DE2854946A1 - PHOTOGRAPHIC COLOR DIFFUSION TRANSFER PROCESS - Google Patents

Description

285494S - // O-

AGFA-GEVAERT 5090 Leverkusen, Bayerwerk

AKTIENGESELLSCHAFT hs-mka -Kü

Patent Department ₁ ^ ^

Color diffusion photographic transfer process

The invention relates to a method for producing color photographic Dye diffusion transfer images as well as a suitable photographic material, the new, diffusion-resistant, oxidizable coloring Contains compounds which, in non-oxidized form, set free diffusing dyes,

Among the heretofore known methods of producing color photographic images by the color diffusion transfer method In recent times, those that are diffusion-resistant have been gaining in importance embedded coloring compounds are based, from which diffusing dyes during development or dye precursors are image-wise split off and transferred to an image-receiving layer.

The coloring compounds suitable for this purpose are, for example, those described in DE-PS 1,095,115 to include non-diffusing color couplers that are used in the

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Development as a result of a reaction with the oxidation product of a primary aromatic amine Color developer compound a preformed dye or dye generated during color coupling in a diffusing form Set form in freedom. The selection of the required developer compound is naturally limited here on color developer.

Reference should also be made here to the hichtdif-forming coloring compounds described in DE-OS 1 930 215, which contain a pre-formed latently diffusible dye residue linked to a residue that makes it diffusible via a cleavable hydrazone group. These compounds are not to be referred to as color couplers, and it has also been found that the selection of developer compounds required to release the diffusing dye residue is by no means restricted to the usual color developers, but that black and white developers, Z ₀ B ₀ pyrocatechins, are very useful »

In DE-OS 1 772 929 non-diffusing colored compounds with a special group are also described, which enter into an oxidative ring closure reaction during development and a preformed one Release dye residue in diffusing form.

The compounds presented there can be divided into two groups. Need the connections of one group to develop a common color developing agent, with whose oxidation product they couple and in a subsequent ring closure reaction set free the preformed dye residue in diffusing form.

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The compounds of the other group are themselves silver halide developing agents and are therefore also capable of In the absence of further developer compounds in the oxidized form, the aforementioned ring closure reaction to enter into release of the diffusing dyes.

Finally, the non-diffusing coloring compounds of the DE-OS should be mentioned at this point 2 242 762. These are sulfonamidophenols and sulfonamidoanilines, which are used after the development carried out oxidation under the influence of the developer alkali with the release of diffusing dyes with a free sulfamoyl group are cleaved.

The coloring compounds mentioned above all work negatively, i.e. the pictorial distribution of the free- Set diffusing dye is produced when using conventional (negative-working) silver halide mule ions in accordance with the negative silver image produced during development. In order to generate positive dye images, it is therefore necessary to use direct-positive tive silver halide emulsions or otherwise using a suitable reversal process.

From the German Offenlegungsschrift 2 402 900 and 2 543 902, non-diffusing coloring agents are still used Compounds known to egg in non-oxidized form a cleavage reaction under alkaline development conditions are enabled, with a diffusing dye being set free, and with those on the other hand in oxidized form the above-mentioned cleavage reaction is difficult or prevented. Such connections are in combination with conventional negative emulsions suitable for the production of positive transfer color images.

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Another class of non-diffusing oxidizable Compounds that release predominantly only from the non-oxidized form of diffusing dyes is the subject matter the German patent application P 28 23 159.6. The compounds described there are essentially around those of the following formula:

where mean:

A is a photographically effective group which, together with the link -Z- (X) _n -, is among alkaline

Conditions are split off from the non-oxidized form of the oxidizable compound;

Y and “T” (identical or different) groups which, owing to their interaction with one another, can be oxidized to form a p-quinoid system;

R is an optionally substituted hydrocarbon radical;

R is hydrogen or an optionally substituted hydrocarbon radical;

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-Ζ ⁵ "

R, R and R ⁵ (identical or different) are hydrogen, halogen, alkyl or alkoxy with up to 18 carbon atoms, acylamino or R together with R denotes to complete a condensed, optionally substituted hydrocarbon

fabric ring required remainder

1 ^ U and where at least one of the substituents R, R, R and R ^ contains a radical which makes it resistant to diffusion.

With the compounds described in the aforementioned German patent application P 28 23 159.6, although Use of conventional negative working silver halide emulsions positive colored transfer images are generated, but these still show a certain color haze on, which indicates that the compounds used are not sufficiently stable in the oxidized state to to be protected against subsequent cleavage under the alkaline development conditions. Are desirable but such coloring compounds of the type described, which are in oxidized form under the development conditions are completely stable.

In the further processing of this technical field it has now been found that one arrives at significantly more favorable results, ie with compounds whose oxidized form is more stable against alkaline cleavage, if those compounds are selected from the class of substances described in the aforementioned German patent application in which neither in the (free) o- nor in the p-position to the ^{carbon atom bearing the cleavable radical ~ S0} 2 "( ^x ^ _m " ^{A is} a deprotonatable group such as -OH or -NH _{2 at the} ^front or can arise in the alkaline developer medium .

It should be noted that one of the two o-positions to the said carbon atom

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be easily substituted with such a group. must, together with a second group of the same species enables the formation of a p-quinoid system in the event of oxidation. It is therefore important that in positions 2 and 4 of the above formula neither a hydrogen atom nor a substituent which can be exchanged by OH "" ions is present.

The invention relates to a photographic diffusion transfer process, in which a photographic material having at least one light-sensitive silver halide emulsion layer and one of these associated non-diffusing oxidizable compound, which in non-oxidized Form under the conditions of alkaline development undergoes a cleavage reaction with the release of a photographically active group, for example a diffusing dye, and those in the oxidized form of the aforementioned cleavage reaction not or only to a much lesser extent than in non-oxidized form, exposed imagewise and is developed with a silver halide developing agent, wherein the silver halide developing agent is oxidized Form, the non-diffusing oxidizable compound is oxidized and thus only slightly or not at all due to alkali fissile form transferred, while from the imagewise distribution of non-oxidized oxidizable compound as Result of cleavage by alkali the photographically effective Group is set free. If it is the photographic effective group is a diffusing dye, this can be applied to an image-receiving layer be transmitted. In the latter case, the non-diffusing compounds are hereinafter referred to as coloring compounds designated. The method is characterized in that as a non-diffusing oxidizable compound Compound of the following formula is used:

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- / Idf

C-SO ₂ - (X) _1n -A

where mean:
A.

the remainder of a photographically active group, especially the remainder of a diffusing group Dye or dye precursor;

a divalent link of the formula -R- (L) - (R) -, wherein R is an alkyl radical with 1-6 Denotes carbon atoms or an optionally substituted arylene or aralkylene radical and where the two radicals R can have the same or different meanings;

-O-, -CO-, -CONR ⁶ -. -SO ₂ NR ⁶ -, -0-CO-NR ⁶ -, -S-, -SO- or -SOp- (R = hydrogen or alkyl);

0 or 1;

0 or 1;

Y ¹ and Y ²

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0 or 1;

(identical or different) groups which, due to their interaction, can be oxidized with the formation of a p-quinoid system, at ^{7 7 8 8}

for example -OR

-NH-SO ₂ -R

y, -NHR ⁷ , -NH-R ⁸ , -N (R ⁸ ), or

wherein R 'is hydrogen or a

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In the photo-inert group hydrolyzable under the alkaline development conditions, R stands for any organic, photographically inert radical that is connected to the N atom or the -SOp group via a C atom, preferably for alkyl, in particular lower alkyl with 1- 4 carbon atoms, or aryl, in particular phenyl or tolyl; However, Y is not a disubstituted amino group -N (R) ₂ ;

R is an optionally substituted hydrocarbon radical, e.g. alkyl with up to 22 carbon atoms, such as Methyl, ethyl, n-hexyl, n-octyl, n-undecyl, n-dodecyl, n-tridecyl, n-heptadecyl, aralkyl such as benzyl or aryl such as phenyl;

R is hydrogen or an optionally substituted hydrocarbon radical, for example alkyl with up to 22C atoms, such as methyl, ethyl, propyl, isopropyl, * i-hexyl, n-octyl, n-undecyl, n-dodecyl, n-tridecyl, n-heptadecyl , Aralkyl such as benzyl,

or aryl such as phenyl;

R ^ is a substituent as ^{defined for R 2} , a

Grouping that condensed on together with R. heterocyclic or carbocyclic, optionally aromatic ring completed

or OH, halogen such as chlorine or bromine, amino, alkylamino, dialkylamino including cyclic Amino groups (such as piperidino, morpholino), acylamino, alkylthio, alkoxy, aroxy or sulfo;

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R is an optionally substituted hydrocarbon radical, Z ₀ B ₀ alkyl with up to 22 carbon atoms, aralkyl such as benzyl, .Aryl such as phenyl or a group which together with R ^ a fused heterocyclic or carbocyclic, against

appropriate, the aromatic ring completed, for example, ₀ a fused benzene or 2-bicyclo ^ 2.2, i7hepten ring;

5
R is an optionally substituted hydrocarbon radical, for example alkyl, aralkyl or aryl

preferably n-propyl,

13 4 and where at least one of the substituents R, R, R and R contains a residue which makes it diffusion-proof.

The present invention also provides a material for carrying out the above method, which accordingly in association with at least one light-sensitive silver halide emulsion layer, a non-diffusing one contains oxidizable compound of the type described above.

The residues of dyes are basically the dye residues all dye classes are suitable, provided they are sufficiently diffusible to pass through the layers of the to be able to diffuse light-sensitive material through into the image-receiving layer »For this purpose, the Dye residues can be provided with one or more water-solubilizing groups. As water-solubilizing groups Carboxyl groups, sulfo groups, sulfonamide groups and aliphatic or aromatic groups are suitable, among others Hydroxyl groups. The sulfinic acid group remaining in the dye after cleavage is capable of the dye molecule already a considerable tendency to diffuse in the alkaline

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To impart medium, so that the presence of additional water-solubilizing groups is not essential is required. Examples of dyes which are particularly suitable for the process according to the invention are to mention azo dyes, azomethine dyes, Anthraquinone dyes, phthalocyanine dyes, indigoid Dyes, triphenylmethane dyes and metal complex dyes or colored metal complexes.

Among the remnants of dye precursors are the residues to understand such connections, which in the course of the photographic processing by usual or additional processing steps, be it by oxidation, be it by coupling or by exposing an auxochromic group in a chromophoric system, for example by saponification, can be converted into dyes »dye precursors in this can be leuco dyes, or couplers Colorants that are converted into other colorants in the course of processing. Unless there is a distinction between dye residues and the residues of dye precursors is of essential importance, the latter should be hereinafter also referred to as dye residues will.

The bivalent link shown in the general formula For example, X can be a residue of one of the following formulas:

,, SO ₃ H

-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ ; -

H ₃

; -Q ^ ; -CH ₂ -CH ₂ -SO ₂ -C ₆ H ₁₂ -;

NH- and -C ₃ H ₆ -NH-CO-C ₂ H ₄ -O AG 1618

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Y ¹ and Y ² preferably have the meaning hydroxyl »If

1-2 8 8

Y and / or Y ^ is an -NH-SO ₂ R group, R has

expediently the meaning of a photographically inert radical, e.g. an unsubstituted alkyl or phenyl radical.

It goes without saying that within the group of oxidizable compounds of the general formula some are more suitable than others. For example, by varying the substituent R, the redox potential of the oxidizable compound can be easily influenced and in this way adapted to practical requirements. It has already been pointed out that, according to the invention, the choice of the substituents R and R- 'is subject to certain restrictions, insofar as hydrogen or other substituents which can be exchanged by OH- ions are out of the question Br to, so that here a larger selection of substituents is available for setting the desired redox potential. In addition to being oxidizable, another important function of the compounds according to the invention is that they are readily hydrolyzable in the non-oxidized form. The hydrolytic cleavage should proceed as quickly as possible in the alkaline developer medium so that the photographically active group is quickly set free. On the other hand, the onset of hydrolytic cleavage should be delayed until the image-wise oxidation of the oxidizable compounds by developer oxidation products is essentially complete. The rate of hydrolytic cleavage must therefore be adapted to the rate of oxidation and this can easily be achieved by varying the substituents, which have a great influence on the hydrolyzability. This is influenced, among other things, by the nature of the link (X), primarily

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Line, however, by the nature of the substituents, R, R Y ² within the given definition. If Y ₀ = OH, then, for example, R is preferably hydrogen. It should be pointed out that the coloring compounds according to the invention should not diffuse as intact molecules in the layers of the photographic material. For this purpose they contain a radical which makes it diffusion-resistant, for example in one of the substituents R to R or in a substituent present on the ring which is fused together with R and which is completed by R.

Sufficient diffusion resistance of the coloring compounds can be given even if the substituents mentioned do not contain any longer alkyl radicals, because even then the molecule, depending on the dye residue, is a sufficient one Can have size. Otherwise there is the option of changing the coloring compounds by selecting To make residues of a suitable size sufficiently resistant to diffusion.

Such residues are to be regarded as diffusion-proofing residues, which make it possible to use the compounds according to the invention in the customary photographic materials used to store hydrophilic colloids in a diffusion-proof manner. Organic radicals, which are generally straight-chain or branched aliphatic, are preferably suitable for this purpose Groups and optionally also isocyclic or heterocyclic or aromatic groups with in general Contains 8-22 C atoms. With the rest of the molecule, these residues are either direct or indirect, e.g. "via one of the following groups:

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-NHCO-, NHSO ₂ , -NR-, where R is hydrogen or alkyl, -0-, -S- or -SO- with groups containing such heteroatoms expediently by at least two carbon atoms or methylene groups from the aro-

3 4 5 matic ring of the general formula (R, R, R) or from which the cleavable group -SO - (X) -A) carries

λ * L ITl

Carbon atom (R) are separated. In addition, the diffusion-proof making radical also contain water-solubilizing groups, such as sulfo groups or carboxyl groups, the can also be present in anionic form. Because the diffusion properties depend on the molecular size of the total compound used depend, it is sufficient in certain cases, e.g. if the total molecule used is large enough to be "Diffusion-resistant residues" can also be used with shorter-chain residues.

Examples of non-diffusing ones suitable according to the invention Oxidizable compounds are listed below:

J ^ -N = N -4 V-OH

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CH

CH ₃

CH ₃ " ¹

^{3 7}

OH

-OH

OH CH-SO ₂ - / " NH-SO ₂ - ^ _V N ₂ CH ₃ OH C ₃ H ₇ Or " CH ₃ - ι
NO ₂ - C-CONH-CH,
Il J
N CH ₃ - 1 \ Τ — 1ST Ur * ... OC

OH ^C 13 ^H 27
CH, -i ^ S- CH-SO ₀ - / y NH-SO, -f \ - NHCOCH,

OH

»- OH

IT = N

Cl

OH. C ₁₃ H ₂

CH ₃ SO ₂ NH-C-CH ₃

OH

NH

SO ₂

CH,

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-Ά-

OH C ₁₇ H ₃₅

-r ^ S- CH-SO ₂ - / ^ - N = NC C- / ~ ^

A ^ -CHr ₇ ^^^ OC N ^^

OH

OH CH,

I ^J

NHSO ₂ - ^ "^ - NHCOCH,

CH,

OH CH ₃ P3

^H 7 ^C 3 ~ fll ~ CH-SO ₂ - (^)

O ~ ^0H

N = N

OCH,

-HC OC

■ C-CONHCH,

Il <

OH. ^C 15 ^H 31

, —CH-SO ₀ -Jf \ _

NHSO

NHCOCH,

OH

k =

-OH

ι
Cl

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-as-

pH

OH

- OH

OH CH, t ->

OH

OH

V-SO ₂ CH ₃

NO.

fe0 ₂ -NH / \ N = N Λ >

NO,

OH

- N = N-HC · OC

pH

'2 V-

1 OH

_? - / "^) - N = N-HC C-CONHCH,

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Vf -

Br-CH ₃ "

_P Hf21

43

'-0, H ₇ 1

N = N-ι

OCOOC ₂ H ₅

OH

CH ₃ O SO ₉ ι * -

CH,

OH

CH ₃ | j ^> pCH-S0 ₂ ~ f ~% - NHSO,

16 ^CH 3 OH

SO ₂ -NH

ro-

OH

ι NO,

HO-

H ₂₉ C ₁₄

f \ -0H

⁵

OH

s ^

CH,

^0H C15H27

HO ₃ S -

-N = N-HC C-

t H

OC N

OH

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? ^H ° 13 ^Η 27

CH ₃ SO ₂

OH

NO,

OH SO ₂ -NH

-ΟΗ

CH ₃ SO ₂ -,

NO,

? ^H ? 15 ^H 31 _ CH ₃ O - ₍ > s- CH-SO - ^ Λ- N = N -

cH ₃ -yc _3H7 ² w

^0H so

? ° 2 CH,

OH ^C 15 ^H 31

^CH 3

N- ^ S- CH-SO ₂ - / ^ - N = N-HC C-

CONHC.H ₀

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pH ^C 15 ^H 31

- CH-SO ₂ -

₂ ^

OH

CH

OH

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Preparation example I

Connection no ₀ 1

Stage 1: 2,3-dimethyl-6-tetradecanoyl-hydroquinone

In a mixture of

138 g (1 mol) of 2,3-dimethylhydroquinone, 370 g (1.62 mol) of myristic acid and
700 ml of methylene chloride

is (C bath temperature 50 ⁰⁾ introduced under lebheftem reflux until saturation boron trifluoride. After standing over

The reaction mixture was decomposed overnight by stirring into 3 liters of 10% strength sodium acetate solution. The methylene chloride was removed with steam. The remaining oily layer solidified after cooling to form a melt cake, which was isolated by decanting. The melt cake was then melted and stirred into 2 l of high-boiling gasoline. The precipitate was filtered off with suction and petrol - ether (50 70 ⁰ C). After drying, the mixture was stirred with acetonitrile and filtered off with suction.

Yield: 260 g / F 100-101 ^° C

Step 2: ^ -hydroxy ^^ - dimethyl-o-tetradecanoylphenyl allyl ether

To a mixture of
105 g of ketone from stage 1
63 g potassium carbonate and
1200 ml of methyl ethyl ketone

43 g of allyl bromide were added dropwise over 2 hours with gentle boiling. After 9 hours of boiling, the mixture was ^{cooled to 30 °} C. and 200 ml of water were added.

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The aqueous layer was separated. The organic layer was extracted once with 25 # saline solution, separated off and the solvent was distilled off. The residue was stirred with 1 l of methanol and filtered off with suction.

Yield: 95 g / F 65-66 ⁰ C

Step 3: 2,3-Dimethyl-5-allyl-6-tetradecanoy / hydroquinone

90 g of allyl ether of step 2 were heated under a nitrogen atmosphere in the course of 2 hours at 210 ⁰ C. After cooling, the melt was dissolved in 300 ml of gasoline (50-75 ^° C.) and placed in the cold. The next day the resulting precipitate was sucked off.

Yield: 73 g / F 68 - 69 ⁰ C

Stage 4: 2,3-dimethyl-S-propyl-δ-tetradecanoyl hydroquinone

16.2 g of the allyl compound from step 3 were in 165 ml Dissolved alcohol and in the presence of Raney nickel below normalbe conditions hydrogenated. After removing the Raney nickel the alcohol was distilled off and the residue was crystallized from 300 ml of gasoline.

Yield: 15 g / F 69-70 ^° C.

Step 5: 2,3-Dimethyl-5-propyl-6-cC-hydroxytetradecylhydroquinone

14 g of the keto compound from step 4 were dissolved in 390 ml of methanol dissolved and slowly mixed with a solution of 1.97 g of sodium borohydride in 24 ml of water while stirring in a nitrogen atmosphere. After 30 minutes, glacial acetic acid was used to make the

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represents and stirred in a solution of 2.5 ml of sulfuric acid in 270 ml of water. The precipitate was filtered off with suction and recrystallized from methanol.

Yield: 10.5 g / F 140-142 ⁰ g

Step 6: dye sulfinic acid

4- (4-Hydroxy-3-N, N-diethylsulfamoyl-8-methylsulfonamido-1-naphthylazo) -benzenesulfinic acid

Under a nitrogen atmosphere, 11.5 g of sodium salts of 4-alino-benzenesulfinic acid and 4.4 g of sodium nitrite dissolved in 70 ml of water, mixed with 85 g of crushed ice and stirred with 18 ml of concentrated hydrochloric acid are added.

The diazonium salt solution was immediately poured into one Solution of

25 grams of 1-hydroxy-2-N, N-diethylsulfamoyl-5-methylsulfonamidonaphthalene
23.15 g of sodium carbonate, 130 ml of water and
45 ml acetone
stirred in.

After 30 minutes the dye solution was in 200 ml of glacial acetic acid stirred in and the precipitated dye is filtered off with suction.

After drying in a vacuum desiccator, 32 g of crude dye remain which, without purification, are converted into a compound was used.

Step 7: Connection 1

A solution was added to a solution, heated to 60 ^° C., of 4 g of the carbinol compound from stage 5 in 300 ml of glacial acetic acid

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from 7 g of dye sulfinic acid from stage 6 1.5 g of sodium acetate anhydrous
120 ml of glacial acetic acid and
40 ml of water

given. Under stirring in nitrogen atmosphere for 2 hours was heated to 9O ⁰ C. After a short time, the dye compound begins to precipitate. After cooling to 60 ^° C., the precipitate formed was filtered off with suction and washed with glacial acetic acid. The dye was purified by stirring with methanol.

Yield: 5.6 g
Preparation example II

Compound No. 11

Stage 1: 2-methyl-5-hexadecanoyl-hydroquinone

In a mixture of

27.2 grams of palmitic acid

13.7 g of 2-methylhydroquinone and

45 ml of methylene chloride

boron trifluoride was introduced under vigorous reflux until saturation. After standing overnight it was still Boiled under reflux for 1 hour and then decomposed in a solution of 25 g of sodium acetate in 220 ml of water with stirring.

After 45 minutes the methylene chloride solution was separated off and evaporated. The residue was stirred with methanol and sucked off.

90-93 ⁰ C were recrystallized from n-chlorobutane 21 g obtained with F.

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Step 2: ^ Hydroxy ^ -methyl-S-hexadecanoylphenyl-allyl ether

Under a nitrogen atmosphere, a mixture of 17.5 g of the keto compound from stage 1 was 10.2 g of potassium carbonate and
200 ml methyl ethyl ketone

while stirring and refluxing, 6.9 g of allyl bromide were added over the course of 60 minutes. After a total of 9 hours of reflux 100 ml of water were added to the reaction mixture. The methyl ethyl ketone layer was separated, twice extracted with 20% saline solution and dried with sodium sulfate. The one after evaporation of the solvent remaining residue was stirred up with methanol and the resulting precipitate, after suctioning off, still from methanol recrystallized.

Yield: 12.5 g / F 44-47 ⁰ C

Step 3: 2-methyl-6-allyl-5-hexadecanoyl hydroquinone

12 g of allyl ether from stage 2 were subjected to the Claisen rearrangement as described in preparation example 1, stage 3. After cleaning with petrol (50 - 75 ⁰ C) 8.5 g yield with F were 65 - 67 ° C obtained.

Step 4: 2-methyl-6-propyl-5-hexadecanoyl hydroquinone

8 g of allyl hydroquinone from stage 3 were hydrogenated as described in preparation example 1, stage 4, and the resulting Product also recrystallized from gasoline.

Yield: 6.5 g / F 66-68 ⁰ C

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Step 5: 2-methyl-6-propyl-5-eC -hydroxy-hexadecylhydroquinone

6.5 g of the wedge connection from step 4 were in 90 ml of methanol dissolved and with a solution of 0.75 g of sodium borohydride in 8 ml of water as in preparation example 1, stage 5, described hydrogenated and the crude carbinol recrystallized from methanol.

Yield: 5 g / F 121-124 ⁰ g

Step 6: dye sulfinic acid

4- (3- / 5- (4-nitro-2-methylsulfonyl-phenylazo) -5-hydroxy-1-naphthyl-7-sulfamoylbenzene -sulfonamidobenzenesulfinic acid

In a solution of

4.9 grams of potassium carbonate

3.75 g of aminobenzenesulfinic acid
44 ml of water and

62.5 ml of acetone

10 g of 3- / S- (4-nitro-2-methylsulfonyl-phenylazo) -5-hydroxy-1-naphthyl7-sulfamoyl- benzene sulfochloride registered. After 30 minutes, it was filtered and to the solution successively 250 ml of water and

31 ml concentrated hydrochloric acid

given. The resulting precipitate was filtered off with suction and washed with water. Dried in the drying cabinet.

Yield: 10.6 g

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Stage 7: Compound No. 11

Under nitrogen atmosphere, 5 ml of glacial acetic acid in 250 at 60 was added to a solution of 4.1 g of carbinol of step - 65 ⁰ C with stirring

a filtered solution of 8.9 g of dye sulfinic acid at 85 ^{° C.}

1 g of sodium acetate sicc in 200 ml of glacial acetic acid and 120 ml of water

added and 1 hour at 60 - 65 ⁰ C stirred. After cooling, the resulting precipitate was filtered off with suction and recrystallized from ethyl acetate / methanol with the addition of activated charcoal.

Yield: 5.5 g

The main aspect of the present invention relates to the case in which the oxidizable compound is a coloring agent Compound is and the photographically effective group is a diffusing dye. For this reason, the following mainly referred to coloring compounds, but this should not be understood as a limitation allowed. Indeed, the oxidizable compounds can be used for a variety of other purposes, with others photographically effective groups can come into question. The coloring compounds according to the invention are used in the casting solutions for the layers of the photographic material incorporated by one of the usual methods. The amount of coloring compound used per liter of casting solution varies within relatively wide limits, with the most favorable concentration being determined on the basis of simple experiments. For example, 5-80 g per liter of casting solution is preferred 20 - 40 g of coloring compound used.

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The one required to achieve the desired effect Assignment between diffusion-resistant coloring compound and silver halide can be established, for example that the diffusion-resistant compounds using existing strongly acidic water-solubilizing groups be introduced from aqueous solution into the casting solutions. The non-diffusing coloring compounds but can also be introduced into the layers by one of the known emulsification processes. Such procedures are for example described in British Patents 791,219 and 1,099,414 to 1,099,417. Furthermore it is possible to prepare aqueous dispersions or coloring compounds and add them to the respective casting solutions. For this purpose, aqueous slurries of the coloring compounds are added, for example by vigorous stirring Fine grinding of sharp-edged sand or using ultrasound. In another embodiment it may be desirable, for example, to combine the coloring compounds with silver halide and optionally To store developer substances in the form of so-called microcapsules in the layer, with two or more different sensitized photosensitive silver halide emulsions and the corresponding diffusion-resistant compounds in a single layer of the so-called type Mixed grain emulsions are combined, as described, for example, in US Pat. No. 2,698,794. The non-diffusing Coloring compounds can be in a photosensitive layer itself or in an adjacent layer be housed. For example, the red-sensitive layer is one which releases a blue-green dye Compound, the green-sensitive layer a compound which splits off a purple dye and the A yellow dye-releasing compound is assigned to the blue-sensitive layer.

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By "assignment" and "assigned" is meant that the mutual arrangement of silver halide emulsion and The coloring compound is of such a nature that an interaction between them is possible, an image-like interaction Correspondence between the formed silver image and the image-wise distribution of oxidized, non-diffusing coloring compound allows.

The assigned coloring compound is expediently incorporated in the silver halide emulsion itself or in a layer adjacent to the silver halide emulsion layer is incorporated, this adjacent layer preferably (viewed in the direction of the incident light during exposure) behind the silver halide emulsion layer lies. The coloring compounds according to the invention are oxidized image-wise during the development of the silver image by developer oxidation products; they don't oxidized portions of the following compounds are then subject to the influence of the developer or activator alkali a cleavage reaction in which the dye residues be set in freedom in a diffusing form. The usual photographic silver halide developing agents are used for development suitable, insofar as they are able, the coloring compounds according to the invention in oxidized form to oxidize. Examples of suitable developers are:

Hydroquinone
N-methylaminophenol
1-ifrenyl-3-pyrazolidone
1-Ehenyl-4,4-dimethyl-3-pyrazolidone
1-phenyl-4-methy1-4-hydroxymethyl-3-pyrazolidone 1-phenyl-4,4-bishydroxymethyl-3-pyrazolidone aminophenols

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N, N-diethyl-p-phenylenediamine
N-ethyl-N-hydroxyethyl-p-phenylenediamine and 3-methyl-N, N-diethyl-p-phenylenediamine N, N, N ¹ , N ¹ -tetraalkyl-p-phenylenediamines such as tetramethyl-p-phenylenediamine

Triethylsulfobutyl-p-phenylenediamine and 1,4-bis-pyrrole-dinobenzene

Reductones

It should be pointed out in particular that the selection of developer substances in the process according to the invention is not limited to color developers, but that conventional black-and-white developers are also preferably used, which is to be regarded as an advantage because of the lower tendency of the latter to discolour.

The developers can already work in the layers of the color photographic Materials to be included where they are activated by the alkaline activator liquid, or in the alkaline processing liquid or paste. Since the inventive coloring compounds themselves have developer properties can dispense with the use of auxiliary developer compounds under certain conditions will. In this case the coloring compound is oxidized immediately by developable silver halide.

Since the pictorial distribution of the released during development diffusing dye corresponds to the imagewise distribution of the undeveloped silver halide, There is no need to use direct-positive silver halide emulsions to generate positive colored transfer images or the use of a suitable reversal process, but conventional negative emulsions can be used be used.

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-33-

The emulsions can be chemically sensitized, e.g. by adding sulfur-containing compounds in the chemical Maturation, for example allyl isothiocyanate, allyl thiourea, Sodium thiosulfate and the like. As a chemical Sensitizers can also be reducing agents, e.g. those in Belgian patents 493,464 and 568,687 tin compounds described, also polyamines such as diethylenetriamine, or aminomethanesulfinic acid derivatives, e.g. according to Belgian patent 547 323 can be used.

TO Precious metals are also suitable as chemical sensitizers or noble metal compounds such as gold, platinum, palladium, iridium / ruthenium or rhodium. This method of chemical Awareness is in the article by R. KOSLOWSKY, Z.Wiss.Phot. 45, 65-72 (1951).

It is also possible to use the emulsions with polyalkylene oxide derivatives to sensitize, e.g. with polyethylene oxide with a molecular weight between 1000 and 20,000, furthermore with Condensation products of alkylene oxides and aliphatic alcohols, glycols, cyclic dehydration products of hexitol oils, with alkyl-substituted phenols, aliphatic Carboxylic acids, aliphatic amines, aliphatic diamines and amides. The condensation products have a Molecular weight of at least 700, preferably more than 1000. These can be used to achieve special effects Use sensitizers in combination, of course, as described in BE-PS 537 278 and GB-PS 727 982.

The emulsions can also be spectrally sensitized, e.g. by the usual mono- or polymethine dyes such as acidic or basic cyanines, hemicyanines, streptocyanines, merocyanines, oxonols, hemioxonols, styryl dyes or others, also trinuclear or polynuclear methine dyes, both

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-to-

for example rhodacyanines or neocyanines. Such sensitizers are described, for example, in the work by FoM. HAMER "The Cyanine Dyes and Related Compounds" (1964) Interscience Publishers John Wiley and Sons, New York _o

The emulsions can contain the usual stabilizers, such as ζ.Β, homeopolar or salt-like compounds of mercury with aromatic or heterocyclic rings such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds. Azaindenes are also suitable as stabilizers, preferably Tetra- or penta-azaindenes, especially those substituted with hydroxyl or amino groups. Such Connections are in the article by BIRR, Z.Wiss.Phot. 47, 2-27 (1952). Other suitable stabilizers include heterocyclic mercapto compounds, e.g. phenyl mercaptotetrazole, quaternary benzothiazole derivatives, benzotriazole and similar.

The preferred binder for the photographic layers is Gelatin used «However, this can be wholly or partly made by other natural or synthetic binders be replaced. Natural binders include, for example, alginic acid and its derivatives such as salts, esters or Amides, cellulose derivatives such as carboxymethyl cellulose, Alkyl cellulose such as hydroxyethyl cellulose, starch or their Derivatives such as ethers or esters, or caragenates are suitable. Synthetic binders include polyvinyl alcohol, partially saponified polyvinyl acetate, and polyvinyl pyrrolidone and the same.

The layers can be hardened in the usual way, for example with formaldehyde or halogen-substituted aldehydes which contain a carboxyl group such as Mucobromic acid, diketones, methanesulphonic acid esters, dialdehydes.

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To carry out the dye diffusion transfer process in accordance with the present invention, a photosensitive element is used which has one or more silver halide emulsion layers as well as the non-diffusing coloring compounds assigned to these contains and a Image receiving element in which by the image-wise transferred diffusing dyes produce the desired color image. For this it is necessary that between the. photosensitive element and the image-receiving element for at least a finite period of time within the Development time there is firm contact, so that the In the photosensitive element as a result of development generated image-wise distribution of diffusing dyes can be transferred to the image receiving element. .

Contact can be made after the development has been set in motion or it may already be established before development begins. The latter is the case, for example, if to carry out of the dye diffusion transfer method, a material is used in which the photosensitive element and the image receiving element form an integral unit, hereinafter also referred to as monosheet material, which also remains after the end of the development process, i.e. a separation of the light-sensitive element from the image receiving element is not provided even after the color transfer has taken place. Such an embodiment is described, for example, in DE-OS 2 019 430.

One for performing the dye diffusion transfer process suitable according to the present invention Monosheet material has, for example, the following layer elements:

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1) a transparent substrate

2) an image receiving layer

3) an opaque layer

4) a photosensitive element having at least one photosensitive silver halide emulsion layer and at least one of these associated non-diffusing coloring compounds

5) a delay layer

6) an acidic polymer layer

7) a transparent substrate

The monosheet material can be put together in such a way that two different parts are produced separately from one another, namely the light-sensitive part (layer elements 1-4) and the cover sheet (layer elements 5-7) which are then placed on top of one another and connected to one another on the layer side, if necessary under Use of spacer strips so that a space is formed between the two parts for receiving a precisely measured amount of a processing liquid. The layer elements 5 and 6, which together form the neutralization system, can also be arranged between the layer support and the image-receiving layer of the light-sensitive part, albeit in a reversed order. Means can be provided to introduce a processing liquid between the photosensitive part and the cover sheet, for example in the form of a laterally arranged splittable container which, when mechanical forces are applied, pours its inside between two adjacent layers of the mono-sheet material.

An essential part of the photographic material according to the present invention is the photosensitive element, that in the case of a single dye transfer process

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285494S

a photosensitive silver halide emulsion layer and associated with this contains a non-diffusing coloring compound. The non-diffusing Compound in a layer adjacent to the silver halide emulsion layer or in the silver halide emulsion layer themselves are located, in the latter case the color of the image dye is preferably selected so that the predominant absorption range of the coloring compound does not correspond to the predominant sensitivity range the silver halide emulsion layer. For the production of multicolored transfer images in lifelike However, the photosensitive element contains three such assignments of coloring compounds and colors photosensitive silver halide emulsion layer, wherein usually the absorption range of the coloring compound with the range of the spectral sensitivity of the associated silver halide emulsion layer will essentially coincide. Prerequisite for a possible However, high sensitivity is then that each coloring combination is in a separate binder layer (viewed in the direction of the incident light during exposure) behind the silver halide emulsion layer is arranged. The developer oxidation products formed during the development of a silver halide emulsion may of course only affect the assigned coloring connection. It is therefore generally separating layers in the photosensitive element present, which the diffusion of the developer oxidation products effectively prevent other unassigned layers.

These separating layers can, for example, contain suitable substances that react with the developer oxidation products, for example non-diffusing hydroquinone derivatives or, if the developer is a coloring '

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developing substance, non-diffusing color couplers. In a preferred embodiment, the photosensitive element therefore has the following structure (from top to bottom below):

blue-sensitive silver halide emulsion layer

Layer with non-diffusing, one diffusing Yellow dye releasing compound

Separating layer

green sensitized silver halide emulsion layer

Layer with non-diffusing, one diffusing Purple dye releasing compound

Separating layer

red sensitized silver halide emulsion layer

Layer with non-diffusing, one diffusing Cyan dye releasing compound

Of course, the silver halide emulsion layers can can also be arranged in a different order, but with the assigned layers with the coloring Systems must also be swapped so that the assignment is retained »

The opaque layer arranged under the photosensitive element is permeable to water alkaline treatment solutions and thus for the diffusing Dyes. It has two main functions: firstly, it serves the purpose of following the development in the image silver remaining on the original photosensitive element as well as that remaining as a color negative to cover coloring compounds, so that when viewed through the transparent support of the photosensitive Partly only the positive color transfer image is visible} secondly, it excludes the light-sensitive one

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-4s-

Element facing the side of the image receiving layer (downwards) light-tight. The latter is particularly important if the monosheet material is still in the after exposure Camera brought into contact with the alkaline processing compound, then pulled out of the camera and outside the camera is to be developed.

Layers with sufficient opacity, but sufficient permeability for diffusing dyes can for example with suspensions of inorganic or organic dark, preferably black pigments, for example with suspensions of carbon black in suitable binders, e.g. in gelatin solutions. in the In general, 0.5 - 2 / U thick layers, which are in Gelatine contain 10-90% by weight (based on the total dry weight) of carbon black to ensure sufficient levels during to guarantee an exclusion of light from the development. The particle size of the pigments used is relative not critical as long as it does not significantly exceed 0.5 / u.

In addition to the black pigment layer, the opaque layer preferably also comprises a white pigment layer arranged underneath. This has the task of covering the black layer and giving the picture a white. To create underground. All white pigments are suitable for this, provided that their opacity is sufficiently high if the layer is not too thick. For example, barium sulfate, oxides of zinc, titanium, silicon, aluminum and zirconium, as well as barium stearate or kaolin, may be mentioned. Titanium dioxide is preferred as the white pigment. Here too, the same information applies with regard to the binder, the concentration and the particle size as for the black pigments. The thickness of the white pigment layer can be varied depending on the desired whiteness of the substrate. Thicknesses between 5 and 20 / U are preferably used.
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Away-

Instead of the opaque layer can also be used in the monosheet material according to the present invention Means for creating such an opaque layer between the photosensitive element and the Image receiving layer may be arranged, for example in the form of a laterally arranged container with a processing liquid containing an opacifier (pigment), which when exposed to mechanical forces pours its contents between the layers mentioned, so that there forms such a pigment layer.

The image-receiving layer consists essentially of a binder, the dye mordant for fixing which contains diffusing dyes.

Long-chain quaternary ammonium or phosphonium compounds are preferably used as mordants for acidic dyes or ternary sulfonium compounds such as those described in U.S. Patents 3,271,147 and 3 271 148. Certain metal salts and their hydroxides, which are sparingly soluble with the acidic dyes, can also be used Form connections, are used. The dye mordants are in the receiving layer in one of the common hydrophilic binders dispersed, e.g. in gelatin, polyvinylpyrrolidone, wholly or partially hydrolyzed Cellulose esters and the like. Of course, some binders can also act as pickling agents, e.g. copolymers or polymer mixtures of vinyl alcohol and N-vinylpyrrolidone, as described, for example in DE-AS 1 130 284, also those which are polymers of nitrogen-containing quaternary bases, e.g.

Polymers of N-methyl-2-vinylpyridine, such as, for example described in U.S. Patent 2,484,430.

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At this point, reference may be made to the crosslinking products of described in DE-OS 2,631,521 hydrophilic binders with glycidyl groups quaternary polyurethanes. Further useful caustic binders are, for example, guanylhydrazone derivatives of Acylstyrene polymers, as described, for example, in DE-OS 2 009 498. In general, however, other binders will be used with the last-mentioned binding agents, e.g. add gelatine.

As a transparent support for the inventive Monosheet material can be common in photographic Transparent carrier materials used in practice, e.g. films made of cellulose esters, polyethylene terephthalate, polycarbonate or other film-forming polymers, use Find. Due to the alkaline processing compound, the photosensitive material has a relatively high pH set (about 11-14), which triggers development and image-wise dye diffusion. It has It has been found that at this high pH the dyes and thus the images obtained are not particularly stable are. It is therefore necessary that, after the development is complete, the material should be nearly neutral or slightly acidic is provided. This can be achieved in a known manner by adding an acidic polymer layer to the material which only gradually becomes accessible to the alkaline processing compound in the course of development. An acidic polymer layer is understood to be a binder layer that contains polymeric compounds with acid groups, preferably sulfo or carboxyl groups.

These acidic groups react with the cations of the processing compound to form salts and thereby reduce them the pH of the mass. It goes without saying that the polymeric compounds and thus the acidic groups are included in the above Layer embedded in a diffusion-proof manner. Multiple

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len the acidic polymers derivatives of cellulose or derivatives of polyvinyl compounds; however, other polymeric compounds can also be used. As useful acidic polymers may be mentioned, for example: cellulose derivatives with free carboxyl groups, e.g. cellulose di car bonsäure haibester with free carboxyl group like Cellulose acetate hydrogen phthalate, cellulose acetate hydrogen glutarate, Ethyl cellulose acetate hydrogen succinate, cellulose acetate hydrogen succinate hydrogen phthalate, Ethers and esters of cellulose with other dicarboxylic anhydrides or with sulfonic anhydrides, for example with o-sulfobenzoic anhydride are modified, carboxymethyl cellulose, also polystyrene sulfonic acid, polyvinyl hydrogen phthalate, Polyvinylacetathydrogenphthalat, polyacrylic acid, acetals of polyvinyl alcohol with aldehydes, which by carboxy or sulfo groups are substituted, such as o-, m- or p-Benzaldehyde sulfonic acid or carboxylic acid, partially esterified Ethylene-maleic anhydride copolymers, partially esterified methyl vinyl ether-maleic anhydride copolymers and the same.

Suitable acidic polymers are described in DE-OS 2,652,464, for example.

The acidic polymer layer must contain enough acid groups to maintain the pH of the processing compound from the start

2 ^ 11 to 14 so far that the material is adjusted to almost neutral or slightly acidic at the end (pH value 5-8).

The time delay of the lowering of the pH value is achieved in a known manner in that the acidic polymer layer is covered with a so-called retardation layer. This retardation layer is an alkali-impermeable one Layer, which is preferably made of an anti-alkali

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inert polymers, for example made of polyvinyl alcohol or a partially acetalized polyvinyl alcohol. By suitable choice of the thickness and the composition of these Delay layer can set the time delay of the lowering of the pH value in the desired manner will. A braking layer with polymers with a new type of permeability behavior is, for example, in DE-OS 2 455 762 described,

Neutralization systems, including combinations of an acidic polymer layer and a retardation layer are described, for example, in DE-PS 1 285 310. Such layer combinations can be used in the invention Material be present, for example in the photosensitive part between the transparent Support and the image receiving layer.

Another possibility is to use the neutralization system from an acidic polymer layer and a retardation layer to be arranged on the cover sheet. Of course, these two layers must be in such a Be arranged in order that the alkali of the processing compound first penetrate the delay layer must to get into the acidic polymer layer.

The dye diffusion transfer method of the present invention can advantageously be carried out in or by means of a suitable self-development camera. This can be done e.g. with Be provided devices that make it possible after the exposure of the photosensitive element between this and to distribute a working solution to the cover sheet and that Cover light-sensitive material opaque to the top. Preferably such a camera has two

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provided nip rollers mounted against one another, between which the mono-sheet material is pulled out, the laterally arranged containers are split and their contents between the layers of monosheet material dismiss. As the photosensitive element passes through the nip rollers on both sides through opaque Layers is protected against unwanted exposure, the exposed material can be used immediately after starting be pulled out of the camera during development.

To process the imagewise exposed monosheet material, the photosensitive element is brought into contact with the aqueous-alkaline working solution. Here will be the imagewise exposed silver halide emulsion layers are developed in the presence of the developer, wherein an image-wise distribution of oxidation products of the developer in accordance with the silver image thus formed r compound is generated, which oxidizes the associated coloring compound, whereupon from the imagewise Distribution of non-oxidized coloring compound under the action of the activator or developer alkali the diffusing dye is split off.

The aqueous-alkaline working solution can increase the viscosity Contain additives, e.g. hydroxyethyl cellulose. Furthermore, in the working solution in a known manner Development accelerators, stabilizers, silver salt solvents, fogging agents, antioxidants and others Supplements may be included.

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- 4 * - ■

The invention has been explained above by means of examples in which the photographically effective group is a diffusing dye or a diffusing dye precursor. However, other embodiments are also conceivable in which the photographically effective group is, for example, an antifoggant, a development inhibitor, a hardening agent, a developing agent or a development accelerating agent. In all of these cases, the photographically active group is set free in terms of images, that is _, "in accordance with the image-wise distribution of undeveloped silver halide when using negative emulsions."

Embodiment 1

On a transparent cellulose triacetate support were in the following order a pickling layer, a light-reflecting layer and a light-sensitive silver halide emulsion layer applied:

Pickling layer:

3.75 g of a copolymer of one part styrene and one part maleimide of Ν, Ν-dimethyl-N-hexadecyl-NW-aminopropyl-ammonium bromide were dissolved in 15 ml of ethanol and this solution was stirred into 75 ml of 5% gelatin solution and homogenized . After addition of 2.6 ml of 5! Täiger saponin and 1 ml of 2 #iger Mucochlorsäürelösung aqueous was adjusted to a common pouring viscosity (ca. 11 mPa.s) and the solution was coated at 40 ⁰ C in a dipping process onto the support (casting speed 5 m / min).

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- 45 -

Light reflecting layer:

A slurry of 42 g of TiOp in 20 ml of water was dispersed with the addition of 5 ml of 5% aqueous solution of sodium dodecylbenzenesulfonate and 5 ml of 5% aqueous saponin solution in 150 ml of 8% aqueous gelatin solution. 1 ml of 2% mucochloric acid solution was added the dispersion to a viscosity of 13 mPa 's is set at 40 ⁰ C and the dipping method on the dried coated mordant layer (casting speed of 5 m / min) "

Silver halide layer:

1 mol of each of the oxidizable compounds listed in the table below was dissolved in 3 ml of caprylic acid diethylamide and 3 ml of ethyl acetate and dispersed in 25 ml of 5% gelatin solution with the addition of 5 ml of 5% aqueous solution of sodium dodecylbenzenesulfonate. After further addition of 50 ml of 5 # gelatin and 1 ml of 2% mucochloric acid solution, each of the dispersions was mixed with 18 g of a ready-to-cast silver halide emulsion. This silver halide emulsion was made with 74 g of AgNO, per kg of emulsion; it had an Ag / gelatin ratio of 1: 1.1 and the halide was mainly bromide with 0.67 mole percent iodide. The mixtures were applied to the dried light-reflecting layer at a speed of 5 m / min at 40 ^{° C. in the dipping process.}

After drying, the various samples were exposed to light through a gray-scale filter on the emulsion side, developed in the developer described below at 18 ^° C. for 4 minutes, rinsed and dried.

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-M -

-Sl

Developer:

1.5 g ethylenediaminetetraacetic acid sodium salt 11.5 g borax 1.0 g sodium hexametaphosphate 2.0 g 1-phenyl-pyrazolidone 3.0 g KBr fill up with water to 1000 ml and adjust to pH 12.5 with 1 η NaOH

Fully developed positive color wedges were obtained from each of the samples and were visible through the transparent support. The color densities (D _min and D_ _ax) were measured behind color filters by means of a reflection densitometer and are shown in the following table:

link Color density blue green purple yellow 1
A. min max min max min max 2
11
3
B. mm 0.12 1.38
0.95 1.48 Ω Vji 0.31 1.72
0.25 1.70
0.27 1.69
0.68 1.65 - - 14th 0.15 1.15
0.53 1.30 - -. 0.14 1.54
0.47 1.48

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The table contains a comparison with corresponding dyes from German patent application P 28 23 159.6, which have a hydrogen atom in the o-position to the carbinol carbon atom (R *) instead of a non-deprotonatable one
Contain substituents. The compounds A, B, C and D have the following formulas:

OH

f °

f2

CH-SO ₂ - -f \ - N = N f ~ \ -

OH

V = /

OH

NH-

SO ₂ CH,

OH

\ SA -rtir

^CH 3 "

/ V-NHSO ₂ - /

OH

SO ₂ NH "

0 ₂ N- / ~ \

. OH

CH ₃

SO ₂ CH ₃

-NHSO ₀ / ~ Λ _ NHCOCH,

OH

\ f ») —IhIIuV ₀ - ^ - ί ' ^ \ - V * ii \ j \ J \ Jii.-z

N = N- (Z V

Cl

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-Ss-

OH

D CIL- ^ V- CH-SO ₂ - // VnH-SOrf ^ -W-HC— C-

_ N = N-HC C-CONHCH

CH

, "3

OH

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Claims (12)

Claims A diffusion transfer photographic process in which a photographic material is comprised of at least one photosensitive silver halide emulsion layer and one of this associated non-diffusing oxidizable compound, which in non-oxidized form under the conditions of the alkaline development is subject to a cleavage reaction with the release of a diffusing photographically active substance and which in oxidized form is not subject to the above-mentioned cleavage reaction or is subject only to a much lesser extent than in unoxidized form, imagewise exposed and developed with a silver halide developing agent wherein the silver halide developing agent in oxidized form oxidizes the oxidizable compound and thereby converted into a form which cannot be split or only slightly split by alkali, while from the pictorial form Distribution of non-oxidized oxidizable compound as a result of cleavage by alkali which is photographically active substance is set free, characterized in that as a non-diffusing oxidizable Compound a compound of the following formula is used: R ¹ R ^2
R X / C-SO ₂ - (X) _1n -A r5 A-G 1618. ORfGINAL INSPECTED 030028/007 7 2854948 S- where mean: A the remainder of a photographically effective group; X is a bivalent link of the formula -R- (L) - (R) -, in which R is an alkyl radical having 1-6 carbon atoms or an optionally substituted arylene or aralkylene radical and where the two radicals R can have the same or a different meaning; L = -0-, -CO-, -CONR ⁶ -, -SO ₂ -NR ⁶ -, -0-CO-NR ⁶ - (R ⁶ = hydrogen or alkyl), -S-, -SO- or -SO ₂ -; p = 0 or 1;
q = 0 or 1; m 0 or 1; 2
Y and Y (identical or different) groups which, owing to their interaction with one another, can be oxidized to form a p-quinoid system; however, Y ^ is not a disubstituted amino group -N (R) ₂ ; R is an optionally substituted hydrocarbon radical; R is hydrogen or an optionally substituted one Hydrocarbon residue; 2 R is a substituent as defined for R, a group / l tion, which together with R is a fused-on heterocyclic or carbocyclic, optionally aromatic Ring completed, or OH, halogen, amino, A-G 1618 030028/0077 Alkylamino, dialkylamino, including cyclic Amino groups, acylamino, alkylthio, alkoxy, aroxy or suIfο; R. an optionally substituted hydrocarbon radical, or a grouping which together with R a fused-on heterocyclic or carbocyclic, optionally aromatic ring completes; R ^{5 is} an optionally substituted hydrocarbon radical 13 4 and where at least one of the substituents R, R, R and contains a diffusion-proofing residue. 2. The method according to claim 1, characterized in that A is the remainder of a diffusing dye or Dye precursor means. 3 * Method according to claim 1, characterized in that as a non-diffusing oxidizable compound Compound of the following formula is used: A-G 1618 030028/0077 R ² R ¹
OH \ / ^R OH
where mean: A is the remainder of a diffusing dye or dye precursor; X is a bivalent link;
m 0 or 1; R is an optionally substituted hydrocarbon residue; 2
R is hydrogen or an optionally substituted hydrocarbon radical; ■ χ 2 R ^ a substituent as defined for R, a Grouping which, together with R, is a fused-on heterocyclic or carbocyclic, optionally complete aromatic ring, or OH, halogen, amino, alkylamino, dialkylamino .. including cyclic amino groups, acylamino, alkylthio, alkoxy, aroxy or sulfo; R is an optionally substituted hydrocarbon radical or a group which, together with Rr, completes a fused-on heterocyclic or carbocyclic, optionally aromatic ring; A-G 1618 030028/0077 R ^{5 is} an optionally substituted hydrocarbon scraps of fabric L at least:
and R contains a residue which makes it diffusible. 1 3 4 and where at least one of the substituents R, R, R 4. The method according to claim 1, characterized in that in the formula of claim 1 R is hydrogen. 5 «The method according to claim 1, characterized in that in the formula of claim 1, R and R ^ each have one Mean alkyl radical. 6. The method according to claim 1, characterized in that in the formula of claim 1 R ^ is an n-propyl radical means. 7. Photographic recording material for color diffusion transfer process with at least one light-sensitive silver halide emulsion layer and a non-diffusing one associated therewith coloring compound, characterized in that as a non-diffusing coloring compound Compound of the following formula is included: γ ^{2 1} C, ^r2 Y ¹ where mean: A-G 1618 030028/007 7 2654946 A the remainder of a photographically effective group; X is a bivalent link of the formula -R- (L) - (R) - ,. in which R is an alkyl radical with 1-6 carbon atoms or an optionally substituted arylene or aralkylene radical and in which the two radicals R can have the same or different meanings;
L = -0-, -CO-, -CONR ⁶ -, -SO ₂ -NR ⁶ -, -0-CO-NR- (R ⁶ = hydrogen or alkyl), -S-, -SO- or -SO ₂ -; p = 0 or 1;
q = 0 or 1; m 0 or 1; Y ¹ and Y ² (identical or different) groups which, because of their interaction with one another, can be oxidized to form a p-quinoid system, but τ is not a disubstituted amino group -N (R ⁸ ) ₂ ; R is an optionally substituted hydrocarbon. Scraps of cloth; R is hydrogen or an optionally substituted one Hydrocarbon residue; R ^ a substituent as ^{defined for R 2} , a group which, together with R, completes a fused heterocyclic or carbocyclic, optionally aromatic ring, or OH, halogen, amino, alkylamino, dialkylamino, including cyclic amino groups, acylamino, alkylthio, alkoxy, aroxy or SuIfο; A-G 1618 030028/0077 R ^ is an optionally substituted hydrocarbon rest, or a group which together with R ^ a fused heterocyclic or carbocyclic, optionally aromatic ring completed; R ^{5 is} an optionally substituted hydrocarbon radical 13 4 and where at least one of the substituents R, R, R and R ^{5 contains} a radical which makes it resistant to diffusion. 8. Material according to claim 7, characterized in that A denotes the remainder of a diffusing dye or dye precursor. 9. Material according to claim 7, characterized in that a compound of the following formula is used as the non-diffusing oxidizable compound: R ² R ¹ H ν / OH
where mean: A is the remainder of a diffusing dye or dye precursor; X is a bivalent link; ". m 0 or 1; A-G 1618 0300 28/007 7 R is an optionally substituted hydrocarbon rest; R is hydrogen or an optionally substituted one Hydrocarbon residue; R ^ a substituent as defined for R, a Grouping which, together with R, is a fused-on heterocyclic or carbocyclic, optionally completes the aromatic ring, or OH, halogen, amino, alkylamino, dialkylamino including cyclic amino groups, acylamino, alkylthio, alkoxy, aroxy or sulfo; R is an optionally substituted hydrocarbon radical, or a group which, together with R, is a fused heterocyclic or carbocyclic, optionally aromatic ring completed; R is an optionally substituted hydrocarbon radical and wherein at least one of the substituents R ¹ , R ³ , R ⁴ and R contains a radical which makes it resistant to diffusion. 10. Material according to claim 7, characterized in that in the Fo:
means. 2
in the formula of claim 1 R is hydrogen A-G 1618 030028/0077 2854945 11. Material according to claim 7, characterized in that in the formula of claim 1, R and R each have one Mean alkyl radical. 12. Material according to claim 7, characterized in that in the formula of claim 1 R is an n-propyl radical means. A-G 1618 03002 8/0077