DE2009693B2 - Photographic reversal process - Google Patents

Description

which has a particularly negative impact on the quality of the color rendering, especially when it comes to color development Even tin (II> salts) cannot be used in alkaline developer solutions be incorporated, as they immediately form an insoluble precipitate, so that the desired Development nucleation does not occur

However, these difficulties are avoided when certain Zhm (II) organophosphorus chelates are used as development nucleators be used.

The invention now relates to a photographic reversal process in which a photographic recording material exposed imagewise with at least one silver halide muLsion surface and with a black-and-white developer, the developed silver is faded and washed out, while in the production of color images the the last-mentioned process steps are omitted, in which the photographic recording material is subsequently used to generate development nuclei in the unexposed part of the emulsion layer is treated with an aqueous development nucleator solution and in which the development nuclei formed are then treated with a second developer solution to a black and white or color positive reversal image are developed, and is characterized in that the development nucleator solution a tin (II) organophosphorus chelate (hereinafter abbreviated referred to as "tin (II) chelate") contains this when a tin (TI) salt is reacted with a phosphonic acid one of the following general formulas is created

RN (CH ₂ PO ₃ M ₂ ),

in which M is a hydrogen atom or a water-soluble cation and R is an optionally substituted -rte alkyl group, an optionally substituted one Means aryl group, an aralkyl group, an alicyclic group or a heterocyclic radical, or

RR ₁ C (PO ₃ M ₄ ),

in which R is a hydrogen atom or an optionally substituted alkyl group, an optionally substituted aryl group, an aralkyl or heterocyclic or alicyclic group or a PO ₃ M ₂ group, R _{1 is} a hydrogen atom, a hydroxy or an optionally substituted alkyl group or a PO ₃ M ₂ group and M has the meanings given above.

When using the above tin (II) chelates are in a photographic Inverse processes of the type characterized above surprisingly good results with regard to the structure of the obtained black-and-white or color B "> s achieved. According to the invention as development nucleators The tin (II) chips used have developed nucleators compared to the previously known developmental nuclei the advantage that they are very strong against both acidic and alkaline solutions are stable and are therefore added to both acidic and alkaline pre-baths before the second development or in the alkaline developing solution used for the second development can. The process of the invention produces both black and white and colored positives Reversal images with excellent photographic reproduction and resolution. According to a A preferred embodiment of the invention is a development nucleator solution in the reversal photographic process used, which apart from the Zinniliyorganophosphor-chelai still a small one

S amount of an organic acid contains so that the solution has a pH of 2 to 7 and a sufficient Has buffer capacity. According to further embodiments of the invention, the development nucleating agent solution used contains in addition to the tin (II) organophosphorus chelate, alkali and a developer compound (preferably a primary aromatic amine) and optionally another reactive one Coupler which reacts with the oxidation product of the developing agent to form a dye reacted.

This gives images with a particularly high density and a particularly good resolution.

In the two general formulas given above, M preferably denotes an alkali metal atom,

ao z. B. a sodium or potassium atom, an ammonium, Pyridinium, triethanolammonium or triethylammonium group and R preferably represents an alkyl group having 1 to 4 carbon atoms, e.g. B. a methyl, ethyl, propyl, isopropyl or butyl group, a phenyl, o, m and p-tolyl, o and p-carboxyphenyl group and their water-soluble salts, such as the sodium and potassium salts, an aralkyl group having 7 to 9 carbon atoms, e.g. B. a benzyl - /? - phenethyl or o-acetamidobenzyl group, an alicyclic group having 5 to 6 carbon atoms, e.g. B. a cyclohexyl or cyclopentyl group, or a heterocyclylalkyl group, e.g. B. a pyrrolidylmethyl, Pyrrolidylbutyl, benzthiazolylmethyl or tetrahydroquinolylmethyl group. The substituent R can also, especially if it is an alkyl group, by a group such as. B.

a hydroxyl, PO ₃ M ₂ , CH ₂ PO ₃ M ₂ or N (CH ₂ PO ₃ M ₂ ) ₂ group.

Examples of compounds which can be used according to the invention of the general formulas given above are the following:

Ethylenediamine-N.N.N'.N'-tetramethylene phosphonic acid,

Nitrilo-N, N, N-trimethylene phosphonic acid, l ^ -Cyclohexanediamine-N.RN'.N'-tetramethylene phosphonic acid,

o-C'arboxyanilino-N.N-dimethylene phosphonic acid, Propylamino-NjN-dimethylene phosphonic acid, 4- (N-pyrrolidino) -butylamine-N, N-bis (methylenephosphonic acid),

l.B-diaminopropanol-N.N.N'.N'-tetramethylene phosphonic acid,

l ^ -propanediamine-N.N.N'.N'-tetramethylene phosphonic acid,

l, 6-hexanediamine-N, N, N ', N'-tetramethylene phosphonic acid,

o-Acetamidobenzylamino-tyN-dimethylene phosphonic acid,

o-toluidine-N.N-dimethylene phosphonic acid, 2-pyridylamino-N ', N'-dimethyIenphosphonic acid, l-hydroxyethylidene-l, l-diphosphonic acid,

Ethylidene-l.l.l-triphosphonic acid, l-hydroxypropylidene-l-diphosphonic acid, l-Hydroxy-Z-phenylethylidene-l-diphosphonic acid.

Tin (II) salts can be used to produce the development nuclei which can be used according to the invention

5 ' 6 y

for example water-soluble tin (II) halides, such as the corresponding positive dye image. According to the f

ZkuiTTn chloride, bromide and fluoride, tin (II) acetate, selective reverse exposure and color development j

Tin (ii) sulfate and tin (II) tartrate can be used. one layer becomes a second layer and then a j

In the reversal photographic process, the third layer of a selective reversal exposure \

Invention usable tin (II) organophosphorus 5 subjected and developed color. The silver pictures and |

chelate development nucleators are in detail the remaining silver halide with \

prepared by, for example, any of the above used to advantage, the last for the farbent- \

specified organophosphorus compounds, such as Ni-wrapped layer required reverse exposure to:

Avoid trilo-N.N.N-trimethylene phosphonic acid, dissolving in water. For this purpose, the develop-!

and then the respective stannous salt, e.g. B. Tin (II) - _lo lung nucleation either in a development nucleation I

chloride, added To prevent the precipitation from forming a solution with which the photographic recording i

soluble tin (IV) compounds in the solution by nungsraaterial after the color development of the second

Air oxidation or in the developer solution through layer and before the color development of the third

Oxidation of the tin ion in the chelate complex will be brought into contact, or in the layer

at least stoichiometric amounts and preferably ₁₅ development of the third layer used color development

incorporated an excess of about 10 mole percent of the organic wrapper solution.

phosphorus compound used to prepare a For the photographic reversal process of the strongly acidic solution having a pH of 2-7 invention, particularly suitable color photographic material and a sufficient buffer capacity is sufficient recording materials consist of a conventional acid, preferably an organic acid such as acetic ₂₀ substrate, for example a cellulose ester, acid added. A good buffer capacity is then achieved on paper, glass, polyester, polyvinyl acetate or polymer when the solution of the tin (II) chelate complex is carbonate, which is 0.1 to 5 molar with at least two acids. The acidic silver halide emulsion layer obtained in this way is provided, the solution can then, following the negative winding with respect to certain areas of the spectrum, be sensed as a stop bath for the generation of debilization. These emulsion layers contain winding nuclei in the unexposed part of the incorporated color-forming components or color silver halide. Subsequent couplers which react with the oxidation products of the final treatment of the precipitated silver halide photographic color developer to form an image with an alkaline developer solution produce the desired color images. A color drawing material preferably used in the method of the invention, depending on the photographic process used, a positive black-and-white or photographic recording material, in the case of a positive color reversal image, consists, for example, of a layer support and one thereon

When the tin-filled organophosphorus chelate developer-applied red-sensitized photographic

nucleating agent in an alkaline developer solution silver halide emulsion layer with a

is to be used, a solution of stoichiometric color couplers is used for the blue-green image (e.g.

metric quantities, preferably with a phenol coupler), a green-sensitized photo-

Shot of the organophosphorus compound of 10 molar graphical silver halide emulsion layer with a

Percent and then the tin (II) salt is incorporated coupler for the magenta image (e.g.

admitted. This solution then becomes the developer - a pyrazolone coupler and a blue sensitized one

solution added. Optionally, these amounts can include a photographic silver halide emulsion layer

of organophosphorus compound and tin (II) salt also a coupler for the yellow image (e.g. a one

in solid form in the order given in the coupling containing the open-chain ketomethylene group

alkalist.ien developer solution can be dissolved. With a ler). The photographic material can

other procedures must be expected, including the usual intermediate layers and filter layers,

that insoluble tin salt is formed in the solution. 45, for example, a blue-sensitized emulsion

The yellow filter layer adjoining the layer in the reversal photographic process to prevent

Invention used tin (II) -organophosphorus-che- the exposure of the red- or green-sensitized

The latex may differ in their ability to be contained in the non- emulsion layer by blue light

wrapped silver halide development nuclei to form color photographic recording materials

and thereby making it developable, from one another 50 of the type described above can be according to a

differentiate. It is therefore usually expedient to develop the less reversal processes

each individual tin (II) organophosphorus chelate in the step requires as the above-mentioned selective conversion

applied reverse photographic development of the multilayer color photographic

drive to check to determine which is the optimal phical recording material. According to the procedure

Delivers results. 55 ren of the invention is to develop emul-

In the case of the reverse development of multi-layer, multi-sions with incorporated coupler compounds only colored 'photographic recording materials required, the exposed color photographic supplies the first developer used a black and white negative drawing material to create a negative image. The multi-layered, multi-colored photographic silver image with a usual black-and-white de-phishing Recording materials that do not have inking 60 winders, then with an aqueous solution of a coupler in the silver halide emulsion layers de-tin (II) chelate development nucleator and thereafter are then given in a silver halide emulsion with a conventional color developer or layer a second selective reversal exposure if with a color developer to which one of the tin (II) is subjected, and then this silver chelate development nucleator has been added to treat halide emulsion layer with a color developer 65.

which contains a color coupler which can be used in the method of the invention When oxidized p-phenylenediamine developer has reacted, conventional couplers can be used. In color under Formation of the positive silver image developer formed in the example 4 below

The bleached emulsion layer was then carefully used Couplers are those in columns 3 to 5 of the folds, rinsed with water and kept for 3 minutes USA.-Patent 29 56 876 enumerated coupler 1 20 ° C redeveloped in the following solution:

to 64. In the same patent _{specification in column 5 N} »,, -„ _ „, _ Qm: _nn „ u. „_ i _c „ if „t η c

t »Li. I ^ ι / -ru · -π · j γ ·· j · j N-methyl-p-aminophenol sulfate .... 0.6 β

Couplers 65 to 77 listed are for the 50% anhydrous in sodium sulfite

Example 2 below explains the reversal development η «Ϊ"T; ^Wdssenrei ^>" ⁸

1 r i_ r L. u-i. n-iL u ι -j hydroquinone 20.0 e

Solution process for photographic silver halide potassium bromide 8 0g

emulsion layers suitable. Others to use sodium thiocyanate 6 0g

Couplers suitable in emulsions are, for example, sodium hydroxide 20 0e

j «ι * ΐΛ -im u '1. · u ix 1 AJ · j ¹⁰ tin (11) chloride solution *) 20.0 ml

and 24 74 294 couplers described. Others m the water ad 101

Couplers which can be used in emulsions are, for example

the couplers substituted by an acylamino group,

as known from US Pat. No. 24 23 730 _. _. . . ,

_s j _nc l _ι The emulsion was then with a usual Na-

The i "! ™ ^. ⁸ , ' ¹ } ^ ™" ^ ^fixes to form a

TinndD organophosphorus chelates have surprising high density black and white silver booths Advantages over the tin (II) aminopolycarbon emulsion layer.

acid chelates, for example tin (II) ethylene. °? ^The method described above can also chelate diamine tetraacetic acid. The organophosphorus ₂₀ ¹ J ¹ . ^de / ^Weis f carried out that after the chelate can namely be used within a wide range in the unexposed silver halide with concentration range. The ^container , ^{an acidic} tin (ll -chelate solution as “Ent-

The meaning of this concentration range lies in the solution that generates winding nuclei «according to the

that these chelates generate development nuclei at higher concentrations following Example 2 and

can be applied, which leads to the fact that the design ₂₅ ^{then this} f ^s . ^s ° treated silver halide with the

Solutions which generate winding ^nuclei do not describe a tin (II) chelate compound

are more resistant to air oxidation, as a larger containing developer solution is developed.

Excess can be present without causing excessive Example 2

Development of the silver halide takes place. For color reversal processes using

_{The poly- 3} o of _a zi _nn (H) _ _c helates have these higher concentrations

aminocarboxylic acid chelates tend to be part of the. .

Silver halide instead of developing only development ^was a multi-layered color film with einge-

to generate germs. While the polyaminocarbons were working! Coupler uses the red, green, and

acid-chelates only within a concentration-blue-limited gelatine-Süberhalideuls.ons-

range from 2 to 2500 mg tin (II) ions (based on ₃₅ layers on a layer substrate, whereby

can be applied to the tin) per liter, ^{zw 'sc} _K ^{hen the h} ^ f * ™ ^m ^ t * T * ^ ^{mu s! ons} -

the organophosphonic acid development seed layers can have a yellow filter layer. The emulsion

formers contained depending on the used photographic ^ "^ reactive methylene and

Recording material within a concentration phenol coupler compound which is associated with p-phenylenedi-

tion range from about 2 to about 7000 mg tin (II) - ₄ o amine developer compounds reacted _ under BiI-

ions per liter can be used. Another advantage ^dun | ^{of the} complementary colors

consists in making more accurate solutions of the sensitivity of the respective layers. The Füm

as larger amounts of the organo- was then in flat or rolled up form b.ldge-

phosphorus chelates to fill in the development ^{right colored and in} a delivery

germogenic solutions are used ₄₅ ^ ^a ' ^zer ' ^ m, as in the USA

can, which leads to a more even development ³⁰²⁵⁷⁷ J is described with staggered,

of the photographic recording materials. driven rollers that feed the film through a

. Row of bins and a drying chamber

Example 1 developed.

",." ,,,,,. _ _{,, - 0} pre-hardener (35 ° C, 150 seconds)

Black and white reversal process using so _{Dimethoxytetrahydrofura} n 4.3 g

of a Zmn (n) chelate, the sodium salt of p-toluenesulfinic acid, 0.5 g

A common gelatin silver bromoiodide emulsion sodium bisulfate 8.0 g

j layer was exposed in an image-appropriate manner and potassium bromide 2.31 g for 3 minutes

! long io of the following solution: J ₅ sodium acetate, anhydrous 92.0 g

N-methyl-p-aminophenol sulfate .... 2.0g sodium sulfate, anhydrous 91.0g

! Sodium Suffit, anhydrous 90.0 g "% ■« * Ρ «™ ^ ¹ » · · 29.2 g

Hydroquinone 8.0g ^WassCT · · · · ■ · · · · · V ' , V ¹ i ? -' ^h ° ^l _u

Sodium carbonate monohydrate 52.5 g sodium hydroxide or sulfuric acid to heat

Potassium bromide 5.0 g *> setting a pH value of 4 to 7

Water ad. 1.01 neutralizing solution (36.1 ° C, 75 seconds)

_,. · Ι i ^ τ- · r-i · · * sodium hydroxide 6.32 g

Then the developed film was carefully used with 10 5 ε

Rinsed with water and immersed in a bleaching sodium bromide for 2 minutes. '.'. '. ".'. '. '. '.'. '.'. '.'. '.'. '.'. '.'. 2 ^ 0 G

bleached solution of the following composition: _6j . Hydroxylamine sulfate 18.0 g

Potassium dichromate 9.4 g sodium sulfate, anhydrous 50.0 g

Sulfuric acid 12.0 ml boric anhydride 0.68 g

Water ad. 1.01 water ad. 1.01

First developer solution (37.8 ⁰ C, 150 seconds) of sodium tetraphosphate (Na ₆ P ₁ O ₁₃₎ 2.00 g ..

Dehydrated sodium sulfate 47.00 g

1-phenyl-3-pyrazolidone 0.35 g

Hydroquinone 5.50 g

Sodium carbonate monohydrate 32.00 g

Sodium bicarbonate 1.00 g

Boric anhydride 0.155 g

Sodium thiocyanate 1.38 g

Sodium bromide 1.30 g

Potassium iodide 0.013 g

Water ad. 1.01

First stop bath (37.8 ° C, 75 seconds)

Sodium acetate anhydrous 3.58 g

Glacial acetic acid 28.85 g

Water ad. 1.001

Wash at 32.2 ° C for 75 seconds

Color developing solution (43 ° C, 150 seconds)

Benzyl alcohol 4.71 g

100% ethylenediamine 3.0 g

Potassium iodide 0.047 g

Sodium bromide 0.80 g

Sodium hydroxide 2.05 g

Dehydrated sodium sulfite 7.60 g

Trisodium phosphate · 12 H ₂ O 36, Cl g

Citrazinic acid 1.35 g

4-Amino-N-ethyl-N- [yI-methanesulfonamidoethyl] -m-toluidine-

sesquisulfate monohydrate 10.50 g

30 ml of a 500 g of 1-hydroxy-ethylidene-l, l-diphosphonic acid, 100 g of SnCl ₂ · 2 H ₂ O and water to make up to 11 containing solution water ad. 1.01

When preparing the color developer solution described above, instead of the 30 ml solution of the previously prepared tin (II) chelate, g l-hydroxyethylidene-l, l-diphosphonic acid and then 3.0 g SnCl ₂ · 2 H ₂ O can be added and with Make up to 1 liter of water.

Second stop solution (43 ° C, 75 seconds)

Sodium bisulfite 10.0 g

Sodium acetate, anhydrous 13.0 g

Sodium Thiosulfate Anhydrous 31.86 g

Water ad. 1.01

Wash at 32.2 ° C, 75 seconds bleaching at 43 ⁰ C, 75 seconds

Fixing solution (43 ⁰ C, 75 seconds)

58% ammonium thiosulfate 163.0 ml

Sodium bisulfite, anhydrous 11.0 g

Boric acid 8.0 g

Glacial acetic acid 19.0 ml

Sodium hydroxide 8.0 g

Zirconium sulfate tetrahydrate 5.0 g

Water ad. 1.01

tir. .id'ung the pH to 4.0 wash at 32.2 ⁰ C, 75 seconds drying at 51.5 ° C for 150 seconds

When the color film was developed in the manner described above, the Tin (II) chelate development nuclei within the not exposed silver halide in the emulsion layers and this silver halide then wuide through the Color developer developed, which then coupled with the couplers in the individual emulsion layers Formation of dye images at the development centers.

In the procedure described above, the stannous chelate could be omitted from the color developing solution and instead of the first stop bath, the following solution could be used:

Solution that generates development nuclei

Sodium acetate, anhydrous 3.58 g

Organophosphorus chelating agent *) .. 1.5 g

Glacial acetic acid 28.85 g

SnCl ₂ -2 H ₂ O 0.3 g

Water ad. 1.01

*) The same chelating agent as in the above-described _ls NEN color developer solution or nitrilo-NNN-trimethylenephosphonic acid.

In this way, development nuclei were generated in the unexposed silver halide, and it was then developed by a color developing solution.

One using a stannous chelate in the color development processes described above The surprising and advantageous result achieved was that with the help of the solutions larger amounts of footage could be developed. This means that the mechanism of the process described above that which is present in the color developing solution during color development Tin (II) chelate or any other

an acidic prebath, the tin (II) chelate introduced before the color development is oxidized to the tin (IV) chelate that did not precipitate out of the developing solution. The tin (II) salt not bound in a chelate complex couldn’t take the place of the color developer solution

of the tin (II) chelate, otherwise the solution would immediately become dirty and unusable and the dirt could not be removed from the emulsion surface. Likewise enriched If in the acidic pre-bath instead of the tin (II) chelate, the dirt does not turn into a chelate complex Bound tin (II) salt was used, in the acid prebath gradually and deposited on the emulsion surface from which it could no longer be removed. Also, each was not in

Tin salt bound to a chelate complex, which is carried away from the acidic pre-bath onto the emulsion layers immediately precipitated as dirt in the subsequent alkaline developer solution.

B e i s ρ i e 1 3

Comparison of reversal processes using tin (II) chelate and borane development nuclei

educate
The procedure of Example 2 was repeated,

but this time the Zittn (II) chelate complex in the color developer solution by 0.073 g of terL-butylaminoborane was replaced. A good subtractively colored positive copy of the object was obtained. When comparing the image structure with that of the in

Example 2 using a tin (H) chelate however, it was found that the image obtained in Example 2 obtained using a tin (H) chelate Dye images less cyan contamination because

had red dyes, that is, the red dyes were much lighter. The blue colors of the color images obtained in Example 2 also contained few! yellow impurities, that is, the blue colors

11 '12

were also brighter. In addition, the yellow-white had good density and good contrast.

green colors and the image resolution occurred in the solutions or on the film itself

Example 2 was considerably better. after a considerable amount of footage

,,, _._.,. had gone through the solutions, no signs

5 of dirt on.

If desired, the above-described tin (II) chelate process can also be carried out in the manner indicated in Example 2 Magenta-red baths free of color couplers lying on top of one another are omitted and the following solution is incorporated into the magenta developer green and blue-sensitized gelatin-silver halide solution: contained emulsion layers. Between the blue and _{20 mI emer solution> 25 N} i _tr iio-N, NN-trigrunsensibilisierten emulsion layers was methylenephosphonic acid, 5.0 g of SnCl ₄ · H 2 O _a and a yellow filter layer. After an image-fair far _{water xam made up to 1 liter} . The film was exposed in a usual 15

Black and white developer solution with N-methyl in this case were not developed in the p-nminophenolsulfa'l and hydroquinone developed. Silver in the green-sensitive layer development washed, germinated again by the layer support from below, and it was immediately caused by the color exposed to red light and developed with a common, one developer solution.

Phenol couplers for forming a yellow-green dye-ao In general, the amount of color developing solution contained in the color image is developed. Sweeping method of the invention used tin (II) -After washing, the film was again exposed to the chelate development nucleator, as in the above emulsion page with blue light and is illustrated with the examples, so high that in the non-conventional, one reactive methylene developed silver halide to the time and coupler for forming a yellow dye image corresponds "5 temperature conditions of the process ausieichend holding color developer solution developed. After many developmental nuclei are formed. The amount of washing, the film was 1 minute and 13 seconds in the emulsion layer (or in the customer emulsion at 28.3 ⁰ C in the following magenta layers) originally present silver halide reversal treated: determines to some extent the concentration

30 of tin (II) ions in the solution. In general

Water 700.0 ml, however, determines the amount of

Na tetraphosphate 4.0 g winding step of the reverse process of the invention

Sodium hydroxide 3.0 g _{still present} silver halide the tin (II) -

Tin (II) chloride solution *) 60.0 ml ion concentration under the process conditions,

Water ad. 1.01 _{35 un ( each} amount of tin (II) ions is generally

*) The solution was prepared from 25 g of Nitrilo-N, N, N-tri- so large that it is sufficient to absorb the available silver

methylenephosphonic acid and 5.0 g SnCl, -2H ₂ O and with water halide to convert into development nuclei. if

made up to 1 liter. _{& htJ} . is used _{to yiel dev} i _c klungskeimbildner,

In the process, part of the silver halide in the unexposed silver halide was reduced, with

In the green-sensitive emulsion layer, an amount of silver halide with developing

development nuclei formed. After washing, germs were left for use in the itself

the film failed for 3 minutes and 33 seconds at 32.2 ° C subsequent color development step

Developed in the following developer solution below is sufficient.

Formation of a crimson image: In a black and white reversal process, the

_{w 8rin n.45} concentration of development nucleator not

^{ss r} · · V · ·; ·· :. , '"so critical. If the developmental nucleators, like

scnwereisaure z, in _the \ _{Beispid 2 er} i ert _äut, in an acidic pre-bath before

* ^υ "'" ⁸ Color development at about 26.7 to 51.5 ⁰ C about 30 to

.'_ ^{g is used} for about 90 seconds is sufficient for

⁸ 50

^ g SSAS

J5J8 _{liter solution d} . _h . an- producing 1 liter unit

3 Whether tin (II) chelate-Lösun _g suffice about 3.8 mg to about

koY 0 25 « ¹³ ' ³ S SnCl ₂ -2 H ₃ O. Although higher con-

anhydrous ". '. Y.'. '.'. '.'. soiog 55 centrations also a development germ imageBiii

Sodium hydroxide 0 32 g ^m *? » Süberhatograid, m an external emulsion

^ e ^ TricMorphenylVSp-nitro ^ ^cht ^ J « ¹ « * ^ei \ Jf des

^ e ^ TricMorphenylVS-p-nitro- ^ ^ J \ Jf.

a _a flino-2-pyrazoBn-5 ^ _B 1.60 g can be reduced, causing instant loss

Hexylenedykol 5 0 ml dye density occurs in this layer.

Sodium bromide 0 * 5 g ^ If, as shown in Examples 2 and 4, in one

0.1% potassium iodide ". '..".'. ". '.'.". ".". '. 7.5 ml »color developer used in the reverse process

Water ad 101 tin (II) chelate is used, so and with by

* sectional emulsion layers also amounts of voi

The film was then washed with a ferric about 2 to about 7000 mg per liter based on dai Cyanide solution bleached to put the silver back into the 65 tin, at a temperature of about 26.7 to 51.5 ° C To convert halide, then suitable as usual, if the development is so alkaline, bi: washed and finished with a sodium hyposulfite solution. In the black explained in Example 1 fixed. The dye images obtained with the film white process is also a lot of sth;

2 to about 7000 mg of tin (II) ions per liter of developer solution, based on the tin, are sufficient, and if the chelate is used in an acidic prebath prior to black and white development, it will suffice an amount from about 2 to about 7000 mg of stannous ions per liter of solution. The skilled person can easily the optimal concentrations of tin (II) ions in the solutions under the process conditions used for the single-layer or multilayer used in each case determine photographic recording materials. As mentioned above, the ligand component should of the chelate are present in an excess of, for example, about 10 mole percent.

The ZinnillJ chelate development nucleators of the The formula given above are, as given in Examples 1 and 2, in particular either in an acidic pre-bath or in a color developer solution to develop the incorporated color couplers, or, as described in Example 4, in one

acidic pre-bath or in a color developing solution used in selective color reversal processes, used as a development nucleator.

The color development described in the above examples can be performed using any of the known color developer compounds are carried out with the color-forming components or can couple the couplers. Particularly suitable color developing agents are the p-phenylenediamines and their substituted derivatives. Examples of preferably used color developing agents are the sulfonamide-substituted p-phenylenediamines known from US Pat. No. 25 48 574, those from the U.S. Patents 25 52 240, 25 52 241 and 25 52 242 known substituted p-phenylenediamines and those from the USA patent 25 66 271 known substituted p-phenylenediamines. Other phenylenediamine color developing agents can also be in the processors

so the invention can be used to advantage.

FnsiJl

Claims (5)

The invention relates to a photographic patent claim reversal process in which a photographic recording material with at least one silver halide 1. Photographic reversal process in which the genide emulsion layer is exposed imagewise and developed with a photographic recording material with a black-and-white developer is bleached -white- developed silver and develops washed developer, said in order to prepare, while far in the production of Farbbil a black and white image, the developed silver loos latter rf ^ ^{e "ssc} ^"^{"te r} _a ^» Is bleached and washed out, while in the case of the subsequent photographic recording of the production of color images, the process steps that are called the last generation material for the production of discovery patterns are omitted photographic recording of an aqueous final development nucleation material for the production of ene Development nuclei is dealt with and in which the formed entin the unexposed part of the emulsion layer is then treated with a second developer solution with an aqueous development nucleator solution to form a black and white or colored positive and in which the reversed image formed is then developed. Development nuclei with a second developer It is known that white black for the production of positive solution to one or color-color reversal images are developed, the exposed photograpositiven reverse image, d a- * ° phical silver halide emulsion characterized by color by that the decision photographic In drawing mate alien first treated with a tin (II) -crgano- a black-and-white developer with a winding nucleation solution, then contains phosphorus chelate, which is subjected to a reverse process during the conversion and finally a tin and D salt with a phosphonic acid is developed with a color developer. The following general formulas * 5 a ^ h are known in the solution that arises after the first development or in the second developer RN (CH ₂ PO ₃ M,), solution instead of renewed reversal To use developmental nucleators. Suitable in which M is a hydrogen atom or a water development nucleator, for example in the solubilizing cation and R given 30 U.S. Patents 29 84 567 and 32 46 987 as well if substituted alkyl group, one optionally specified in the German version 12 67 V / /. substituted aryl group, an aralkyl group, one of the borane, phosphine, acyclic group ode? The amino radical has a heterocyclic arsine and selenium compounds mean or boranes as particularly valuable development nuclei 35 educators proven. These well-known development nuclei However, RR ₁ C (PO ₃ Ma) ₂ formers have the disadvantage that their resistance speed is relatively low. The boranes have b; i- in which R is a hydrogen atom or an optionally substituted alkyl group, an optionally to generate development nuclei in a substituted aryl group, an aralkyl or hetero-acid stop solution before the second development to form a cyclic or acyclic group or for example decompose one. Therefore, the PO ₃ M ₂ groups described therein. R, a hydrogen atom, a special borohydride and boranes in alkaline Lo-Hydroxyl or an optionally substituted solutions, for example in an alkaline developer-alk}! _{Group or a PO., M 2} group mean solution, are stored in which they but always and M has the meanings given above 45 are still subject to decomposition by air oxidation. 2. The method according to claim 1, characterized thereby, the object of the invention is to improve draws that a development nucleator solution indicates developmental nucleators that are involved in their used in addition to the tin (II) organo- use in a photographic reverse phosphorus chelate a small number of people drive both positive black-and-white and colored ones contains organic acid, so that the solution has a 5 ° 1 Vikehrbild with a better photographic Provide a pH of 2 to 7 and adequate buffer reproduction and image resolution. has capacity. It has now been found that this task 3. Verfahrennach claim 1, characterized can be solved in that one in photographic draws that a development nucleator solution reverse process a development nucleator solution is used, the except the tin (II) -organo- 55 used, the certain tin (II) -organophosphorophosphorus chelate still contains alkali and a developer chelate. In British Patent 5 00 796 connection contains. and in US Pat. No. 22 95 013 it is 4. The method according to claim 3, characterized «ekenn- use of tin (H) salts in photographic draws that a development nucleator solution described reversal processes, but has used it which shows as a developer compound a 60 that the tin (II) salt described therein is primary contains aromatic amine. Solutions only with relatively high concentrations 5. The method according to claim 2 and / or 4. detrations development nuclei in the silver halide characterized in that a development nuclei form, so that this subsequently with an alkaline Forming solution is used, the additional silver halide developing solution is developed contains a reactive coupler that can react with 65. The tin (II) salts are subject to acidic solution the oxidation product of the developing agent, on the other hand, a gradual air oxidation and that reacts to form a dye. The resulting tin (IV) oxide is deposited on the photographic emulsions in the form of dirt