DE2406664A1 - PHOTOGRAPHIC COLOR DIFFUSION TRANSFER PROCESS - Google Patents

Description

AGFA-GEVAtERTAG

PATENT DEPARTMENT

LEVERKUSEN
HS / MB

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 for this, the new diffusion-resistant, coloring compounds contains.

Among the heretofore known methods of producing color photographic images by the color diffusion transfer method, have recently become increasingly important, which are based on the use of diffusion-resistant embedded Coloring compounds are based, from which dyes or dye precursors that diffuse during development image-wise split off and transferred to an image-receiving layer.

The coloring compounds suitable for this purpose include, for example those described in DT-PS 1 095 115 non-diffusing Color couplers to be counted in the development as a result of a reaction with the oxidation product of a a primary aromatic amine, a preformed color developing agent or a color coupling agent Set the generated dye in diffusing form in freedom. The selection of the required developer compound is limited naturally on color developer.

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Furthermore, reference is made here to those described in DT-OS 1 930 215 indicate non-diffusing coloring compounds that have a cleavable hydrazone group contain pre-formed latently diffusible dye residue linked to a residue that makes it diffusible. These connections are not to be referred to as color couplers, and it has also been found that the choice of developer compounds, which are required to release the diffusing dye residue, by no means to the usual color developer is limited, but that black-and-white developers, e.g. pyrocatechins, are also very useful.

DT-OS 1 772 929 also describes non-diffusing colored compounds with a special grouping, which enter into an oxidative ring closure reaction during development and thereby a pre-formed dye residue in diffusing Set form in freedom. The compounds presented there can be divided into two groups. The connections One group needs a common color developing agent for development, with its oxidation product they couple and in a subsequent ring-closing reaction the Set pre-formed dye residue in diffusing form in freedom. The compounds of the other group are themselves silver halide developing agents and can therefore also in the absence of further developer compounds in the oxidized Form the aforementioned ring-closing reaction with the release of the to enter into diffusing dyes.

Finally, the non-diffusing ones should be mentioned at this point coloring compounds of DT-OS 2 242 762. These are sulfonamidophenols and sulfonamidoanilines, those after the oxidation which took place during development under the influence of the developer alkali with release diffusing dyes are split.

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The coloring compounds mentioned above all work negatively, i.e. the image-wise distribution of the released diffusing dye is formed when using conventional (negative working) silver halide emulsions in Correspondence with the negative silver image produced during development. To produce positive dye images it is necessary hence the use of direct positive silver halide emulsions or otherwise the use of an appropriate reversal process.

The object of the present invention is to provide new non-diffusing coloring compounds for the color diffusion transfer process to propose that deliver an increased dye yield with the same layer load or vice versa to produce the same dye density with less coloring compounds and less silver halide in terms of quantity get along.

It has now been shown, contrary to expectations, that the splitting off of the sulfonamide group after oxidation in no way affects such Compounds is limited to the aromatic.Hing in the p-position carry a hydroxyl, amino or alkylamino group to the sulfonamide group, but also an o- or p-position Sulphonamide group or carbonamide group is a sufficiently activating one Exerts influence on the ring system.

The present invention relates to a color diffusion transfer photographic process for producing colored ones Images comprising a photographic material having at least one light-sensitive silver halide emulsion layer and one of these associated, non-diffusing, color-giving sulfonamidoaryl compounds, which in oxidized form in the alkaline Developer medium capable of releasing a diffusing dye, exposed imagewise and with a silver halide developing agent is developed with the silver halide developing agent in oxidized form, the color-giving sulfonamidoaryl compound is oxidized and the latter as a consequence of this Oxidation with the production of an imagewise distribution of the

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released diffusing dye by the developer alkali is cleaved, characterized in that the non-diffusing arylsulfonamido compound of the following formula is equivalent to:

Y-NH-Ar-NH-SO ₂ -X

where mean:

Ar is an arylene radical such that the group Y-NH- is bonded to the group -NH-SO ₂ -X via a chain of n (n = 1,2,3,4) vinylene groups which are part of the arylene radical;

X is the remainder of a dye or dye precursor Y — COR or —SO ₂ R

R is an alkyl, aryl or heterocyclic group, optionally can be further substituted

In the simplest case, the arylene radicals Ar represent a phenylene radical, e.g. a p-phenylene radical. You can also use multinuclear be aromatic groups, e.g. a 4,4'-biphenylene group, a 1,4-naphthylene group, a 1,5-naphthylene group or a 9,1O-anthracenylqgpxppe. Of course, the Arylene groups carry one or more further substituents in order to facilitate the oxidation of the coloring compounds, e.g., alkyl, alkoxy, aryl, or acylamino. Similarly, among the above-mentioned vinylene groups, there are groups represented by the following formula

- CR ^! = CR'-

to be understood in which the two radicals R ^{1 can be} identical or different and denote hydrogen or, for example, one of the aforementioned substituents; alternatively, two radicals R 'of the same or different vinyl group together can represent the carbon atoms required to complete the arylene group.
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The radical R can perform various functions in the context of the present invention. It can, for example, be a residue which gives the coloring compound sufficient diffusion resistance. The fact that the radical R is _{split off together with the -CONH- or -SO 2} -NH- group in the course of development can also be used for coloring if R has the meaning of a dye radical. In this case, for example, the radical R is an aryl group which is further substituted so that it contains a chromophoric group. R can be the same dye residue as X, so that in cases Y = -SOgR the two residues split off imagewise during development are identical and thus have the same color. It is evident that in this case an increased yield of diffusing dyes is achieved per equivalent of the giving compound compared to previously known coloring compounds. The dye residues X and R can, however, also be structurally different and therefore also be different in shade. With a suitable selection of the two dye residues, a color correction can be achieved in this way in order to set a desired hue. The radical R can furthermore mean any group which, if it is present in diffusing form after cleavage, has a certain activity and the effect of which is desired in terms of image. Examples thereof are functions as a development inhibitor, a stabilizer, a silver salt solvent and the like.

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 diffusion-resistant solubilizing group, for example, in the radical R. A further possibility ^ a difftisionsfestmachenden residue in the molecule of the coloring compound to _introduce} is the arylene group Ar ,,: select those which diffusion resistance already in a suitable manner by a Radical are substituted. It is not critical whether the diffusion-proofing residue is split off during development, since apparently a chionidic compound with an extremely low diffusion tendency is derived from the arylene group.

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2 ^ 06664

iitelit.

! Particularly suitable coloring compounds according to present invention correspond to the following formula II

II Y-NH-

X and Y have the meanings already given;

Z denotes hydrogen or one or more identical or different substituents, e.g. alkyl, AHioxy, mono- or dialkyl amide, where the alkyl radicals can have up to 20 carbon atoms, aryl, e.g. phenyl, aroxy, e.g. phenoxy, acylamino, where the Acyl radicals are derived from aliphatic or aromatic carboxylic or sulfonic acids; and

b denotes hydrogen or one of the radicals mentioned under Z; or both b together do the rest to complete one mean fused aromatic ring system.

Coloring compounds of the following formula III are very particularly preferred:

¹¹¹ R ₁ -SO ₂ -NH- ^ ^> - NH-SOp-X

CL

wherein X has the meaning given;

R ₁ denotes an expression-proofing radical or the radical of a dye or dye precursor, preferably the radical X; and

₂ and R, are identical or different radicals, namely alkyl with up to 20 carbon atoms; preferably with up to 4 carbon atoms.

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Sufficient diffusion resistance of the coloring compounds can already be given if Y or R ₁ denotes a dye residue, even if Z (formula II) or R ₂ and R ^ (formula III) contain no longer alkyl residues, because then the molecule depends on the dye residue can be of sufficient size. Otherwise there is the possibility of _{making the coloring compounds sufficiently resistant to diffusion by selecting radicals Z or R 2} and R ^ of a suitable size.

Radicals which make it diffusion-proof are those radicals which make it possible to use the compounds according to the invention in the ones customarily used in photographic materials. to store hydrophilic colloids in a diffusion-proof manner. Organic radicals which generally contain straight-chain or branched aliphatic groups and optionally also isocyclic or heterocyclic aromatic groups with generally 8-20 carbon atoms are preferably suitable for this purpose. These radicals are connected to the rest of the molecule either directly or indirectly, for example via one of the following groups: -NHCO-, -NHSO ₂ -, -NR-, where R is hydrogen or alkyl, -0- or -S-. In addition, the diffusion-proofing radical can also contain water-solubilizing groups, such as, for example, sulf groups or carboxyl groups, which can also be present in anionic form. Since the diffusion properties depend on the molecular size of the total compound used, it is sufficient in certain cases, for example if the total molecule used is large enough, to also use shorter-chain radicals as "diffusion-proofing radicals".

Dye tests are basically the remains of dyes All dye classes are suitable, provided they are sufficiently diffusible in order to be able to diffuse through the layers of the photosensitive material into the image-receiving layer. For this purpose, the dye residues can be provided with one or more water-solubilizing groups. As a water-solubilizing agent Groups are suitable, inter alia, carboxyl groups, sulfo groups, sulfonamide groups and aliphatic or aromatic hydroxyl groups. However, the sulfonamide group remaining in the dye after cleavage gives the dye

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substance molecule already has a considerable tendency to diffuse in the alkaline medium, so that the presence of additional water-soluble agents Groups is not essential. Of dyes which are particularly important for the process according to the invention are suitable, for example: azo dyes, anthraquinone dyes, phthalocyanine dyes, indigoid dyes and triphenylmethane dyes.

Among the residues of dye precursors are the residues of such To understand compounds that occur in the course of photographic processing by conventional 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 sense can be leuco dyes, Couplers or dyes that are converted into other dyes during processing. Provided not a distinction between dye residues and the residues of dye-off precursors is of essential importance, the latter should also be understood in the following by the term dye residues.

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Examples of color-changing compounds according to the invention are the following:

Connection No. 1

Carry over color

OCH ₃

gel

HC

JTi

CONH-CH ^

Connection No. 2

OCH

-NH-SO ₂ -X ₂

blue green

(CH ₃ ) ₂ CH-NH 0

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OCH

OCH (CH ^),

Connection No. 4

Compound No. 5

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Connection No. 3

Carry over color

OCH

-NH-SO ₂ -X ₃

OCH, purple

-CO-NH-

OC ₂ H

-NH-SO ₂ -X ₃

₂ H ₅ purple

X ₃ -SO ₂ -NH-

- NH-SO ₂ -X ₃ purple

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Compound No. 6

Carry over color

- NH-SO ₂ -X ₃ purple

Compound No. 7

CH

' ^NH "x

OCH

Compound No. 8

.OC ₂ H ₅

OC ₂ H ₅

Compound No. 9 purple

purple

OC ₄ H ₉ -n

X ₃ -SO ₂ -NH- ^ y x> -nh-so ₂ -x ₃

0C ₄ H _g -n purple

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Compound No. 10

• 'V'

^0C 12 ^H 25 ~ ⁿ

- NH-SO ₂ -X ₃

Carry over color

purple

Compound No. 11 X ₃ -SO ₂ -NH

-SO ₂ -X ₃ purple

Compound No. 12 X ₃ -SO ₂ -NH-

OC ₅ H ₁ -

2 5-purple and yellow

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Preparation of the coloring compounds according to the invention

General way of working

The arylamine or arylenediamine in question is dissolved or suspended (or optionally salts thereof, e.g. HCl salt) in 5 to 50 times the amount of anhydrous pyridine and contributes under Stir at room temperature a little more than the theoretically required amount of sulfochloride or sulfobromide of the relevant Dye or dye precursor, in which case a pyridine complex of the sulfhalide may precipitate. To When the reaction has ended, usually after a few hours, any undissolved material is suctioned off and the pyridine solution is added while stirring slowly with enough water (water volume usually approximately equal to pyridine volume) that the desired sulfonamidoaryl compound precipitates, while the by-product sulfonic acid of the dye or dye precursor is in solution remain. It is cooled in an ice bath, filtered off with suction, washed with pyridine / water and dried or slurried with a suitable low-boiling point Water-miscible organic solvents such as acetonitrile, sucks off again and dries.

If the reaction is followed by thin-layer chromatography, then one can observe that the two amino groups of arylenediamines implement one after the other. This makes it possible to introduce two different radicals into the compound.

Example: Establishing connection no.12

3.9 g of 2,5-diethoxy-1,4-phenylenediamine in 50 ml of dry pyridine are mixed with 11.2 g of the dye sulfochloride in portions with thorough stirring A shifted. The mixture is stirred for a few hours

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after, sucks off and the clear filtrate is mixed with stirring:; o a lot of water that the intermediate product B precipitates. This is filtered off with suction, washed with water and dried.Yield: H, 6 g, melting point 233-235 ° C (decomp.)

3.4 g of dye sulfochloride C are added in portions to 3.2 g of B in 50 ml of dry pyridine with thorough stirring. After several hours, enough water is added to the reaction solution with stirring for compound no. 12 to precipitate. This is filtered off with suction, washed with water and dried. ., Yield 4.3 g, mp 265-266 ⁰ C (dec.) Compound No. 12 60 of the firm Merck (grain size from 0.063 to 0.200 mm) by column chromatography on silica gel to be cleaned; Eluent chloroform.

The isolation of intermediate B indicated can be verified will. In this case, the dye sulfochloride C is added directly to the filtered pyridine reaction solution Dye sulfochloride A with 2.5-diethoxy-1,4-phenylenediamine.

A CH ₃ NHCO _n N = N

^B N = N

N ^ ^ OH

OC ₂ H ₅

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OH N = N Λ, I. sy Ns / Κ / χ CH, (CH ₃ ) ₂ CH-O

SOpCl

Production of 2-amino-5-hexadecylsulfonamido-1,4-dimethoxybenzene (Intermediate for compounds No. 1 -3)

Level 1 ; 2-acetamido-5-hexadecylsulfonamido-1,4-dimethoxybenzene

To a solution of 42 g of 2-acetamido-5-amino-1,4-dimethoxyt> enzene 65 g of hexadecyl sulfochloride are added to 250 ml of anhydrous pyridine at room temperature and the mixture is stirred for 1 hour.

After dilution with a little water, it is stirred on ice and acidified with concentrated hydrochloric acid. The precipitate is suctioned off, stirred in a little acetonitrile, suctioned off again,

washed with acetonitrile and getrocknet.Ausbeute 79,4g, mp 139-140 ⁰ C.

Step 2: 2-Amino-5-hexadecylsulfonamido-1,4-dimethoxybenzene

74.3 g of the product from step 1 are refluxed in 500 ml of ethanol with 24.8 ml of concentrated hydrochloric acid until no more starting material can be detected (approx. 4-6 hours). The product precipitates on cooling. It is filtered off with suction and dried over potassium hydroxide in vacuo. Yield 67 g, decomp. at approx. 178-180 ⁰ C.

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Manufacture of 2.5-diamino-1.4-didodecyloxybenzene (intermediate product for connection no.10)

Stage 1: 2-nitro-1,4-didodecyloxybenzene

To a suspension of 67 g of hydroquinone didodecyl ether (described in US Pat. No. 2,067,960) in 1000 ml of glacial acetic acid, 11.7 ml of nitric acid with a density of 1.39 are added dropwise at room temperature while stirring. The hydroquinone ether goes into solution and its nitro compound separates out. After stirring overnight, the filtrate is suctioned off, the filtrate is concentrated in vacuo to about 1/4 of its volume, suctioned off again and the combined filter residues are dried in vacuo over potassium hydroxide. Yield 69 g, mp 34-36 ⁰ C.

Step 2: 2-amino-1,4-didodecyloxybenzene

24.6 g of the product from stage 1 are dissolved in 200 ml of tetrahydrofuran at 30-35 ° C under 50 atm pressure in the presence of Raney nickel catalytically hydrogenated. The hydrogenation solution filtered off from the nickel is used directly in stage 3. A small A sample of the solution left a solid residue with a melting point of 54 ° C. on evaporation.

Step 3: 2-acetamido-1,4-didodecyloxybenzene

The filtered hydrogenation solution from stage 2 is mixed with 6.3 ml of acetic anhydride and left to stand for a few hours, shaking occasionally. The product is dropped 1-2 times Volume of acetonitrile, sucks off and dries. Yield 22, m.p. 68-69 ° C.

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Level 4; 5-nitro-2-acetamido-1,4-didodecyloxybenzene

The product from stage 3 (22.8 g) is suspended in 250 ml of glacial acetic acid. 4.9 ml of nitric acid with a density of 1.39 are added dropwise at room temperature with stirring, the mixture becoming mushy. After adding a further 50 ml of glacial acetic acid, the mixture is stirred for a few hours, filtered off with suction, the filter residue is slurried twice with acetonitrile, filtered off with suction and dried. Yield 20.5 g, m.p. 70 - 71 ⁰ C.

Step 5: 5-nitro-2-amino-1,4-didodecyloxybenzene

4.6 g of the product from stage 4 are refluxed for a few hours in ethanol with 1.5 ml of concentrated hydrochloric acid, until starting material is no longer detectable. To set the mixture with strong caustic soda neutral to alkaline, falls with plenty of water, the precipitate is suctioned off, washed with water, stirred with acetonitrile, filtered off again and trocknet.Ausbeute 4.0 g, mp 85-86 ⁰ C.

Level 6: 2.5-diamino-1.4-didodecylaxybenzene

The product from stage 5 (4.0 g) is dissolved in 250 ml of warm ethanol and at 50 ⁰ C under 50 atm. Pressure catalytically hydrogenated with Raney nickel. After concentration of the extracted from the nickel hydrogenation is obtained 2.8 g of product, mp 75-76 ⁰ C.

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* ff

The coloring compounds according to the invention are added to the casting solutions for the layers of the photographic material incorporated by any of the usual methods. The per liter casting solution The amount of coloring compound used varies within relatively wide limits, the most favorable concentration being is determined by means of simple experiments. For example, per liter of casting solution 5 to 80 g, preferably 20 to 40 g of coloring compound used.

The assignment required to achieve the desired effect between diffusion-resistant coloring compound and silver halide can be produced, for example, that the diffusion-resistant compounds using existing water-solubilizing groups from aqueous-alkaline Solutions in the casting solutions are introduced The non-diffusing Coloring compounds can, however, also be introduced into the layers by one of the known emulsification processes will. Such methods are for example in the English patents 791 219 and 1,099,414 to 1,099 described. In a further embodiment it can for example It is desirable to share the subject connections with silver halide and, if necessary, developer substances to be stored in the layer in the form of so-called microcapsules, with two or more different sensitivities. light-sensitive silver halide emulsions and the corresponding diffusion-resistant compounds in a single layer are combined in the manner of so-called mixed grain emulsions, as described, for example, in US Pat. No. 2,698,794. The non-diffusing coloring Compounds can be accommodated in a photosensitive layer itself or in an adjacent layer. For example the red-sensitive layer is a compound that splits off a blue-green dye, the green-sensitive layer Layer a purple dye-releasing compound, and the blue-sensitive layer a yellow dye-releasing compound Connection assigned.

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The color-giving compounds according to the invention are at the development of the silver image of developer oxidation products oxidized imagewise and are then subject to the Influence of the developer or activator alkali of a cleavage reaction in which the dye residues are in a diffusing form be set free as dye sulfonamides. The usual photographic developer compounds are used for development suitable as long as they are able to oxidize the coloring compounds according to the invention in oxidized form. Examples of suitable developers are:

Hydroquinone

N-methylaminophenol

1-phenyl-3-pyrazolidone

1-phenyl-4,4-dimethyl-3-pyrazolidone>

Ascorbic acid

Aminophenols

N yN-diethyl-p-phenylenediamine
N-ethyl-N-hydroxyethyl-p-phenylenediamine and 3-methyl-N, N-diethyl-p-phenylenediamine

It is particularly important to note that the choice of developer substances in the method according to the invention is not limited to color developers, but also conventional black-and-white developers can be used, which is to be regarded as an advantage because of the lower tendency of the latter to discolour is. The developers may already be contained in the layers of the color photographic material, where they will pass through the alkaline activator liquid, or in the alkaline processing liquid or paste.

Since the pictorial distribution of the released during development diffusing dye coincides with the developed silver image, it is necessary to produce positive colored ones Transfer images of the use of direct positive SiI overhalide emulsions or, if conventional negative emulsions are used, the use of a suitable reversal process .

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One such reverse process is the silver salt diffusion process to disposal. The photographic inversion using the silver salt diffusion process for generation of positive color images using conventional color couplers is disclosed, for example, in U.S. Patent 2 763 800. By exchanging the color couplers for the mentioned coloring compounds, one comes to one photosensitive element used for dye diffusion transfer process suitable is. Such a photosensitive element has, for example, at least one combination on of a light-sensitive silver halide emulsion layer and a binder layer assigned to it, contains the development nuclei for physical development and a coloring compound.

During development, the silver halide photosensitive emulsion layer the exposed portion of the silver halide is chemically developed; the unexposed portion becomes transferred into the associated binder layer containing development nuclei by means of a silver halide solvent and physically developed there. If a developer is used for physical development who is skilled in oxidized form as a result of a reaction with the coloring compound present in this layer a diffusing one Is able to set free dye, then there is the formation of an image-wise distribution of diffusing Dyes that can be transferred to an image-receiving layer and form a positive colored image there.

In the case of the reversal using compounds which split off imagewise development inhibitors, there is the photosensitive effect Element of at least one layer combination of a light-sensitive Silver halide emulsion layer and a second unexposed developable emulsion layer, which is the color-imparting Connection contains. The photosensitive silver halo

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Genidemulsionsschicht is made with, for example, color developers developed in the presence of certain compounds which inhibit development when reacting with oxidized color developer Splitting off substances. The development-inhibiting substances that are imagewise set free in the light-sensitive layer diffuse into the adjacent, unexposed, developable emulsion layer and image-wise inhibit the development there. Included the uninhibited (positive) parts of the unexposed developable emulsion layer are caused by the remaining developer developed, whose oxidation products then with the non-diffusing coloring compounds according to the invention with the release of diffusing dyes .reagieren that image-wise the image receiving element are transmitted. Suitable compounds which react with color developer oxidation products Splitting off development-inhibiting substances are, for example, the well-known DIR couplers (DIR = development inhibitor releasing), which are color couplers which contain a cleavable inhibitor residue in the coupling point. Such DIR couplers are described, for example, in U.S. Patent 3,227,554 beach ·, '·? - ben.

Another group of compounds that reacts with color developer oxidation products to produce development-inhibiting substances split off is described in U.S. Patent 3,632,345. This acts they are not color couplers. Accordingly, when the development-inhibiting substances are released, none are produced either Dyes. According to DT-PS 1 229 389, suitable substituted, non-diff founding hydroquinone compounds are used, which in the reaction with developer oxidation products to the corresponding Quinones are oxidized and thereby split off development-inhibiting mercaptans.

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As direct positive silver halide emulsions are principle all direct positive silver halide emulsions are suitable, which with a simple development a positive Generate silver image and a corresponding image-wise distribution of developer oxidation products. In In the case of typical silver halide emulsions, the question arises in which a developing fog has been produced by exposure or by chemical treatment, which under Compliance with certain conditions in the imagewise exposure is destroyed imagewise. In the unexposed areas the fog is retained, so that a direct positive silver image is obtained in the subsequent development, and in accordance therewith, an image-wise distribution of diffusing dye when the direct positive silver halide emulsion a coloring compound according to the invention is assigned.

Another group of direct positive silver halide emulsions, which are preferably used according to the present invention includes the so-called unveiled direct positive silver halide emulsions that are photosensitive predominantly in the interior of the silver halide grains. In the imagewise exposure of this In emulsions, a latent image is formed predominantly in the interior of the silver hulogenide grains. The development of such Unfogged direct positive silver halide emulsions are made under different conditions, however, whereby a fog is produced predominantly in the unexposed areas and a positive silver image during development is being developed. The unveiled direct positive silver halide emulsions are characterized by that exposed samples are developed using a typical surface developer of the following composition:

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p-hydroxyphenyl glycine ^ 10 g Sodium carbonate (crystallized) 100 g make up to 1 000 ml with water

preferably no silver image, or only one with a very low density, while using an inner nucleation developer of the following composition:

Hydroquinone 15 g

Monomethyl p-aminophenol sulfate 15 g Sodium sulfite (anhydrous) 50 g

Potassium bromide 10 g

Sodium hydroxide 25 g

Sodium thiosulphate (crystallized) 20 g make up to 1 000 ml with water

° Λη silver image with sufficient density is created.

The selective obfuscation of the imagewise exposed, unveiled Direct positive emulsions can be treated with a fogging agent before or during processing be made. Suitable fogging agents are reducing agents such as hydrazine or substituted ones Hydrazines. Reference is made, for example, to US Pat. No. 3,227,552.

Unfogged direct positive emulsions are, for example, those that are inside the silver halide grains Have defects (US Pat. No. 2,592,250) or silver halide emulsions with a layered grain structure (DT-OS 2 308 239).

"Assignment" and "assigned" ¹ mean that the mutual arrangement of the silver halide emulsion and the coloring compound is of such a nature that an interaction between them is possible which allows an imagewise correspondence between the silver image formed and the imagewise distribution of the diffusing dye released .

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Appropriately, here the assigned, coloring Compound incorporated in the silver halide emulsion itself or in a layer adjacent to the silver halide emulsion layer, this adjacent layer preferably behind (viewed in the direction of the incident light during exposure) the oilberhalide emulsion layer lies.

To carry out the dye diffusion transfer process, According to 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 them, and a Express receiving element in which the desired color image is obtained through the image-wise transferred, diffusing dyes is produced. For this it is necessary that between the photosensitive element and the image receiving element a permanent contact at least for a finite period of time within the development period exists, so that the image-wise formed in the photosensitive member as a result of development Distribution of diffusing dyes can be transferred to the image receiving element. The contact can be made after development has started, or it can already be made be before development begins. The latter is the case, for example, if to carry out the dye diffusion transfer process a material is used in which the photosensitive member 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 photosensitive member from the image receiving element is not provided even after the color transfer has taken place. Such an embodiment is described, for example, in DT-OS 2 019 430.

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

1) a transparent substrate

2) an image receiving layer

3) an opaque layer

4) a photosensitive element with at least one photosensitive element Silver halide emulsion layer and at least one of these associated non-diffusing, coloring compound

5) a delay layer
C) an acidic polymer layer

7) a transparent substrate

The sheet 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_J ) _1, which are then placed on top of one another and with one another
are connected, if necessary using spacer strips, εο that a space for receiving a precisely measured amount of a working fluid is formed between the two parts. The layer elements 5 and 6, which together form the neutralization system, can also, but in the reversed order, between the layer support and the
Image receiving layer of the photosensitive part be arranged.

Means may be provided to pass a working fluid between the photosensitive member and the cover sheet
to be introduced, e.g. in the form of a laterally arranged,
fissile container, which when exposed to mechanical
Forces its contents pours between two adjacent layers of monosheet material.

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A substantial part of the photographic material according to the present invention Invention is the photosensitive element which, in the case of a monochrome transfer process, is photosensitive Silver halide emulsion layer and associated therewith, contains a non-diffusing coloring compound. The non-diffusing connection can be in. one to the silver halide emulsion layer adjacent layer, or in the silver halide emulsion layer themselves, 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 match the predominant one Sensitivity range of the silver halide emulsion layer. In order to produce multicolored transfer images in true-to-life colors, however, the light-sensitive element contains three such assignments of coloring compound and light-sensitive silver halide emulsion layer, wherein in the Usually the absorption range of the coloring compound with; the range of spectral sensitivity of the assigned Silver halide emulsion layer will substantially coincide. Prerequisite for the highest possible sensitivity is then, however, that in each case the coloring combination in a separate binder layer (viewed in the direction of the incident light during exposure) the silver halide emulsion layer is arranged.

Those resulting from the development of a silver halide emulsion Developer oxidation products may of course only affect the assigned coloring compound impact. Separating layers are therefore generally present in the photosensitive element to facilitate diffusion of the developer oxidation products in other unassigned layers effectively prevent. These separating layers can

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e.g. contain suitable substances that interact with the developer oxidation products react, for example non-diffusing hydroquinone derivatives, or if it is the developer is a color developing agent, non-diffusing Color coupler. In a preferred embodiment, the photosensitive element therefore has the following structure (from top to bottom):

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 also be arranged in a different order, wherein however, the assigned layers with the coloring systems must also be exchanged, so that the assignment is retained.

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The one arranged under the photosensitive element The opaque layer is permeable to aqueous alkaline treatment solutions and thus to the diffusing ones Dyes. It essentially has two functions. Firstly, it serves to do that after development leaded in the originally photosensitive element To cover image silver, as well as the color-giving compounds remaining as a color negative, so that at when viewed through the transparent substrate of the light-sensitive part, only the positive color

wear pattern is visible. Second;.: -: closes aie the photosensitive Element on the side of the image receiving layer (downwards) light-tight. The latter is special then of importance if the monosheet material is still in the camera with the alkaline after exposure Brought processing mass into contact, then pulled out of the camera and developed outside the camera shall be.

Layers with sufficient opacity, but more 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 general, 0.5 to 2 / U thick layers are sufficient, those in gelatine 10 to 90 wt .- ^ (based on the total (Dry weight) of carbon black to be sufficient to exclude light during development guarantee. The particle size of the pigments used is relatively uncritical as long as it is not essential to 0.5 / u exceed.

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50983 47 0794

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 creating a white background for the picture. 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 additives apply with regard to the binder, the concentration and the particle size as for the black pigments. The thickness of the cracked pigments cannot be varied depending on the desired color of the substrate. Thicknesses between 2 and 10 / rev are preferred.

instead of the opaque layer can be used in the Monoleaf fluterial, according to the present invention, also Means for producing such an opaque layer between the light-sensitive element and of the image receiving layer, for example in the form of a side container with a Working fluid containing opacifying agents (pigments), which when exposed to mechanical forces its content pours between said layers so that such a rigment layer is formed there.

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

His mordants for acidic dyes are preferably used

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long-chain quaternary ammonium or phosphonium compounds or ternary sulfonium compounds, such as those described in American patents? 271 147 and 3 271 143. Further Certain metal salts and their hydroxides that form with the acidic Pur "o? Tofi'en sparingly soluble compounds, related to ver s '.'.. LiIe dye mordants are

Receiving layer dispersed in one of the usual hydrophilic binders, for example in gelatin, polyvinylpyrrolidone, completely or partially hydrolyzed cellulose esters and the like. Of course, some binders can also act as mordants, for example copolymers or polymer mixtures of vinyl alcohol and N-vinylpyrrolidone as described, for example, in DT-AS 1 130 284, and also those which are polymers of nitrogen-containing quaternary bases, e.g. polymers of N-methyl 2-vinylpyridine, as described, for example, in US Pat. No. 2,484,430. Other useful pickling binders are, for example, guanylhydrazone derivatives of alkyl vinyl ketone polymers as described, for example, in US Pat -OS 2 009 498. In general, however, other binders, for example gelatin, will be added to the last-mentioned binding agents.

As a transparent support for the inventive Monosheet material can use the usual transparent carrier materials used in photographic practice, e.g. films made of cellulose% »t« nL> Polyatiiyl «nt« rephthalate, Polycarbonate or other film-forming polymers, use.

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. 3 / 1-

Due to the alkaline processing masae it becomes light-sensitive Material is set to a relatively high pH (around 11-14), which helps develop and the imagewise dye diffusion is triggered. It It has been found that at this high pH the dyes and thus the images obtained are not particularly good are stable. It is therefore necessary that, after the development is completed, the material should be nearly neutral or is made weakly angry. This can be achieved in a known manner by adding the material contains an acidic polymer layer that is only gradually accessible to the alkaline processing compound in the course of development. Under an acidic polymer layer a binder layer is understood, the polymeric compounds with acid groups, preferably sulfo- or Contains carboxyl groups. These acidic groups react with the cations of the processing compound to form salts and thereby lower the pH of the mass. Of course, the polymeric compounds and thus the acidic groups in the layer mentioned are embedded in a diffusion-proof manner. The acidic polymers are often derivatives of cellulose or derivatives of polyvinyl compounds, but other polymeric compounds can also be used Find use. Suitable acidic polymers are, for example, cellulose derivatives with free Carboxyl group, e.g. cellulose dicarboxylic acid half ester with free carboxyl group such as cellulose acetate hydrogen phthalate, Cellulose acetate hydrogen glutarate, ethyl cellulose acetate hydrogen succinate, Cellulose acetate hydrogenBuccinate hydrogen phthalate, ethers and esters of cellulose, which are further processed Dicarboxylic acid anhydrides or with sulfonic acid anhydrides, modified, for example, with o-sulfobe acid anhydride

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.η.

are, carboxymethyl cellulose, also polystyrene sulfonic acid, Polyvinyl hydrogen phthalate, polyvinyl acetate hydrogen phthalate, Polyacrylic acid, acetals of polyvinyl alcohol with aldehydes substituted by carboxy or sulfo groups are, such as o-, m- or p-benzaldehyde sulfonic acid or carboxylic acid, partially esterified ethylwa-maleimic acid anhydride copolymers, partially esterified methyl vinyl ether-maleic anhydride copolymers and the like,

This acidic polymer layer must contain enough acid groups to maintain the pH of the processing composition from the start 11 to H so low that the material is set to be almost neutral or slightly acidic at the end is (pH 5 to 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 delay layer represents a is alkali-permeable layer, which is preferably made of a polymer inert to alkali, for example consists of polyvinyl alcohol or a partially acetalized polyvinyl alcohol. By suitable choice of thickness and the composition of this retardation layer can delay the pH decrease in the desired way.

Neutralization systems, including lombimationenraus · 1ρ · Γ acidic polymer layer and a retardation layer are described in, for example DT-PS 1 285 310. Such layer combinations

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can be present in the material according to the invention, for example in the photosensitive part between the transparent support and the image-receiving layer. Another option is to use the To arrange a neutralization system consisting of an acidic polymer layer and a retardation layer on the cover sheet. Of course, these two layers must be arranged in such an order that daa The alkali of the processing compound must first penetrate the retardation layer in order to get into the acidic polymer layer to get.

The dye diffusion transfer method of the present invention can advantageously be carried out in or by means of a suitable self-development camera. These can be provided, for example, with devices that make it possible, after the exposure of the photosensitive Element between this and the cover sheet to distribute a working solution and the photosensitive material to cover opaque at the top. Preferably is a similar camera with two stacked against each other Nip rollers are provided, between which the mono-sheet material is pulled out, the laterally arranged Containers are split open and their contents released between layers of mono-sheet material.

Since the photosensitive element after the The nip rollers are protected against unwanted exposure on both sides by opaque layers exposed material can be withdrawn from the camera immediately after the development has started.

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509834 / 079A

For processing the image-wise exposed mono-sheet material the photosensitive element is brought into contact with the aqueous alkaline working solution. This will be in the present of the developing agent, the image-wise exposed silver halide emulsion layers developed, an imagewise one in correspondence with the positive silver image thereby formed Distribution of oxidation products of the developer compound is generated, which is associated with the coloring compound oxidizes, whereupon this splits off the diffusing dye by reacting with the alkali of the activator.

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example 1

A photosensitive element of a photographic material according to the invention was prepared by placing on top of a The following layers were applied one after the other to a transparent carrier made of polyester film (the quantities refer to each on 1m)

1. An image-receiving layer of 3.8 g of octadecyltrimethylammonium-methyl sulfate and 9.5 g gelatin

2. A reflective layer made of 48.5 g TiO ₂ and 4.85 g gelatin

3. A dye layer containing 0.77 g of compound 1 (yellow) 0.1 g carbon black and 2.56 g gelatin

4. A silver bromide emulsion layer made from 3.15 g AgBr and 2.65 g gelatin.

5. A protective layer of 1.3 g gelatin

A transparent cover sheet made of cellulose acetate was placed on the top layer of the photosensitive element. To develop the imagewise exposed photosensitive element, a separable container with an alkaline Working fluid of the following composition is used:

20 g sodium hydroxide

30 g Natrosol HHR 250 (hydroxyethyl cellulose) 0.5 g phenidone
make up to 1000 ml with water

The image set was passed through a pair of nip rollers, the developer paste being distributed between the photosensitive element and the cover sheet. After a development time of 10 minutes at 20 ^° C., the picture element was separated and removed from the

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adhering paste freed. Through the transparent support with the titanium dioxide layer as the image background, a negative yellow dye image of good color quality visible.

Example 2

The procedure described in Example 1 was repeated with the exception that Compound 1 in Layer 3 was performed Compound 2 was replaced. After the same processing as in Example 1, a negative blue-green dye image resulted good color quality.

Example 3

The procedure described in Example 1 was repeated with the exception that Compound 1 in Layer 3 was performed Compound 3 was replaced. After the same processing as in Example 1, a negative purple dye resulted image of good color quality.

Example 4

The procedure described in Example 1 was repeated, with the exception that Compound 1 in Layer 3 passed through each time Compound 4-11 was replaced. After the same processing as in Example 1, negative purple dye images resulted in each case.

Example 5

A multilayer, multicolor photosensitive recording material was produced by placing on a base, consisting of transparent support, layer 1 (pickling layer) and layer 2 (titanium dioxide layer) of Example 1 as follows Layers ■ were worn (the quantities refer to

2
each on Im).

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• 'Λ.

3. A gelatin layer with 1 g of compound 2 (blue-green) and 0.1 g of carbon black

4. A red-sensitive negative-working gelatin-silver bromide emulsion from 3 * 15 g AgBr and 2.65 g gelatin

5. An intermediate layer of 0.25 g of octadecylhydroquinone sulfonic acid and 2.5 g gelatin as a barrier layer for oxidized auxiliary developer.

6. A gelatin layer with 1.4 g of compound 3 (purple)

7. A green-sensitive negative-working gelatin-silver bromide emulsion from 3.15 g AgBr and 2.65 g gelatin

8. A barrier layer for oxidized auxiliary developer, identical to layer 5

9. A gelatin layer with 0.78 g of compound 1 (yellow)

10. A blue-sensitive negative-working gelatin-silver bromide emulsion from 3 * 15gAgBr and 2.65 g gelatin.

11. A protective gelatin layer made from 1.3 g gelatin

The photosensitive recording material was exposed through a color separation wedge and then as in Example 1 The result was a multi-colored negative image of the original with good color separation and good color quality.

Example 6

a) Positive working picture element

The following were applied to the same substrate (transparent carrier, layers 1, 2 and 3 as described in Example 5) Layers applied

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509834 / 079A

240666A

-ί. 1 ''. LiH! GeLatines looks with a rotüerisibillerten, uncovered direct-positive working silver chloride bromide demulsion, Silver application 1.8 g

^l ). No barrier as in example 5

() liine l * urpur color Lo l "f layer as in example 5

f. Cinema gelatin layer with a green-sensitized, non-fogged, direct-positive silver chloride bromide emulsion, silver application 1.8 g

8. No barrier layer as in example 5

9- Kine yellow dye layer as in Example 5

10. A gelatin layer with a blue-sensitive one unveiled direct positive working silver

. chloride bromide emulsion, silver application 1.8 g

11. A protective gelatin layer made from 1.3 g gelatin

b) Cover sheet, consisting of a transparent film made of cellulose triacetate

A stripe of the picture element (a) was identified by a color separation wedge exposed and then in conjunction with a paste bag at one end of the image strip over two spacing strips 18o / U thick and arranged on the side 0.5 cm wide connected to the cover sheet (b) on the layer side to form a picture set.

A paste with the following composition was used as the developer:

25 g of potassium hydroxide
10 ml of benzyl alcohol

5 g of N, N, N ¹ , N ^f , tetramethyl-p-phenylenediamine

1 g acetylphenyl hydrazine
Make up 35 g of hydroxyethyl cellulose to 1 liter with water.

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'509834/079'

In the same processing as in Example 1, a direct positive multicolored image of the original was obtained.

Example 7

Example 6 was repeated, with the exception, however, that in layer 6 instead of 1.4 g of compound 3, 0.8 g of Compound 8 were used. The photosensitive recording material was then exposed as described in Example 6 and developed. In this way, as in Example 6, a direct positive multicolor image was formed in the image-receiving layer received the template.

Example 8

The procedure described in Example 1 was repeated with the exception that Compound 1 was replaced in Layer 3 by Compound 12 was replaced after the same processing as in example 1 resulted in a negative red dye image consisting of yellow and Purple dye.

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Claims (3)

2 ^ 06664 Patent claims: Diffusion transfer photographic process for the production of colored images which utilizes a photographic Material having at least one light-sensitive silver halide emulsion layer and one of these associated non-diffusing, coloring sulfonamidoaryl compounds, which, in oxidized form in an alkaline medium, is able to set free a diffusing dye, imagewise exposed and developed with a silver halide developing agent, this being the coloring agent in oxidized form Sulfonamidoaryl compound oxidizes and the latter as Follow this oxidation to produce an imagewise distribution of the diffusing dye released is split by the developer alkali, characterized in that the non-diffusing sulfonamidoaryl compound corresponds to the following formula: I Y-NH-Ar-NH-SO ₂ -X where mean: Ar is an arylene radical such that the group Y-NH- is bonded to the group -NH-SO ₂ -X via a chain of ή (η = 1,2,3,4) vinylene groups which are part of the arylene radical, χ the remainder of a dye or dye precursor Y -COR or -SO ₂ R. R. An alkyl, aryl, or heterocyclic group. 2. Diffusion transfer photographic process according to Claim 1, characterized by the use of a non-diffusing, coloring Compound of the following formula: II ^ .TTT / • xx -NH-SO ₂ -X A-G 1212 - 40 - 5098 34/0794 where mean: X is the remainder of a dye or dye precursor Y -COR or -SO ₂ R R is an alkyl, aryl or heterocyclic group, Z is hydrogen or one or more identical or different groups Substituents, and b denotes hydrogen or one or more identical or different substituents; or both b together do the rest mean to complete a fused ring system. 3. A diffusion transfer photographic process according to claim 1, characterized by using a non-diffusing one coloring compound of the following formula: ¹¹¹ R ₁ -SO ₂ -NH - <^ _ ^ v> -NH-SO ₂ -X X is a residue of a dye or dye precursor R ^ is a diffusion-proof residue or the residue of a dye or dye precursor, and R ₂ and R are identical or different alkyl radicals with up to 20 carbon atoms; A-G 1212 - 41 - 50983A / 0794