DE2230047A1 - Photographic material for color images - Google Patents

Description

concerning
Photographic material for color images

The invention relates to a photographic material or a photographic one Process for the production of color images, which are built up in that an intermediate colorant containing a carbonyl group, i.e. an aldehyde or ketone, with a color-supplying reactants by converting a complete Form dye, and this is done in an image-wise distribution of the dye precursor or the color-providing Reagent, this distribution being obtained in ab-. dependence on the development of an exposed silver halide emulsion layer. According to a preferred embodiment according to the To this end, the invention is a sulfur- and nitrogen-containing one Compound provided that is able to split in the presence of silver ions and / or a soluble silver complex, the latter having become available as a function of development. The splitting leads to the release of one or both of the active substances mentioned in an image-wise distribution corresponding to that of the silver ions and / or the silver complex.

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WMi

Diffusion transfer techniques are well known in the phototech community. In the production of silver images after such Process is an exposed photosensitive recording material, containing a photosensitive silver halide emulsion by treating with a developing solution in Developed in the form of an aqueous alkaline solution of a developer and a solvent for the silver halide. The developable Silver halide is reduced to image silver, while the silver halide solvent is an image-wise distribution forms soluble silver complex with the undeveloped silver halide. This image-wise distribution of the soluble silver complex is then at least partially transferred to an image receiving layer arranged above it, in which a Silver transfer image is built up.

According to a simultaneous proposal, a 'contains photographic material an inert substance which, in the presence of image-wise distributed silver ions, is able to break down during the Developing and thereby releasing a reactant such as a photographically active agent or a dye, in the same way Distribution like the silver ions. Depending on the photographic process and the results sought, it is considered an inert substance selected one that is diffusible or substantially nondiffusible in the developing solution. The reactant to be released may be diffusible or substantial in the developing solution not be diffusible.

According to this simultaneous proposal, color images are produced using photographically inert substances within the photographic material, namely color-providing substances that are essentially non-diffusible in the developing solution, but are capable of splitting off in the presence of imagewise distributed silver ions and / or a soluble silver complex in the undeveloped or partially developed areas of the * Depending on the development, the emulsion layer is a more mobile one

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ORIGINAL INSPECTED

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and to split off diffusible color-providing substance, namely in the same distribution as the silver ions and / or the silver complex. The following structure of the color image is the result the different diffusibility between the inert starting substance and the released color-providing substance, wherein the more diffusible color-providing substance residing in the undeveloped or partially developed areas in image-based distribution is available for transmission stands.

As substances that lead to the release of a reactant are capable in the presence of silver ions, sulfur- and nitrogen-containing compounds containing the group

I IiI!

-S-X-N- or -S-X-K =, suggested, wherein X -G-; -C-G = G-;

IIII A- * ^ r- ^ I ^{! l}

-C = GG-: -Cc / ^X V or -C > -C-. It can turn out to be

be linear or cyclic structures; in the case of the cyclic, the nitrogen and / or the sulfur atom can be part of the hanging system belong. Particularly preferred cyclic compounds contain

I I I

the grouping -S-C-II = or -S-G-N- within the ring.

Like the 1 ^ -sulfur-nitrogen compounds in general, these substances can be broken down gradually, between the sulfur atom and the carbon atom, to which the nitrogen atom is attached, and between the nitrogen atom and the carbon atom to which the sulfur atom is attached.

According to the simultaneous proposal show the sulfur-nitrogen compounds e.g. Thiazolidines, very good stability in alkaline media, as in aqueous-alkaline development s fl uidity, as it is usually used in tank development or in the context of di ffusi ο ^ transfer processes. In Presence of silver ions and / or a soluble silver complex

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as they «become available during development, they are in the Location, a. To release reactants with a smaller molecule in the same imagewise distribution. So they split Thiazolidines from a diffusible dye, so that a diffusion transfer image is obtained in useful development times can.

The present invention now relates to the use of sulfur-nitrogen compounds of the above type for the release of a substantially colorless and preferably colorless intermediate dye in the form of an aldehyde or ketone, which then to form a dye image with a coloring agent Material or reactant is able to react.

The photographic material according to the invention makes use of the Reaction of an aldehyde or ketone with the color-providing reagent, e.g. a methylene coupler, in a photographic System for making dye images. The above sulfur-nitrogen compounds containing the grouping I i I

-S-X-N = or -S-X-N-, preferably with one carbon atom as

X, especially within a ring system, are particularly suitable for the release of one or both reactants in an image-wise distribution, which reactants then become a complete Dye react in the same distribution. Examples of cyclic sulfur-nitrogen compounds are

a) S N-R and b)

where Z indicates the atoms, preferably carbon atoms, the are necessary to complete the ring system containing up to about 20 ring members. R can be a hydrogen atom or a be monovalent organic group. X has the above meaning and is preferably a carbon atom. There were already dye images obtained by releasing a complete dye

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directly from such substances. It is therefore surprising that A photographic image can be obtained in a two-step process for cleaving one or both of the reactants from the sulfur-nitrogen compound, whereupon this both reactants react with each other and now provide a dye image.

The object of the invention is therefore to produce a dye image by reaction of a dye precursor containing a carbonyl group, i.e. in the form of an aldehyde or ketone, with a color-providing reagent to form a complete one Dye, one of these two reactants in an image-wise distribution as a function of the development of the silver halide occurs. According to the invention, a sulfur-nitrogen compound is used for this purpose, which is in the presence an imagewise distribution of silver ions and / or a soluble silver complex, which depends on the development an exposed silver halide emulsion layer were available, is capable of splitting and thereby said dye Able to release intermediate product.

As mentioned above, according to the invention, a dye image is produced obtained by a dye precursor containing a carbonyl group, ie in the form of an aldehyde or ketone, with a color-supplying reagent is converted to a complete Dye. This reaction happens after the exposed silver halide emulsion layer with an aqueous alkaline Developed developer solution and, depending on the development, an imagewise distribution of the dye intermediate and / or the color-providing reagent vmr de. The dye precursor and the dye-providing one Reactants then react with one another, via the Carbonyl group, so that a complete dye is formed in an image-wise distribution. This image-wise distribution of at least one of the reactants is reached by application

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a sulfur-nitrogen compound within the photographic material, which is able to split up in the presence of silver ions or a corresponding soluble complex and thereby the dye precursor and / or to release the color-providing reagent. The two-step process of releasing an aldehyde or ketones made from, for example, a 1,3-sulfur-nitrogen cyclic compound and reacting this released aldehyde or ketone with a color-providing reagent, e.g. Methylene coupler, can proceed through the following stages:

R ¹ + H ₀ O ^ g ⁺ ^ R'-GHO + HRN SH

b) R'-CHO O CH ₀ 0H ~ ν R «-CH = C:

_c ) <R »\ R ¹ + HO Ag + ^ R ¹ R" - C = 0 + RHN SH

d) R ¹ R "-C = O + ^ GH ₂ OH _> R ¹ R" - C =

The dye precursor and / or the color-providing reagent can be diffusible in the developer solution. The complete dye is also formed when both reactants are relatively non-diffusible.

According to one embodiment of the photographic material according to the invention the sulfur-nitrogen compound is in a layer associated with a light-sensitive silver halide emulsion layer, e.g., the emulsion layer on a film support which is developed after exposure in the presence a color-providing reagent with the aid of an aqueous alkaline developer solution, which contains a developer and a

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Contains solvent for the silver halide. The silver ions and / or soluble silver complexes formed in an image-wise distribution migrate to the assigned sulfur-nitrogen compound, which is preferably not diffusible in the developing solution. This now splits in the presence of the silver ions and / or the silver complex with release of the dye precursor in the same imagewise distribution. The educated Dye precursor now reacts with the dye-providing reagent and results in a dye in the same distribution, the can then be transferred to an image receiving layer, namely depending on its diffusibility in the developing solution.

According to another embodiment of the invention The color-providing reactant (and not the dye precursor) is dependent on the photographic material in an image-wise distribution released from the development, whereupon this in the same distribution with a dye precursor to form the Dye image reacts. The image-based distribution of the color-providing Reagent can be obtained, for example, by choosing a reactant which is able to react with the oxidation product of the developer or vice versa the non-oxidized developer reacts.

As mentioned above, one can use a sulfur-nitrogen compound apply for the release of the color-providing reagent in an image-wise distribution. If desired, you can however, also use an appropriately substituted sulfur-nitrogen compound, which in the presence of image-wise distributed Silver ions are both the color-providing reactant and the dye precursor, which then work together to form the dye can react, be able to release.

Becomes a 1 ^ -sulfur-nitrogen-compound for the figurative Distribution of the dye precursor and / or the coloring

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supplying reagent used, e.g. to release an aldehyde dye precursor, 'so the carbon atom, to which the sulfur and nitrogen atoms are attached, instead of a hydrogen atom, a group that "when released as an aldehyde is essentially colorless and with a color-providing Reactant, such as a methylene coupler, is able to react to form a dye. This substituent can be one act any hydrocarbon radical that substitutes or may be unsubstituted, provided that the split off Aldheyd can act as a dye precursor, i.e. in the Is able to give a complete dye with a certain color-providing reagent. Should be a ketonic Dye precursor are split off, then the two remaining valences of the carbon atom common to the heteroatoms are substituted with groups which, after cleavage, give a ketone which is essentially colorless and has a color-providing one Reactant capable of reacting, e.g. a methylene coupler. As with the aldehydic dye precursors, the two can Substituents can be any hydrocarbon radicals, provided that they meet the above requirements. The nitrogen atom of the The sulfur-nitrogen compound can be substituted with hydrogen or, if appropriate, a hydrocarbon radical.

The substituent or substituents on the common carbon atom can be attached to this directly or via a bridge member, which can be acyclic or cyclic. Such bridge members are e.g. the cycloalkyl groups, such as cyclohexyl-, -CONH-, -alkylene-CONH-, arylen-CONH- or alkylene groups, furthermore arylene groups, where the Alkyl engrupp e Athyleny propylene, butylene group and the arylene group can be a phenylene group. Under the name "Dyestuff precursor" here also includes all bridge members. The term "aldehydes" or "ketones" also includes polynuclear ones aromatic compounds such as 4-Dimeth.ylaminonaphthald-ehyd.

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For, the release of a color-providing reagent can be in the 2-position or elsewhere in the basic molecule either directly or via a bridge member, as mentioned above, the corresponding substituent hang. It can be, for example, a methylene coupler that is in the 4-position. In 2 position Corresponding hydrocarbon radicals can optionally be present which lead to an aldehydic or ketonic dye precursor can be split off. In this way you get both the aldehydic and ketonic as well as the color-supplying reaction partner, namely in a distribution corresponding to the undeveloped and partially developed areas of the silver halide emulsion layer.

It is desirable to have the matrix substantially non-diffusible in the developing solution. So this can be substituted with an immobilizing or anchoring group. One or more substituents can be used for this purpose together then exclude migration of the substance from its original position in the photographic material. If that to be released Reactants, e.g. an aldehyde dye precursor, If it is to be diffusible, the immobilizing groups must be arranged in such a way that they reduce the mobility of the Do not adversely affect aldehydes in the developing solution. If, for example, several groups are used to immobilize the Substance applied, one or more can belong to the part, which is ultimately split off as a dye precursor, as long as these groups do not have an undue degree of mobility or Reduce diffusibility in the developing solution. Will only have a single immobilizing group to anchor the basic substance applied, their position should be such that they do not relate to the diffusible dye precursor to be split off heard.

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The selection of the special immobilizing groups for anchoring the basic substance depends primarily on whether only one such group or two or more should be used. If there are two or more immobilizing substituents lower alkyl groups such as butyl or propyl groups are suitable. If only one immobilizing substituent is used, then to prefer higher alkyl groups, such as octyl, decyl, dodecyl, Stearyl or oleyl group or optionally substituted carbocyclic or heterocyclic ring systems with at least 6 ring links. The cyclic substituents can have a single carbon atom or two adjacent carbon atoms be connected to the basic substance.

As mentioned above, the sulfur-nitrogen compounds can be used for the release of a dye precursor with appropriate Hydrocarbon radicals may be substituted after cleavage result in the aldehyde or ketone which can be converted with the color-supplying reagent, e.g. aliphatic, cycloaliphatic, aromatic or heterocyclic radicals. You can have double and triple bonds contain. The carbon chain can be made up of heteroatoms or hetero groups are interrupted, such as S, O, N, SO, NH. These radicals can also carry substituents, such as halogen atoms, Phenyl, alkyl carbalkoxy, carboxy, hydroxyl, sulfo, cyano, Nitro or alkylamino groups or alkyl ethers and aryl ethers. For example, it may also be desirable to have a hydrocarbon residue containing solubilizing groups such as -COOH or -HSO. ,, apply to the diffusibility of the dye to be released οff to improve the preliminary product.

Examples of useful hydrocarbon radicals are optional substituted alkyl groups, such as methyl, ethyl, octyl, dodecyl groups, optionally substituted cycloalkyl groups, such as cyclohexyl, cyclopentyl, cyclooctyl, if appropriate substituted alkenyl groups, such as vinyl, allyl, butenyl, Decenyl, octadienyl, hexatrienyl groups, optionally sub-.

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Stituiexte cycloalkenyl groups, such as cyclopentenyl, cycloheptenylimd Cyclohexadienyl groups, optionally substituted alkynyl groups, such as ethynyl, hexynyl, octynyl groups, if appropriate substituted aryl groups such as phenyl, tolyl, benzyl and Naphthyl groups, optionally substituted heterocyclic groups Groups with a 4- to 6-membered ring and oxygen, nitrogen or sulfur as a hetero atom and combinations thereof, e.g. Pyrrole, pyrazole, oxazole, thiazole, imidazole, pyrimidine, piperidine, Piperazine, thiophene, pyrrolidine, azetidine.

! The sulfur-nitrogen compound can also have other compounds Substituents than those required for the cleavage of the dye precursor, provided that they are useful do not adversely affect in phototechnology, such as carboxy, sulfo, nitro, hydroxyl, cyano groups, halogen atoms, such as Chlorine and bromine, hydrocarbon radicals as listed above, and aliphatic ^, cycloaliphatic, aromatic or heterocyclic, which can be saturated or unsaturated and whose carbon chain is interrupted by heteroatoms or hetero groups can be and which in turn are optionally substituted again.

It is possible to use sulfur-nitrogen compounds that are capable of releasing a color-providing reagent, but one will usually use those which contain an aldehydic or ketonic dye precursor in an image-wise distribution deliver, which then with a dye-providing reagent, which is present in a layer of the film unit and / or the developing fluid is able to react. As a color supply Reactants can be used any substance that reacts with aldehydes and / or ketones to produce a colored Substance supplies, e.g. methylene couplers or reactants, which are used in color tests to identify aldehydes and ketones are common. The term "methylene coupler" here includes substances which contain an active methylene group, but also

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those that have an active methyl group, those in alkaline Medium capable of delivering a methylene base. BeispMe for substances containing a reactive methyl group are quaternary ammonium compounds, such as pyridinium compounds with a methyl group in the 2- and 4-position of the heterocycle. The nitrogen atom can also be substituted, e.g. with an alkyl group such as methyl, ethyl or propyl group, aryl group, such as phenyl group or aralkyl group, such as phenyl and benzyl group. They can be present as a free base or as a salt, the anion of which belongs to any acid, e.g. a tosylate.

Couplers contain an active methylene group which is directly bonded to at least one activating group, such as a Keto or aldehyde group, an ester or nitrile group, usually a carbonyl or nitrile group. The methylene group can also be attached to two such activating groups, which are the same or can be different, be bound. It can be part of an open chain or a ring link. Such couplers can also have more than one methylene group, e.g. up coupler.

Such substances with at least one active methylene group are customary couplers for color-developing agents in phototechnology Substances, e.g. of the series p-phenylenediamine (Mees, The Theory of the Photographic Process, 1966, pp. 382-395). Any desired methylene coupler substance can be used according to the invention serve, such as acylacetic acid ester, acylacetoacetic acid ester, Malonic acid ester, acetonitrile, acylacetonitrile, aroylacetonitrile, Cyanoacetic acid ester, Gyanacetοphenone, Cyanacetylcoumarone, Cyanoacetylhydrazones, acetoacetamides, cyanoacetamides, 1,3-indandiones, Thioindoxyls, oxindoxyls, indazolin-3-ones, isoxazol-5-ones, Pyrimidazolones and homophthalimides. The couplers are usually colorless, but they can also have their own color (USA Patent 3,087,817).

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Methylene couplers which can be used according to the invention are, for example:

(1) N-methyl - ^ - picolinium tosylate

(2) N-methyl-y 1-picolinium tosylate

(3) N-methoxy ^ -picollnium methosulfate

(4) N-ethyl- Γ-picoliniunibromide

(5) N-Benzyl-2-picolinium bromide

(6) N-methyl-2-methylquinolium chloride

(7) N-phenyl-2-methylquinolium chloride

(8) 4- (n-Octadeeylaminocarbonyl) -N- (1-phenyl-5-

pyrazolyl-3) phthalimide

(9) ot- (m -nitro'benzoyl) -2-methoxyaoetanilide

(10) oC-pivalylacetanilide

(11) aoetoacetanilide

(12) Benzoylaceto-2-me "thoxy-3-dodeoyl-oxyoar" bonyl anilide

(13) benzoylacetone

(14) β-liaphthoylacetone

(15) 2- (oC-cyanoacetyl) -oumarone

(16) '2-Cyanoacetyl-5-sulfonedimethylamide

(17) Benzoyle3 acetic acid ester

(18) Cyancroetylhydrazone des Acetoessigsäureäthylestera

(19) ethyl acetoacetate

(20) Ethyl-rC-benzoyl-ri-fluoroacetate

(21) 3- (Stearoylacetamido) -isophthalic acid _t

(22) N, N'-di- (aoetoaoetamino) diphenyl-oyanooetophenone

(23) p-nitro-phenylacetonitrile

(24) benzoylacetonitrile

(25) Bromthioindoxyl changed according to

Received on .... t:, 7 ..'—

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(37)

(38)

_ _u _ 2230047 _u . ₄₁₂₈₇

, y. ] / eingegaiiEj-

(26) 1-Cyanocetaminobenzothlazole

(27) £ -phenylisoxazol-5-one

(28) pyrimidazolone

(29) N-Athyloxindole

(30) indazolin-3-one

(31) thioindoxyl

(32) 1,3-indondione

(33) N-phenyl-ß-andinoglut aconimid

(34) N-phenyl homophthalimide

(35) 1,3-Diethylthiobarbituric acid

(36) p ρ

Depending on the particular way in which the dye image is to be built up, the dye-providing reagent can either be diffusible or non-diffusible, i.e. it is in the Able to diffuse into the developer fluid and through the photosensitive and other layers of the recording material

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or it is essentially in the developer liquid immobile and does not migrate from its initial position within of the hiotomaterial. A common way to do this is Making color-providing reactants, such as the above methylene couplers, non-diffusible is the introduction of a bulky one Substituents, such as a long chain alkyl group, how to get them can also be used to anchor the sulfur-nitrogen connection. In addition, non-diffusible couplers can also have a salt-forming group, e.g. a carbonyl or sulfo group, which makes these couplers easier to incorporate into the insert the desired layers of the Ehot © material. Of the However, non-diffusible couplers can also be used in the desired layer in a certain dispersion technique high and / or low boiling solvents are introduced. It is evident that the bulky substituent and the salt-forming group is in a non-coupling position within the molecule.

The color-providing reactant can initially be in the Recording material are present, e.g. in the silver halide emulsion layer, or in a separate layer behind and / or in a layer on the emulsion layer, but also in the image receiving material, e.g. in the dyeable image layer itself or a layer arranged above it and finally also in the developer liquid. The sulfur-nitrogen compound can initially be in the photographic material in the emulsion layer or in a separate layer behind and / or above this in the image receiving material, namely in the image layer itself or in one of these assigned layers. You kaan however, they can also be present in the same layer as the color-providing reagent or in a different one. If the Sulfur-nitrogen compound and / or the color-providing reagent in the silver halide emulsion layer itself exist, they should be ineffective from a photographic point of view and in any case should not have a detrimental effect on the image.

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develop structure at least to a sufficient extent. If they are not completely photographically ineffective, the reactants should be modified so that "at the No disturbance occurs in any way and the reactants are deactivated in such a way that they also respond to the development photosensitive emulsion have no adverse effect.

It is evident that the initial arrangement of the color-providing reagent and the sulfur-nitrogen compound within the photographic material and the selection of the particular color-providing reagent and the aldehyde or ketonic dye precursor to form a diffusible or non-diffusible dye to a certain extent Degree depends on the desired results. For example, single-color images are to be produced within the recording material the sulfur-nitrogen compound can initially be present in this, as can the color-providing reagent or the latter will be in the developer liquid. If the aim is to produce a transfer image, the Sulfur-nitrogen compound initially in the recording material or in the image receiving material and the color-providing material Reactants either in the recording material or in the image receiving material or in the developer liquid. Depending on the mobility required, the dye-providing reagent may initially be non-diffusible or diffusible be.

According to a preferred embodiment of the invention multi-colored images can be produced, e.g. with the help of a photographic material in the form of a multilayered photosensitive Recording material containing at least two selectively sensitized silver halide layers which simultaneously and can be developed without separation to obtain multicolored images which are then transferred to a common image receiving element will. In this system, the required "

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color-providing reactants and sulfur-nitrogen compounds which are capable of releasing the desired aldehyde or ketonic dye precursor are assigned to the respective light-sensitive silver halide emulsion layers. These two substances are preferably present in a mixture in a layer which is separate from the emulsion layer, namely separated therefrom by one or more spacer layers. The dye formed can be non-diffusing, so that the colored image is formed in the recording material, or the dye is diffusible and can therefore be transferred to an image-receiving material, in which the colored image is then built up. To prevent undesired migration of silver ions, such as those present in the soluble silver complex, from one silver halide layer to another during development, spacer or intermediate layers can be provided to trap silver ions.

In addition to forming a dye of the desired color, it can also be colorless or of a different color than that which is ultimately desirable in a certain environment - as in a certain pH, but by changing the Milieus, e.g. Transition from alkaline conditions to acidic conditions, a color change occurs. The complete dye can also be a so-called "temporarily shifted dye". That is a color, which is a color shift or Suffers color change after development. It can also be a metal complex of the dye, its non-complex Form is essentially colorless, which, however, changes to the complex state after the image is built up and now shows the desired color.

The developing liquids are an aqueous alkaline solution of a developer and preferably a solvent for silver halide, but the latter is not essential. These substances can be present in the aqueous medium from the start or somewhere else in the photographic material, e.g. in the

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Emulsion layer and / or the image receiving layer and / or spacer layers, as is generally customary. Are these substances in the film unit from the beginning, the developing liquid is obtained, by bringing the material into contact with an aqueous medium so that these substances are in Solution can go.

The alkali used in the developer liquid can be any alkaline product such as caustic soda or potassium hydroxide. The silver halide solvents are also common substances, such as sodium or potassium thio sulfate, Sodium ihodanide or uracil. It can also be a forerunner act for the silver halide solvent.

Common substances such as diaminobenzenes, e.g. p-phenylenediamine, aminophenols such as methyl-p-aminophenol can be used as a developer and dihydroxybenzenes such as hydroquinone. In addition to these substances, antifoggants, preservatives, Viscosity-increasing substances and other common additives are present. However, these substances are not for the invention essential.

The invention is further illustrated by the figures.

1 shows a schematic cross section through a photographic material for producing a color image.

Fig. 2 shows another embodiment of the invention Photographic materials.

According to Fig. 1, a dye image is to be produced. That Recording material consists of a transparent carrier 10, a layer 11 containing a color-supplying reagent and a sulfur-nitrogen compound which is able to free a dye precursor in the form of an aldehyde or ketone

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set, and finally a photosensitive silver halide emulsion layer 12, which is located above the spacer layer 13. The developer layer 15 is an aqueous-alkaline solution a developer and solvent for silver halide and is located between the recording material and the distribution layer 13. In the exposed areas of layer 12, silver halide is reduced to image silver, while in image

. moderate distribution dissolves in the unexposed areas Form silver complex compounds. These are at least partially transferred into the layer 11, where they eliminate the dye precursor accelerate from the sulfur-nitrogen compound, in the same image-wise distribution as in the Emulsion layer 12. The dye precursor in turn reacts

'with the color-providing reagent present with formation image-wise distributed, non-diffusible dye in the

. unexposed areas of the emulsion layer, creating a color image is being built.

The developer composition 15 can be applied to the emulsion layer by coating, dipping or spraying or on any other way. All of the substances can also be in a destructible container from the start (USA patent 2,543,181). This is provided in the film unit in such a way that its contents are essentially uniform when destroyed able to distribute between the two facing layers.

Color slides can also be obtained using a film unit, its layer / color-providing reagent and contains the sulfur-nitrogen compound for the cleavage of a dye precursor, with one option (e.g. as in Fig. 2). This is where the silver halide emulsion layer lies 12 on a carrier 20. The developer layer 15 is located between the emulsion layer and the layer 11, which in turn is covered with another transparent one Carrier 14. In the exposed areas of the emulsion layer 12

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the silver halide is reduced to image silver and from the transferred to undeveloped areas of the silver complex. The accelerated splitting of the sulfur-nitrogen compound takes place in layer 11 by the migrated silver complex with the release of an aldehydic or ketone dye precursor in areas corresponding to the undeveloped areas of the emulsion layer. The reaction of the pre-dye product with the color-supplying reagent now leads to the Color image directly on the transparent carrier.

The film units, as indicated in the figures, can be varied, for example by providing one or more intermediate layers between the emulsion layer and the reactant layer, as well as other layers are included or the reactants are present in separate sublayers or the like. According to the invention The dye images obtained can also be produced as top view prints if a translucent layer is present, which provides the necessary background for image viewing, e.g. one containing a white pigment such as Titanium dioxide.

It is evident that in the sulfur-nitrogen

Compound contain more than one grouping -S-X-N = or -S-X-N- can be (as shown in Example 5 below). Substances used according to the invention with two ' Sulfur-nitrogen ring systems correspond to the formulas

(c) · Z ^f - X— Y — X ^ -

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ifi III I,.

where Y -c- (C = »C-) _n> (-C = C) _n -C-,.- C- ^" ^ ₁ -ζ y

or -C can be V and Z ¹ and Z ⁿ the

-C-

Atoms, preferably carbon atoms, indicate the completion a ring system with up to 20 members is necessary

are. X has the above meaning and is preferably a carbon atom.

; In the above formula, the two sulfur-nitrogen groups can be the same or different. The same applies to Z ¹ and Z ″. The two groups are preferred

-S-C-N-. So they are derived from the thiazolidines and / or

Benzothiazolines. Also, Z ¹ and Z ^{M are} preferably the same rings.

Linear sulfur-nitrogen compounds that can be used according to the invention are those of the formula

(d) R-S-X-N (^, ■

R ¹

wherein R is a hydrogen atom or a monovalent organic

1 2
Remainder, R and R is a monovalent organic group. But it can also be substances of the formula

(e) R ² -SXK = R ⁵

act where R is a divalent organic group. In the For formulas (d) and (e), the group X is preferably a carbon atom.

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The linear compounds as well as the cyclic compounds of the formulas (a) and (b) can be substituted by a group which by splitting off represents a dye precursor in the form of an aldehyde or ketone and which with a color-providing one Reactant able to react to form a complete dye. Analogous to the cyclic 1,3-sulfur-nitrogen compounds can be the linear substances on the common carbon atom with one or more hydrocarbon radicals be substituted, which can be split off and give aldehyde or ketone, which is essentially colorless. The hydrocarbon residues can be bound directly to the carbon atom or via a bridge member. When the substance is essentially Should not be diffusible in the developer liquid, the basic molecule can have a voluminous group or with several such groups may be substituted, which together cause the immobilization of the substance, e.g. the substituents R in the compounds of formulas (d) and (e). Useful hydrocarbon residues, bridges and immobilizing groups were enumerated above. V / ie set out on the basis of the cyclic compounds, the linear compounds can also be more than contain a sulfur-nitrogen group. So can the substituent R of the compounds according to formulas (d) and (e) be a second linear sulfur-nitrogen group, specifically the same or a different one, whereby a ring system can also be included here.

In various modifications of the photographic material according to the invention binderless silver halide layers can also be used. The usual silver halide is used Products such as chloride, bromide, bromide iodide, chloride bromide or chloride bromide iodide. Instead of the usual silver halide emulsions one can also use direct working positive emulsions. In this way, the recording material is obtained a positive image. If the recording material is a color image contains, this can be viewed in transmitted light

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be .. The concentration of silver halide in the corresponding The layer is preferably such that when fully developed the image silver has poor hiding power, i. lower maximum density.

A wide variety of materials, as is customary, can be used as supports, in particular high-polymer Fabrics, whether of synthetic or natural origin. For example, the polymeric products can be polyethylene glycol terephthalates, Polyvinyl chloride, polyvinyl acetate, polyamides and cellulose derivatives, such as -ac et at, -tr iac et at or -riitrat act, but also regenerated cellulose or glass. useful. The transparent material must allow viewing of the image allow light to pass through.

Customary materials which contain a dyeable polymer, such as nylon, partially hydrolyzed, can serve as the image-receiving layer Polyvinyl acetate and polyvinyl alcohol. You can ... a Have dye stain.

The term "color" here also encompasses the multiplicity of Colors that lead to black.

It is obvious that other precursors or intermediates can be released according to the invention than that Above mentioned and in image-related distribution can be present in other film units than they have already been listed. So For diffusion transfer processes, a negative component can include at least one photosensitive layer and one positive component contain at least one image layer and represent separate elements that occur during development and are then brought together and remain as a copy or are separated from each other according to the composition of the image.

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Instead of these two separate elements, the light-sensitive Layer and the image receiving layer also belong to a single material. Such film units are constructed in such a way that that the image-receiving layer is on a support and the light-sensitive layer is on the image-receiving layer is provided. The developer liquid is distributed between the combined negative and positive components. To the A distribution film is expediently used for distribution.

Other possibilities are film units, their negative and positive component form a uniform structure, so so-called integral negative-positive film units, which at least before the composition of the picture are held together. They generally comprise a variety of essential layers including one negative component, which is at least one photosensitive layer such as a silver halide layer. and a positive one Component which contains an image-receiving layer and which are combined into a single material. In the production of Color transfer images can cause the dye image Reagents are present in the vicinity of this component and form a diffusible dye for transfer to the image-receiving layer

These units also include those for producing a transfer image - which is viewed without separation i.e. the positive component containing the transfer image need not be separated from the negative Component to look at the picture. In addition, such film units can also have a reflective layer between them the image receiving layer and the negative component in order to effectively mask the silver image and residual associated, to shield the reagents that make up the dye image and moreover provide a background for viewing the transfer image in the image receiving component without separation in the conspicuous Enable light. This reflective layer can

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be preformed and contain a reflective agent and "is located within the essential layers of the film units or the reflective agent can also be added after exposure, e.g. by being in the developer liquid is located.

The essential layers are preferably arranged on a transparent support as close as possible to the image receiving layer and this preferably includes a further support on the opposite side of the essential layer so that these layers are bounded sandwich-like by the two supports. At least one of the carriers should be transparent to the Allow viewing of the image. Such film units usually come with a breakable container applied, in which the developer liquid is located and the release of its contents by the application of pressure Allowed development of the exposed film unit.

The invention is further illustrated by the following examples.

example 1

Malononitrile and 2- (p-dimethylaminophenyl) -3-propylthiazolidine

were dissolved in N-ethyldodecanamide and dispersed in gelatin. The dispersion was applied to a transparent cellulose triacetate film support. A silver iodobromide emulsion in gelatin, applied to a paper support which was completely obscured, was used as the photosensitive element. Half of it was 10 min with a mixture of hydroquinone and

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Methyl-p-aminophenol developed, then development stopped with dilute acetic acid, rinsed and dried. The two materials became more uniform over a developer layer Thickness of about 0.8 mm stacked on top of each other. The developer mass contained 3.4 g of hydroxyethyl cellulose per 100 cnr v / water, 5 g sodium hydroxide, 50 g titanium dioxide and 4 g potassium rhodanide.

A yellow image was obtained almost immediately in the areas of the image receiving material which did not develop the Corresponding areas of the recording material. In the rest Substantially no yellow dye was visible in areas.

Example 2

Example 1 was modified so that N-At hy! Oxindol was used in place of the malononitrile. A yellow 3 image appeared only in the areas of the image receiving material that had the undeveloped parts' of the recording material corresponded.

Example 3

Example 1 was modified so that c6-cyanoacetanilide was used instead of malononitrile. Received here too you will see a yellow image in the corresponding areas.

Example 4

Example 1 was modified in such a way that N-methyl-cC-picolinium tosylate was used instead of malononitrile, namely this was in the developer liquid and not in the layer with the thiazolidine. In the undeveloped ones Areas of the image receiving element corresponding to areas of the emulsion layer formed an orange image.

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Example 5

Example 1 was repeated using the substances of the following formula as "sulfur-nitrogen compound" or as the color-providing compound Reagent:

s _vx

X ^ and

In the image-receiving element, only those areas were obtained which corresponded to the undeveloped parts of the emulsion layer. a purple picture.

Claims

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61 xxi

Claims (1)

Claims 1 _# Photographic material consisting of A) a photosensitive recording material containing a film base and at least one photosensitive silver halide emulsion layer, B) an image receiving material containing at least one image layer and C) an aqueous-alkaline developing solution containing a developer and a solvent for silver halide, characterized in that at least in one of the layers-A and / or B and / or in a layer arranged on the same side of the support as the emulsion layer, a sulfur-nitrogen compound containing the group -SXU =, in which Σ. or C -; C- i 1 C = 0-; I is contained in the presence of silver ions in an image-wise distribution in this Distribution to release an essentially colorless dye precursor in the form of an aldehyde or ketone in the Is able to soft with a color-forming substance to a dye able to form 2. Photographic material according to claim 1, characterized in that the sulfur-nitrogen compound is cyclic, in particular contains up to 20 ring members and the group -S-X-N = is located within the ring system. 209853/10 72 «A 3 · Photographiscb.es material according to claim 2, characterized in that the cyclic system is a thiazolidine, in particular 2- (p-dimethylaminophenyl) -3-propylthiazolidine, which is able to split off the corresponding benzaldehyde, or 2.2 ^f - (if-butylthiazolidyl ) -methane is, 4. Photographic material according to claims 1-3 characterized in that in the same layer, which contains the sulfur nitrogen compound, or in the Developer solution also contains a color-providing material. 5. Photographic material according to claim 4 characterized in that the color-providing material a methylene coupler, preferably ct-cyanoacetanilide, N-Ethyloxindole, ΪΓ-methyl-cC-picolinium-tosylate, 1,3-dimethylthiobarbituric acid or malononitrile. 2 09853/107 2 OH. ING. F. WTHRSTHOFF BR. E. τ. PKOKM.VNPX *) ■>'J Π Π / Π DR. ING. P. BKIiUKNS Z /. 0 UU Η · / DIPt. ING. K. fiOE'f /, PATENT LAWYERS M Ü N C II ΙΟ N 9 O Λ, ι ^ 1 Λ-4.1 Contingent Claim Photographic process in which a photosensitive Material containing an exposed silver halide emulsion with an aqueous alkaline developing solution and an imagewise distribution of at least a first and a second reactant is formed and the first reactant contains an aldehydic or ketonic CO group and the second reactant contains of this CO group is able to react with the formation of a dye, so that as a result of the development an image-like Distribution of the dye results.