DE2228361A1 - COLOR PHOTOGRAPHIC DIFFUSION TRANSFER PROCESS AND RELATED PHOTOGRAPHIC MATERIAL - Google Patents

Description

AGFA-GEVAERTAG

PATENT DEPARTMENT

LEVERKUSEN _Jftio

0 JUNE 9-1972

Color diffusion transfer photographic process and related photographic material

The invention relates to a color photographic diffusion transfer process, in which a photosensitive material having at least one silver halide emulsion layer is used to form a color image is exposed and developed and in which a dye that has become diffusible through development is intact or partially image-wise transferred to an image-receiving layer, as well as material for carrying out such a method.

In black and white photography, it has long been known to use an exposed silver halide emulsion layer to produce direct positive images to develop into a silver image and the silver halide remaining undeveloped image-wise to be transferred to a receiving layer, where it is, for example, converted into a positive image by a precipitant. These so-called Silver salt diffusion processes have also been tentatively transferred to the field of color photography. In the As a rule, only a diffusion of silver salts takes place, while the dye is generally only used in the rec appears to be formed by chromogenic development.

There are also diffusion processes for producing color photographic ones Negative or positive images known at

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where a color coupler or an already preformed dye diffuses into an image receiving layer. One known method makes use of the fact that the dye formed during the chromogenic development is diffusion-resistant is, while the color coupler on which it is based is in principle diffusible due to its average molecular weight is, in the photosensitive layer in the form of "oil packages", i.e. dissolved in droplets of a high-boiling, low-molecular, practically water-insoluble organic solvent, is embedded in a diffusioris-proof manner. This procedure is for example described in German patents 1,150,278 and 1,272,716. By the nature of the materials needed for diffusion hydrophilic groups and by the nature of the use In this process, however, future developers are forced to work at very high pH values in order to achieve the To achieve diffusion of the coupler. This process leads to azomethine dyes with all of their known disadvantages, e.g. poor durability and poor stability against light.

Another known method makes use of " so-called dye developers, i.e. of compounds that contain a dye residue and a group in the same molecule, capable of developing silver halide. This method is for example in the German patents 1 036 640, 1 111 936 and 1 111 938 for implementation however, this method requires extremely complicated materials. Furthermore, one is through here as well the nature of the hydrophilic caching agents which impart diffusibility Groups - in general these are phenolic hydroxyl groups - forced at very high pH values to work.

In a third color photographic diffusion process, which is described in German patent specification 1095 115, for example is, non-diffusing couplers are used in which in the course of development with color developers, a bond in the coupling position is cleaved, which has a Intermediate member the diffusion-resistant coupler radical with a diffusible dye or second coupler radical or a diffusion-proofing radical with a -an A-G 943 - 2 -

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diffusible coupler residue connects. It will be here the usual types of couplers known in photography, such as pyrazolinone (5) derivatives, phenol or oc -naphtol derivatives and open-chain ketomethylene compounds. Under In the case of the pyrazolinone (5) compounds, the "coupling position" of the coupler molecule is the carbon atom in the 4-position, in the case of the phenols and * C-naphthols also the carbon atom in the 4-position and, in the case of the open-chain ketomethylene couplers, the carbon atom of the methylene group in the grouping -CO-CHp-CO- understood.

When coupling with oxidized color developers, the subatituent becomes split off in the coupling position and either a diffusing AEomethine colorant or, if the coupler part is diffusion-resistant, a diffusing dye that can also belong to a different dye class. The resulting Diffusible dyes diffuse from the photosensitive layer into one in close contact with it located image receiving layer and are fixed here by pickling.

The individual steps of this process have been known for a long time. For example, there is the process of image-wise dye diffusion the Technicolor process based on · In this context reference is also made to BeIa Gaspar's imbibition process. The principle of splitting off residues in the coupling position of color couplers for formation is also known of a color image. This can be seen, for example, from American patents 2,435,616, 2,453,661 and 2,455 169.

If, by linking the individual known process steps, there is undoubtedly a very interesting and technically advanced combination process for color diffusion results, so there are some disadvantages to this process. For example, the diffusing dyes generally represent azomethine dyes as has already been pointed out, and therefore

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accordingly only moderate durability and light intensity. Besides, and this is also the case, so far as this is the case from the coupling position of diffusion-resistant couplers diffusing dyes are split off which are of a different class of dyes belong and can therefore be more lightfast, other serious disadvantages come to light.

The part of the molecule to be split off in the oxidative coupling is linked to the "coupling position" via a "cleavable bond" connected. The following are mentioned as cleavable bonds, for example:

-Hg -, - 0 -, - N = N -, ^ CH-J = CH -, - S- or- -S-S-

The proposed groups do not all prove to be equally beneficial. So are some of them, e.g. the groups -Hg-, -0- and = CH- unsuitable for use in practice because they are split off too slowly. Also is in the appropriate Patents, e.g. in German patent 1,095,115 as a cleavable bond between lightfast dye and diffusion-proof dye Coupler part only specifically discloses the azo bond. However, if the azo group is chosen as the bridge member, Thus, in the reaction with oxidized color developer, nitrogen is produced in a known manner, which in the form of microscopic Some of the bubbles escape from the layer and interfere with the necessary contact between the dye-donor and image-receiving layer. This is particularly the case when working at a higher temperature to accelerate the process.

The thioether group, which is known from the coupling position of couplers in the reaction with oxidized color developer is also very easily split off, but can only be used as a bridge member with disadvantages in this color diffusion process between diffusion-resistant coupler and diffusible dye use part. It is known that mercaptans, which are formed in this reaction, very easily with silver halide either by chemical conversion to silver mercaptides

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react or are adBorptiv held by the silver halide. This fact is used, for example, with the use of EH couplers (couplers releasing development-inhibiting compounds) or DIR coupler ("development inhibitor releasing") use. However, these properties are in line with the requirement for rapid and quantitative diffusion of the released dyes opposite. In DT-OS I 930 215 there is another color diffusion material described, which works with sulfonylamidrazones, which are linked to a dye or a dye precursor on the sulfone group. The dye residues are during development by reaction with the developer oxidation product diffusible and can contribute to the construction of an image in a suitable image-receiving layer.

The sulfonylamidrazones used as color-imparting compounds according to the laid-open specification mentioned are however, they are generally complex connections, the production of which is often cumbersome and, above all, expensive is. Above all, the quaternization of the required N-heterocycles often causes considerable difficulties, if In the heterocycle there is at the same time a residue that makes it diffusible.

The object of the present invention is now to develop a simple color diffusion process associated with the To provide a suitable photographic material which does not have the defects of the aforementioned methods and which is based in particular on easily accessible compounds that can be synthesized cheaply. It now became a color diffusion transfer photographic process found, in which for the production of a color image a material which is in at least one light-sensitive SiI-berhalide emulsion layer or contains a coloring compound in an adjacent hydrophilic colloid layer, imagewise exposed and developed, either the coloring compound itself or one of it during development obtained diffusible cleavage product as color

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fabric or dye precursor imagewise onto an image-receiving layer is transmitted.

The process is characterized by the use of a coloring Compound of the following general formula:

AYZG-NH-NH-SO ₉ - h < Il

in which mean

A the remainder of a dye or dye precursor, or:

a residue that makes it diffusion-proof,

B is an aliphatic or aromatic group, preferably alkyl having 1 to 4 carbon atoms or phenyl, if A is the remainder of a dye or dye precursor or;

the remainder of a dye or dye precursor if A denotes a residue which makes it diffusible.

X is oxygen, sulfur or an imino group (= NR, in which R is hydrogen or an alkyl group)

Y is a chemical bond or linking member such as oxygen, sulfur or an imino- (-NR-, where R Means hydrogen or an alkyl group), carbonyl, sulfonyl, sulfonamide or carbonamide group

y is a chemical bond between Y and C or together with C and X is a heterocyclic group with a 5- or 6-membered hetero ring in which X is nitrogen.

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Suitable heterocyclic groups which are formed by Z, C and X are nitrogen-containing hetero rings to which optionally Benzene rings can be fused, for example the oxazole, thiazole, imidazole, pyrrole, oxadiazole, thiadiazole, Triazole, pyrazole, pyridine, pyrimidine, pyrazine and triazine ring. In addition to the substituent A, of course may also contain water-solubilizing groups, further water-solubilizing groups can be used with the heterocyclic group such as sulfo or carboxyl groups, directly or for example be linked via a short-chain alkyl group.

In principle, the residues of dyes of all dye classes are suitable as dye residues, provided they are sufficiently diffusible to diffuse through the layers of the photosensitive material into the image receiving layer can. Because of this requirement, the dye residues are preferably provided with one or more water-solubilizing groups. Suitable water-solubilizing groups include carboxyl groups, sulfo groups, hydroxyl groups or hydroxyalkyl groups. Dyes which are particularly suitable for the process according to the invention are, for example name: azo dyes, anthraquinone dyes, phthalocyanine dyes, indigoid dyes and triphenylmethane dyes.

The remnants of dye precursors are to be understood as meaning those residues that are formed in the course of photographic processing by customary or additional processing steps, be it by oxidation, be it by coupling or by exposure an auxochromic group in a chromophoric system, for example by saponification, converted into the residues of dyes will. Dye precursors in this sense can be Leuco dyes, "couplers or dyes, which are converted into other dyes in the course of processing. If a distinction between dye residues and the residues of dye precursors is not of essential importance is, the latter should be understood in the following also under the term dye residues. In the same way are under

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Dyes are also to be understood below as dye precursors.

Residues which make it diffusion-resistant are to be regarded as residues which enable the compounds according to the invention to be incorporated in a diffusion-resistant manner in the hydrophilic colloids customarily used in photographic materials. Organic radicals which in general can contain straight-chain or branched aliphatic groups and optionally also isocyclic or heterocyclic aromatic groups are preferably suitable for this purpose. The aliphatic part of these radicals generally contains 8-20 carbon atoms. These radicals are connected to the rest of the molecule either directly or indirectly, for example via one of the following groups: -CONH-, -SO ₂ NH-, -CO-, -SO ₂ -, -NR-, where R is hydrogen or alkyl, -0- or -S-. In addition, the diffusion-proof radical can also contain water-solubilizing groups, such as sulfo 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 when the total molecule used is large enough, to also use shorter-chain radicals as "diffusion-proofing radicals".

With the aid of the compounds according to the invention, the color diffusion transfer process can be carried out basically perform in two different, equally advantageous embodiments, depending on whether the dye residue is in the compound used is represented by A or B.

If B is a dye radical, then A is preferred a diffusion fet-making residue. In this preferred Embodiment will be originally in the layer firmly embedded coloring compounds split in the reaction with developer oxidation products and the dyes or dye precursors are thus released from their anchoring. There If they usually contain one or even more solubilizing groups, they are able to get into the image-receiving layer

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diffuse where they are set with the help of a particle stain can be. The rest of the diffusion-proofing residue remains in the emulsion layer. As in this embodiment of Verfarens Diffusible dyes are only set free in the exposed areas, one obtains when using conventional dyes negative-working silver halide emulsions in the image receiving scanner a negative of the original. The coloring compounds should be as diffusion-resistant as possible in this embodiment be stored in the layers. Since the diffusion resistance decreases with an increasing number of solubilizing groups, the coloring compounds should therefore contain as few such solubilizing groups as possible. On the other hand, however it is to facilitate manufacture and * processing The appropriate materials are beneficial if the coloring compounds have sufficient solubility in aqueous-alkaline Have media. Also, the split off dyes should diffuse as quickly and quantitatively as possible, with a sufficient one Number of solubilizing groups in turn is conducive. Hence, a wonl is a good balance between size the diffusion-resistant radicals and the number of solubilizing groups required to produce the coloring compounds on the one hand, to make it sufficiently resistant to diffusion and, on the other hand, to allow the dyestuffs which are split off to diffuse quickly enough.

It therefore proves to be special in this embodiment It is advantageous that coloring compounds can also be used whose dye residues are not soluble or are numerically less soluble containing making groups as necessary for diffusion, since a solubilizing group is latently present in the molecule which arises from the sulfonyl group during cleavage by developer oxidation products and in the case of the dye part (B) remains. A good diffusibility of the split off dyes is achieved in this way with simultaneous extreme insolubility and thus the diffusibility of the coloring compounds embedded in the layer.

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In a second special embodiment, coloring Compounds used in which A is a dye radical and B is preferably a phenyl or kurakettige alkyl group represents. These compounds are not diffuaionafest and are therefore diffusible in photographic layers in an alkaline medium without any prior reaction. When these layers are developed in the presence of a diffusion-resistant developer, the coloring compounds react only in the exposed areas with the developer oxidation product and are thereby defined imagewise. At the unexposed, that is, the non-developable areas, the coloring compounds remain diffusible and can transferred to an image receiving layer where, if used, a normal negative working silver halide emulsion will form a positive color image of the original without prior photographic reversal.

Suitable coloring compounds for the purposes of the present invention are, for example, the following:

.CO -NH-NH -SO ₂ -

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-CO-NH-NH-SO ₂ -

SO ₂ -NH ₂

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3)

_CO_NH_NH_SO ₂ _CH ₅

SO ₀ -NH,

4)

_C0_NH.NH_S0 ₂

5)

CH ₃ -CO-NH

OCH,

SO ₂ -NH-NHJDO-C ₁

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6)

CH ₃ -CO-NH

OCH,

SO ₂ NH-NH-CO-NH-C ₁₄ H ₂₉

>> -. NH-CO

NH-CO-CH,

SO ₂ -NH-NH-CO-OC ₁

N ■ N _- /?

NH-GO-GH,

9)

CHi-CO-NH

00Η,

Supreme Court,

SO ₂ -NH-NH- /

NH-GH ₂ -CH ₂ -SO ₃ H

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10) CH, -C0-NH

OCH,

-CO-NH-CH ₁ J-CH ₀

^ά ι ^

CH ^ -CO-NH

S0, H

OCH,

OCH,

S0 ~ -NH-NH_ /

SO ₂ -NH-C ₁₂ H ₂₅

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The synthesis of the coloring compounds according to the invention can be carried out by generally customary methods. It is expedient to start from compounds which already contain the grouping -ZO-NH-NH ₀ , for example carboxylic acid hydrazides

"" -X or of heterocyclic hydrazine compounds

bonds, and reacts them with a suitable sulfonyl halide, advantageously in the presence of basic condensing agents, e.g. pyridine, with one of the two reaction partners a dye residue or a residue of a dye precursor contains. In the latter package, the product of the above reaction can either already be used as a color-giving.de compound according to the invention can be used, the color-forming reaction in the processing of the color photographic material during or after diffusion takes place. But it can also be such a non-colored coloring compound according to the invention in one further conversion into a colored coloring compound, e.g. by coupling with a diazonium salt, if the non-colored coloring compound contains a couplable part of the molecule. The synthesis is based on a few in the following Examples explained.

Coloring compound 1

a) 1-Hydroxy-2-taphthoic acid hydrazide "

52 g of 1-hydroxy-2-aaphthoesäur®phenyl © 8ter are in 300 ml of ethanol suspended and added at the boiling point to a solution of 20 ml of flydrazine hydrate in 100 ml of ethanol. After heating for 30 minutes let stand overnight. The precipitate is filtered off with suction, washed with ethanol and dried on the steam bath.

Yield: 33 g. Mp .: 210-213 ° C (dec.)

b) Coloring compound 1

)H

.-00-NH-NH-SO,

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20 g of the compound obtained under a) are suspended in 150 ml of absolute pyrldine. At room temperature, 17.6 g of benzenes μl foahlrLd are allowed to drip ₍ stirred for 3 hours and left to stand overnight. A small amount of precipitate is filtered off with suction, the mother liquor is mixed with approx. 500 ml of water, the precipitated oil is poured off and triturated again with water. The crystalline precipitate is filtered off with suction and dried.

Yield: 34 »7 g m.p .: 230 ⁰ C (dec.) Sarking compound 2

8.5 g of 3-aminobenzoliulfoneäurtanit ¹ are dissolved in 15 ml of concentrated hydrochloric acid and mixed with 30 ml of water. At 70 ^° C., solution occurs. It is cooled to ⁰ ° C. and diazo benefits with a solution of 3.8 g of NaNO ₂ in 10 ml of water. After stirring, the nitrite overo is sutured with sulfamic acid. The resulting solution is aerated dropwise at room temperature with stirring to a solution of 17.0 g of the coloring compound 1 in 100 ml of pyridine, the pH host being kept at pH 8-9 with concentrated sodium hydroxide solution. After stirring for 30 minutes, 100 g of 3it / i30 ml of concentrated hydrochloric acid are poured out. The precipitate is filtered off with suction, washed with water and dried.

Yields 26.0 g, melting point 13S ⁰ O (Ztr.)

coloring compound 5

a) C ₁₅ H ₃₁ - OO - NH - NH ₂

130 g of hydrazine hydrate are placed in 370 ml of water. at 54.9 g of palmitic acid chloride are added dropwise at room temperature. After stirring for 30 minutes, the precipitate is filtered off with suction, with Washed water, dried and recrystallized from ethanol. At the same time formed dihydrazide becomes from the boiling Methanol solution filtered off.

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Yield: 25 g M.p .: 105-108 ⁰ C. b) Color-providing compound 5

6.35 g of dye sulfobromide of the following formula I are added to a solution of 2 _{x 48 g of palmitic acid hydrazide in 100 ml of pyridine}

OCH,

SO ₂ Br

The mixture is heated to 60-70 ^° C., after one hour the same amount of dye sulfobromide I is added and the mixture is heated again for 30 minutes. After standing overnight, 400 ffll water is added and the precipitate is filtered off with suction. The coloring compound 5 is precipitated from the filtrate by adding saturated sodium chloride solution and 2η sales acid and is filtered off with suction.

Yield: 2.8 g, mp 300 ⁰ C.

Coloring compound 9

jff ^ (CH2) -j -j -OH ·, a) II _G ^ y

^^ L - UH ₂ -CH ₂ - SO ₃ H

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18, 5 g of cyanuric chloride are dissolved i ⁿ 100 ml of acetone and poured with stirring to a mixture of 200 ml of water and 200 g of ice. 70 g of a neutral solution of 12.5 g of aminoethanesulfonic acid in water are added dropwise to the suspension at 0-5 ° C. over the course of one hour, a pH of 6 being maintained with 10% soda solution . The mixture is stirred for one hour at pH 6.5 and a small residue is cleared. 18 g of dodecylamine in 50 ml of acetone are added to the solution, the pH is adjusted to 8 with 5 η HCl, heated to 40 ° C. and a pH of 7 is maintained with 5 η sodium hydroxide solution for 1 hour. The mixture is adjusted to pH 1, the precipitate is filtered off with suction and with. Water washed. The residue is stirred in acetone, filtered off with suction, washed with acetone and dried.

Yield: 23 g

NH - (CH ₀ ) .. - CH-

III ^NH 2 - ^NH - \

NH - CH ₂ - CH ₂ - SO ₃ H

10.5 g of 2-chloro-4-dodecylamino-6-ß-sulfoethylamino-1,3,5-triazine (compound II) are refluxed in 90 ml of water and 10 ml of ethanol with 10 g of hydrazine hydrate for 2 hours. After cooling, it is precipitated with 10 g of NaCl and filtered off with suction. The precipitate is dissolved in 50 ml of warm water at pH 10,
then precipitated again by adjusting to pH 2-3 with 5 η HCl, filtered off with suction and washed with water. The mixture is stirred with methanol, again suctioned off and dried.

Yield: 3.7 g

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-ΙίΓ

c) Coloring compound 9

4.5 g of the dye sulfobromide I used to synthesize the coloring compound 5 are gradually sprinkled into a solution of 2.7 g of the above compound III in 160 ml of water and 8 ml of pyridine with stirring. After stirring for 30 minutes, the reaction solution is added

80 ml of methanol and

4 g NaCl, heated until the precipitate has dissolved and allowed to cool with stirring. _O The precipitate is filtered off with suction and washed with a mixture of 2 parts of 2.5% NaCl solution and 1 part of methanol. The residue is stirred in acetone, filtered off with suction, washed with acetone and dried.

6 g of the dye obtained in this way were stirred in 30 ml of dimethylformamide, undissolved constituents were filtered off with suction and the dye with

60 ml of acetone precipitated from the solution. It is suctioned off, washed with acetone and dried,

Yield: 5.5g

The materials required to carry out the method according to the invention basically consist of two elements; a light-sensitive material which contains at least one silver halide emulsion layer and at least one of the coloring compounds according to the invention and a light-insensitive image receiving material which can contain a dye stain and is intended to take up the diffusing dye.

Conventional silver halide emulsions are used in the present invention suitable. These can be called silver halide

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Silver chloride, silver bromide or mixtures thereof; eytl. with a contain a low content of silver iodide of up to 10 mol%.

The preferred binder for the photographic layers is Gelatin used. However, this can be completely or partially replaced by other natural or synthetic binders will. 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 ether or esters or caragenates are suitable. Synthetic binders include polyvinyl alcohol, some of which are saponified. Polyvinyl acetate, polyvinyl pyrrolidone and the like.

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

Precious metals such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable as chemical sensitizers, and compounds of these metals. This method of chemical sensitization is described in the article by R. Koslowsky, Z. Wiss. Phot. 46, 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, also with condensation products of alkylene oxides and aliphatic alcohols,

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Glycols, cyclic dehydration products of hexitols, 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. To achieve special Effects can of course be used in combination with these sensitizers, as in Belgian patent 537 278 and in British patent specification 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, for example Rhodacyanines or neocyanines. Such sensitizers are described, for example, in the work by F.M. Hamer "The Cyanine Dyes and Related Compounds" (1964), Interscience Publishers John Wiley and Sons.

The emulsions can contain the usual stabilizers, such as homopolar 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, 2-58 (1952). Other suitable stabilizers include heterocyclic mercapto compounds, e.g. phenyl mercaptotetrazole, quaternary benzothiazole derivatives, benzotriazole and the like.

The emulsions can be hardened in the usual way,

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for example with formaldehyde or halogen-substituted aldehydes that contain a carboxyl group, such as mucobromic acid, Diketones, methanesulfenic acid esters, dialdehydes and like that.

These can be conventional negative emulsions or direct positive emulsions, e.g. those that have a high sensitivity in the interior of the silver halide grains, or those that work on the principle of polarization. The choice of emulsions depends on the intended use. For example, should from If a positive image is produced from a color negative, negative-working emulsions are used. If on the other hand A positive image is required from a positive original, e.g. from a color slide, then one uses Direct positive emulsions. But you can also get positive images from positive templates with a usual negative working one Obtained silver halide emulsion when, as mentioned earlier, such coloring compounds are used that only through the reaction with developer oxidation products be made diffusion-resistant, so that a color transfer takes place at the non-image areas.

It is of course also possible to process a negative-working emulsion in a continuous development into a corresponding positive image. If colored images are desired, a material can be used in which the photosensitive material contains only one photosensitive layer and, for example, only one dye according to the invention.

In general, however, a multilayer photographic light-sensitive material is used to produce multicolor images with at least three separate silver halide conversion layers, for example one of which is sensitive to red, one to green and one to blue light. Any of the aforementioned photosensitive Layers is in close contact with one of the coloring substances according to the invention.

The tightness required to achieve the desired effect Contact between coloring compound and silver halide A-G 943 3 0 9 8 8-1 2Ό & 1 8

can be prepared by introducing the coloring compounds into the silver halide emulsion layers from aqueous alkaline solutions using any water-solubilizing groups that may be present. The coloring compounds can, however, also be introduced into the layers by one of the known emulsification processes. Such processes are described, for example, in English patents 791 219 and 1,099,414 to 1,099,417. In a further embodiment, it may be desirable, for example, to store the coloring compounds together with silver halide and optionally developing substances in the form of so-called microcapsules, with two or more differently sensitized light-sensitive silver halide emulsions and the corresponding coloring compounds in a single layer in the manner of so-called mixed grains Emulsions can be combined, as described, for example, in US Pat. No. 2,698,794. The coloring compounds can be accommodated in a photosensitive layer itself or in a hydrophilic colloid layer adjacent to it. For example, the red-sensitive layer having associated therewith a magenta dye-forming blue-sensitive layer and a yellow dye-color forming compound is a cyan dye-forming, the green-sensitive layer. Furthermore, the multilayer material can contain intermediate layers in which further substances are accommodated, for example filter dyes, white couplers or antioxidants, in order to limit the activity of the developer oxidation products to a light-sensitive layer in each case. As a further addition, the layers of the photosensitive material can, as already indicated, also contain developer substances, e.g. conventional color developers of the p-phenylenediamine type, but also other developers, such as hydroquinone, N-methylaminophenol, Brenzka techin or phenidone

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their free molecules, but also in the form of their salts in the layer. Since they should only develop their effect at the beginning of the actual development process, a diffusion-proof storage of the developer substances in the layers is sought if possible. For example, the developers can be brought back into the shift in the form of the packages already mentioned. Another possibility is the use of so-called "masked developers", ie developer derivatives which are not developers themselves, but which release the actual developer after a cleavage reaction caused, for example, by heat or alkali. Such masked developers, as well as their use in photographic layers, are described, for example, in German patent specification 1 246 406, in German Auslegeschrift 1 019 560, in English patents 632 836, 691 815, 783 887, 2 069 and 1 114 277 as well as in U.S. Patents 3,243,294 and 2,342,599.

Developer substances that are not only diffusible into the Emulsion layers are embedded, but also during processing, i.e. in an aqueous-alkaline medium. do not diffuse, are preferably used in the embodiment in which the coloring compounds are intrinsically diffusible and in the unexposed areas to form a positive image on the image-receiving layer are transferred while they are imagewise in the exposed areas by reaction with developer oxidation products Shift. Such developers are known. Developers with diffusion-proofing residues are for example described in the German Offenlegungsschrift 1 931057,

The light-insensitive material generally consists of

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any substrate, e.g. a transparent film or a suitable paper, e.g. a plastic laminated paper and a binder layer, which represents the image-receiving layer and which defines the diffusing Dyes may contain a dye mordant.

Long-chain dyes are preferably used as mordants for acidic dyes quaternary ammonium or phosphonium compounds or ternary sulfonium compounds, e.g. those as described are in U.S. Patents 3,271,147 and 3 271 148, and certain metal salts and their hydroxides, the compounds that are sparingly soluble with acidic dyes form, be used.

The dye mordants are dispersed in the receiving layer in one of the customary 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, especially those which are polymers of nitrogen-containing quaternary bases, e.g. polymers of N-methyl-2-vinylpyridine, as described, for example, in American Patent 2,484,430, or of aminoguanidine derivatives of alkyl vinyl ketones, As described, for example, in the American patent _{specification 2,882,156 O.} In general, however, other binders, for example gelatine, will be added to the last-mentioned acidic binders.

The image-receiving layer can also contain further additives, especially if the residues A or B of the coloring compound according to the invention is not about dye residues, but about residues of dye precursors acts. In this case, the image

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Dye precursors transferred to the receiving layer are converted into the final »image dyes by a reaction taking place in the image receiving layer or already during the transfer. Such additives can be, for example, oxidizing agents for the oxidation of leuco dyes or for the oxidative coupling of color couplers with color developer substances. The latter can also be present in the image-receiving layer, but they can also be available in terms of the processing compound.

In order to obtain multicolored images according to the method according to the invention, the light-sensitive material is first briefly immersed in a developer solution behind a colored original after exposure and then in an effective manner with the light-insensitive receiver material, which has also previously been soaked with a developer solution Brought in contact. Silver halide is reduced in the exposed areas; the developer oxidation product formed imagewise reacts with the coloring compounds according to the invention, where these are either split with the release of diffusible dyes or are fixed imagewise in the respective emulsion layer. In the former case , dyes diffuse at the exposed areas and form a negative image in the image-receiving layer. Otherwise, if the coloring compounds themselves can diffuse, they are only transferred to the image-receiving layer in the unexposed areas and form a positive image.

Effective contact is to be understood as meaning that the contact is of such a type that diffusion of the cleaved dye can take place between the light-sensitive material and the image-receiving layer. This does not rule out that the layers of the photosensitive material containing the coloring substances according to the invention and the

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Image receiving layer can be separated from one another by further colloid layers, provided that this results in diffusion of the split off Dyes or dye precursors are still guaranteed is.

According to another embodiment of the method, the two elements can be arranged one above the other on the same layer support be. In this case, the support initially bears the image-receiving layer, which contains a dye stain in a binder may contain and above the various layers of the photosensitive material. After exposure and development and after the dyes, which have become image-wise soluble as a result of the development, in the lower-lying image-receiving layer have diffused, the photosensitive layers are washed off. In general, it is easy to use in this case soluble emulsions, for example based on polyvinyl alcohol or alkali-soluble cellulose ether phthalate.

Of course, the liquid or pasty mixtures required to initiate the development process can also be used housed in fragile containers or containers that can be torn open by slight mechanical action and, for example be arranged between the photosensitive material and the photosensitive image-receiving layer, such as described in U.S. Patents 2,698,244, 2,559,643, 2,647,049, 2,661,293, 2,698,798 and 2,774,668. Such a combined material is preferably suitable for use in self-development cameras. In this case the containers with the developing or activator solutions are arranged and dimensioned so that after exposure Desire the content set free in an amount suitable for the development and formation of diffusing dyes will.

The photosensitive element and the image receiving material can also be combined to form an integral film unit, as described, for example, in U.S. Patents 3,415,644, 3,415,645 and 3,415,646 or in DT-OS 2,052,145. In this case, the photosensitive element and the Image receiving material between two firmly connected

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transparent supports or between a transparent and a opaque carrier and remain firmly bonded to one another even after development. If necessary, between the photosensitive Element and the image receiving material an opaque, for alkaline working fluids and diffusing dyes permeable, light-reflecting layer may be arranged, or there will be an opacifier-containing layer between these layers Injected working fluid so that such a light-reflecting layer is formed after exposure.

As the developer, those commonly used in color photography can be used coloring developers can be used, e.g. derivatives of p-phenylenediamine. A particular advantage of the invention The reason for the process, however, is that the choice of developer substances is not based solely on the usual ones Color developer is limited, but black and white developers can also be used for development, e.g. 4-aminophenol, 4-methylaminophenol, 3-methyl-4-aminophend or catechol and its descendants.

Can be used as developing baths for the process according to the invention for example the baths used in conventional development processes, for example in color photography will. However, by varying the mineral salt content of the baths, the pH value, the Viscosity, as well as by adding organic solvents to create the prerequisites for optimal diffusion. For this only a few routine preliminary tests are generally necessary for the person skilled in the art.

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example 1

A color photographic material is prepared by sequentially placing the following on a cellulose triacetate support Layers are applied.

1.) a 2 # aqueous gelatin solution containing 10 g per kg Compound No. 4, 1 g of saponin and 0.1 g of 1,3,5-trisacryloyl-hexahydro-1,3,5-triazine; Layer thickness 2 / U

2.) a silver chloride bromide emulsion, containing per kg 55 g of silver (of which 6 mol $> in the form of silver chloride), 25 mg of a green sensitizer (dye 13 of DT-PS 1,177,481), 1.5 g saponin, 0.5 g 1,3,5-trisacryloyl-hexahydro-1,3,5-triazine and 25 g of Nn-octadecyl-N-ß-sulfoethyl-p-phenylenediamine; Silver application 0.7 g / m.

The film is exposed through a step wedge and then developed by soaking it for 30 seconds at 24 ⁰ O with an aqueous activator solution containing 30 g of potash and 0.1 g of phenidone per liter and then for 3 minutes with an image receiving material containing a dye stain is brought into contact. The image receiving material consists of a white-pigmented cellulose triacet substrate, which is coated with a solution of 20 cetyltrimethylammonium bromide in 1 1 of 5 # aqueous gelatin solution to a thickness of 10 / U.

After the light-sensitive material has been peeled off, there is a positive, purple reproduction of the original in the image-receiving material developed.

Example 2

A green-sensitive iodide-containing silver bromide emulsion is applied to a layer support made of cellulose triacetate, containing per kg 50 g of silver (of which 3 mol $> in the form of silver iodide), 30 mg of the dye No. 13 from DT-PS 1 177 481, 0.53 g saponin, 0.25 g of 1,3,5-trisacryloyl-hexyhydride, 3,5-triazine, and 25 g of compound no. 5; Silver application 0.9 g / m.

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22283B1

As in Example 1, it is exposed and developed, using as a developer the following is used:

1 g sodium sulfite

10 g N-ethyl-N ~ ß-hydroxyethyl-p-phenylenediamine 20 g potash

2 g sodium hydroxide

fill up with water to 1000 ml.

A negative purple image of the original is reproduced. Example 3

A corresponding result (negative purple image) as in the example 2 is obtained when Compound No. 5 is replaced with the same amount of Compound No. 6.

Example 4

The following layers are applied one after the other to a layer carrier made of cellulose triacetate:

1.) a green-sensitive iodide-containing silver bromide emulsion such as in Example 2, but where compound No. 5 is replaced by -25 g ' of connection no. 9 is replaced.

2.) a 5% aqueous gelatin solution containing 5 g of pyrocatechol, 0.5 g of phenidone and 0.3 g of saponin per kg; Layer thickness 1.5 / ^u

The film is exposed through a step wedge and then Developed for 2 minutes by placing an activator pair between it and the image receiving material (as in Example 1) the following composition is distributed:

20 g of hydroxyethyl cellulose

10 g sodium carbonate

10 g sodium hydroxide

fill up with water to 1000 ml.

A negative image of the original is reproduced. A-G 943 - üy -

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Claims (3)

Claims ; y. Color photographic diffusion transfer process in which, to produce a color image, a material which contains a coloring compound in at least one light-sensitive silver halide emulsion layer or in a hydrophilic colloid layer adjacent thereto is exposed imagewise and developed, either the coloring compound itself or a diffusible one obtained therefrom during development Cleavage product is transferred imagewise to an image-receiving layer as a dye or dye precursor, characterized by the use of a coloring compound of the following general formula: AYZG-NH-NH-SO ₉ -B where mean: A is the remainder of a dye or dye precursor or
a diffusion-proof kest B is an aliphatic or aromatic group, if A is the residue of a dye or dye precursor,
or the remainder of a dye or dye precursor, if A denotes a residue which makes it diffusible, X is oxygen, sulfur or an imino group, Y is a chemical bond or a connecting member, and Z is a chemical bond between Y and C, or together with C and X a heterocyclic group with 5- or 6-membered Hetero ring in which X is nitrogen. A diffusion transfer color photographic method according to claim 1, in which a diffusion-resistant coloring compound ver is applied, which in the development aiaen diffusing dye or a diffusing dye precursor imagewise in 309 8 81/0618
AG 943 - 30 - Freedom, and which corresponds to the following general formula: A ₁ -YZ - C - MH - NH --fO ₉ - B ₁ ^ Il ² where mean: A _{1 is} a diffusion-proofing aliphatic radical or a diffusion-proofing aromatic radical which carries an aliphatic group with 8 to 20 carbon atoms. B _{1 is} the remainder of a dye © the dye precursor, X is oxygen, sulfur or an imino group, Y is a chemical bond or a connecting link, and Z is a chemical bond between Y and C, or together with C and X is a heterocyclic group with 5- or 6 -linked hetero ring in which X is nitrogen. 3. Color photographic diffusion transfer method according to claim 1, in which one diffusible in the alkaline medium coloring compound which is imagewise immobilized upon development, and those of the following general formula corresponds to: A ₉ - Y - ZC - NH - NH - SO ₃ where mean: A _{2 is} the remainder of a dye or dye precursor, B _{2 is} alkyl with 1 to 4 carbon atoms or phenyl, X is oxygen, sulfur or an imino group, Y is a chemical bond or a connecting member, and Z is a chemical bond between Y and C, or together with C and X a heterocyclic group with 5- or 6-membered Hetero ring in which X is nitrogen. 303881/0618
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