinone, repeated with the exception that 0.5 g of 2,5-di- 3. The method according to claim 2, characterized in that hydroxy-n-nonanophenone and 0.4 g of pyridine borane indicates that the reverse exposure were used in place of KBHi. There were ⁶⁰ blue-sensitive layers, the silver halide equally good results are obtained, the correct layer being incompletely exposed. Dyes in the blue- and green-sensitive 4. The method according to claim 2, characterized in that Emulsion layers were formed. indicates that the In the same way, other multilayer blue-sensitive layers can use the silver halide Color films with at least two differently sensitive ⁶ 5 green-sensitive layers were not exposed emulsion layers, of which at least is. an emulsion layer against blue light 5. The method according to claims 1 to 4, da- is sensitive and one or more emulsion characterized in that as a boron compound an alkali metal borohydride, a borazine, an aminoborane, a phosphinoborane, an arsinoborane or a stibinoborane is used. 6. Process according to Claims 1 to 5, characterized in that the hydroquinone t-butyl hydroquinone, n-octyl hydroquinone, n-nonyl hydroquinone or a 2,5-dihydroxyacylphe- non with 8 to 10 carbon atoms in the acyl group is used. 7. The method according to claim 6, characterized in that as 2,5-dihydroxyacylphenone, 2,5-dihydroxy-n-octanophenone, 2,5-dihydroxy-nonanophenone or 2,5-dihydroxy-n-decanophenone is used.