DE2451628A1 - PHOTOGRAPHIC RECORDING MATERIAL - Google Patents

Description

Photographic recording material.

The invention relates to a photographic recording material comprising a layer support and at least one coated thereon Layer with an oxidizing agent and one or more photographic

and/

to-sensitive silver halide emulsion layers / or an image-receiving layer.

In the context of the color diffusion transfer process, it is known that photographic recording materials are used, which consist of a support, at least one silver halide emulsion layer and an image dye-forming rail contained in the silver halide emulsion layer itself or can be accommodated in a layer adjacent to this. After the imagewise exposure, it becomes photographic Recording material with an alkaline developing liquid deals with what causes the development. The compound producing the image dye can initially be used in the Development fluid can be immobile or mobile. During the alkaline development of a recording material with initially immobile Image dye forming compounds, a mobile dye or a mobile dye precursor compound can be imagewise are released or the compounds producing image dyes can be made soluble in oil and thus made mobile. If the image dye-producing compounds initially consist of mobile compounds, the developing solution typically leads This means that these image dye-producing compounds are made image-wise insoluble and thus immobile. Indifferent, Whether mobile or immobile image-generating compounds are used first is determined in the treatment of the recording material oxidizes the image dye-forming compound with the developing liquid, typically under alkaline conditions, whereby an image is generated in the recording material.

For example, U.S. Patents 2,698,798 and 2,559,643 teach color diffusion transfer processes known in which silver halide latent images are developed with color developing agents.

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BATH ORIGINAL

_ 2 -

As the development process progresses, the color developer compound is reduced the exposed silver halide to metallic silver, with the color developer compound as a function of the development process is oxidized and forms immobile compounds, whereas the non-oxidized color developing agent enters an image-receiving layer diffused. After diffusion, the color developing agent becomes in the image receiving layer or the image receiving element oxidized. The oxidized developing agent then undergoes coupling with itself or couples with a color coupler producing a positive dye image.

From BE-PS 792 598 and DT-OS 2 260 194 is more recent a photographic process has become known in which an image dye is generated by an oxidation process. In the off the BE-PS 792 598 un <£:> of the DT-OS 2 260 194 known processes, so-called oxichromogenic compounds are used, which a chromogenic oxidation can be subjected to the formation of a new chromophore. Suitable for the known method Oxichromogenic compounds are characterized by a developer residue and an oxichromogenic residue of the general formula D- (OC), in the D is a residue that has a silver halide developing function, e.g. a hydrophenone residue, and further in which OC is a residue which is subject to chromogenic oxidation to form an image dye, characterized. Advantageously, such Oxichromogenic compounds used in image transfer units, in which the corresponding, initially diffusing oxichromogenic compounds or the initially non-diffusing compounds in combination with corresponding silver halide emulsion layers be used.

For best results it is when using oxichromogenic Compounds desirable to use an oxidizing agent easily incorporated into a photographic material can be incorporated, has good stability and easily oxidizes the oxichromogenic residue without the other components a photographic material or a photographic film recording unit disadvantageously

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to affect. The oxidative conversion of oxichromogenic compounds or other color-forming substances, as already stated, are required to achieve the color image formation. As a result There is a need for compounds which bring about the oxidation process described in the desired manner can.

It has already been proposed, see, for example, the U.S. Patent Application Serial Number 367,304 filed June 5 1973, free nitroxyl residues as photographic oxidizing agents to use.

The object of the invention was to provide oxidizing agents for photographic Find recording materials that are less mobile than the nitroxyl compounds of the US patent application with the Serial Number 367 304 to prevent their migration or diffusion in the photographic recording material.

Nitroxyl compounds or nitroxyl radicals are known compounds with the remainder ^ N-O with an unpaired electron. the The structure of the fragment can be represented as a superposition of two resonance structures according to the following equation:

^ N® - o ° i > ^ u - ο

O) (2)

The contribution of each of structures (1) or (2) to the ground state can be different depending on the effects of conjugation and the polarity of the medium.

In the following, the nitroxyl radicals are simply represented by the resonance structure (2), without the electron pair am Represent nitrogen atom as is common practice.

There are already polymeric polymers containing nitroxyl groups

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- A -

knows. Those with a high content of nitroxyl radicals or residues are typically insoluble in water comparatively low molecular weight or are unstable or are desirable properties by virtue of a combination of these marked.

From the journal JACS, 89 ,, (1967), page 5072 is the synthesis and the anionic polymerization of a monomer of the formula I is known:

CH,
CH- 0 \ CH

I ³ Il

I Il / \

CH ₂ -CC 0— < J * Ο *

V ^ CH-

CH

and also the reaction of a copolymer of maleic anhydride and methyl vinyl ether in a 1: 1 molar ratio with the nitroxyl alcohol of the following formula II:

OH

II

The polymers that can be obtained from the monomer of the formula I. must be prepared by anionic polymerization, in which only polymers with a comparatively low molecular weight attack. Furthermore, the polymers which are derived from the monomer of the formula I are insoluble in water. the Polymers that can be prepared from the nitroxyl compound II can be soluble in water, but are considered strongly colored Connections described which tend to instability. However, polymers containing nitroxyl groups should only have a light red hue that is typical of the nitroxyl radical or the nitroxyl radical. The known polymers have

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Nitroxyl residues, which via ester bonds to the polymer chain are bound, which are known to be less stable than, for example, amide bonds.

From the dissertation by VA Golubev, University of Moscow (1966), it is also known to convert poly (acryloyl chloride) with the nitroxyl compound II to form insoluble cross-linked polymers, but are not suitable for use in ßeschicatungsmassen and can therefore not be used for photographic purposes . From the magazine Vysolconol. Svedin. / B / §_, (1967), page 866, the reaction of bialkylbis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-oxyl) silane with sulfur dichloride to produce a polymeric reaction product is also known. This polymer is a highly branched, water-insoluble polymer.

It is also known to convert nitroxyl groups into a wide variety of Polymers, especially in biopolymers and proteins, as labels to facilitate analysis by the "spin-labeling method". This method is comparatively low ! • 'close to the nitroxyl compound covalently to the investigated Bound to polymers. The N-O · bond of the nitroxide is unpaired Electron, which has a characteristic electron-spin-resonance spectrum. This spectrum, briefly below referred to as the "ESR spectrum", is very sensitive to the environment around the N-0 · bond, which is why there is a lot of information changes in the arrangement or design of the polymer can be obtained in the LSR spectrum of the ^ itroxides. These polymers have very low concentrations of nitroxyl groups and the processes for their manufacture require the handling of comparatively difficult to handle chemicals, e.g. Grignard reagent, nitroxyl chloride, free iodine, metallic lithium and the same. For example, from the journal J. Prakt. Chem., 2Γ7, (1963), 137 the treatment of mercurized, i.e. Polystyrene treated with mercury with nitrosyl chloride, the conversion of the obtained nitroso derivative to hydroxylamine

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with Grignard reagent and the oxidation of the reaction product known with silver oxide to the NitroxyIpοIymer. The polymer obtained contains about one nitroxyl radical for every 7 repeating styrene units. It is also known from the journal "Polymer", £ 8 (1972), polystyrene with t-butylnitroxyl radicals

in 4 to mark Geiger's yield. Finally it's over US Pat. No. 3,453,288 discloses nitroxy compounds of the following Use formulas III and IV for ESR marking methods:

N = C = O

Ill

However, none of these known polymers is in terms of its Instability, insolubility in water and the like, or because of the difficulty of making it on a large scale suitable for photographic purposes.

The invention was based on the knowledge that a certain IQasse of polymers containing nitroxyl residues are excellent for Photographic purposes can be used and can be used in particular in an advantageous manner for the production of photographic recording materials suitable, for example, for those used for the ear diffusion transfer method are determined because the polymers containing nitroxyl radicals are extremely stable, non-migrating Are oxidizing agents. As a result, they can be used with advantage wherever a stable, non-wandering Oxidizing agent should be used.

The new polymers containing nitroxyl radicals can be used more advantageously Use way for the production of photosensitive recording materials, which consist of a layer support and at least a photographic image applied to it -

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the layer and at least one layer with a stable compound containing nitroxyl radicals. In an advantageous manner However, the polymers containing nitroxyl radicals can also be used, for example, for the production of image receiving materials use, i.e. photographic recording materials which consist of a support and at least one image-receiving layer applied thereon.

The invention thus provides a photographic recording material of a layer support and at least one layer applied thereon with an oxidizing agent and one or several photosensitive silver halide emulsion layers / or an image-receiving layer which is characterized in that it contains a water-soluble polymer as the oxidizing agent, that is at least 40 moles from repeating units of the following Formula:

. (3) - CH — CH -

R CQ)
* ■ jrn

C = O
2 '

ir— ν !

(NIOX)
in which:

* Z Λ

Q is a divalent radical of the formula -R- (L) - (R) -,

34 m P

in which R and R are alkylene, arylene or alkarylene radicals and R is also a residue of one of the formulas:

0 OR ²

-COR * or -CNR ^ ⁵

can be, in which R is defined in the same way as R and in which the carbonyl group is directly on the polymer backbone sits, and m and ρ are each = 0 or 1;

η = 0 or 1;

L is an onium salt residue;

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R is a hydrogen atom or an alkyl radical; R is a hydrogen atom or a carboxy radical or together

where R is a carbonyl link;
2
R is a hydrogen atom or an alkyl radical or together

with R is a carbonyl radical and
(NIOX) a stable free nitroxyl residue,

and at least 5 MoI-I from recurring units with one Water-solubilizing remainder consists.

If R " ⁵ and R have the meaning of alkylene radicals, these preferably have 1 to 6 carbon atoms. If R and R ^ represent arylene radicals, these preferably have 6 to 12 carbon atoms. If R and R ^{4 have} the meaning of alkarylene radicals of the structure -Alk-Ar- or -Ar-Alk-, in which Alk is an alkylene radical and Ar an arylene radical of the definitions given, these radicals preferably have 7 to 12 carbon atoms.

For example, L can be a phosphonium salt residue represented by the following formula be:

(4) R ¹ -Al ¹ X®,

wherein R ^{1 is} an alkyl radical having preferably 1 to 10 carbon atoms and X ^ is an anion.

L can furthermore, for example, be an ammonium salt residue of fol following formula:

,. , R'-NR 'X ⁰ (4a) ι

where R 'and X® have the meaning given. Furthermore, L can be, for example, a cyclic ammonium salt, for example a radical of the following formula:

R ¹ V ^X J— Χ ^θ (4b) / \ /

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where R ^{f has} the meaning given and J stands for the atoms which are necessary to complete a 5- or 6-membered heterocyclic ring, for example to complete a piperidinium or piperizinium radical.

Finally, L may be, for example, a sulfonium salt residue of the following Formula be:

R '- S - X ⁰

where R 'and λ have the meanings already given.

If R has the meaning of an alkyl radical, this preferably has 1 to 6 carbon atoms.

If R has the meaning of an alkyl radical, this also preferably has 1 to 6 carbon atoms.

In addition to recurring units of the specified structure, the polymers according to the invention have at least 5 mol-I recurring units which have attached or bound water-solubilizing radicals, for example an onium salt radical, for example an ammonium, sulfonium or phosphonium salt radical, as described for L, or acid radicals , including acid salt residues, for example residues of the formulas -COOH, -COONa, -COONH ₄ , -SO ₂ H, -SO ₃ Na and the like.

Typical suitable nitroxyl radicals or nitroxyl radicals (NIOX) correspond for example the formula:

0 ·

(6) -R ⁶ -NR ⁷
where mean:

R is an optionally substituted alkylene radical with preferably 1 to 12 carbon atoms, especially 3 to 8 carbon atoms and no hydrogen atom on the carbon atom in the α-position with respect to the nitrogen atom of the indicated

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Formula, i.e. immediately adjacent to the nitrogen atom of the formula given, or an arylene radical with preferably 6 to 20 carbon atoms, which can optionally be substituted, for example by alkyl radicals with preferably up to 10 carbon atoms, alkoxy radicals with preferably up to 10 carbon atoms and the like;

R / is an alkyl radical with preferably 1 to 5 carbon atoms, which can optionally be substituted, preferably an alkyl radical having 3 to 5 carbon atoms and no hydrogen atom on the carbon atom in the α-position with respect to the

en
Nitrogen atoms or an aryl group with preferably 6 to 20 carbon atoms, which can optionally be substituted, for example by one or more alkyl groups with preferably up to 10 carbon atoms or one or more alkoxy groups with preferably up to 10 carbon atoms or one or more nitro groups.

Particularly advantageous nitroxyl radicals are heterocyclic radicals of the following formula:

(7)

where mean:

9 10 11

R, R, R and R each individually represent a short-chain alkyl radical with preferably 1 to 5 carbon atoms;

R and R or R "" and R imino radicals (= NH), which can optionally be substituted and can ^{correspond to the formula -NR 1} , in which R ^{1 is} an alkyl radical having 1 to 25 carbon atoms or together with the carbon atom on which they are attached , the carbon atoms which form a 5- or 6-membered cycloalkyl or cycloalkenyl nucleus including the corresponding 5- or 6-membered substituted nuclei having 5 to 25 carbon atoms

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are required, with the proviso that one of the radicals R or R together with Z has a double bond in the one completed by Z. Can represent core, in which case R ° or R represent / (1) an aryl radical having 6 to 25 carbon atoms, including a substituted aryl radical, for example a tolyl, Aminophenyl, diethylaminophenyl, chlorophenyl or diphenylaminephenyl radicals or (2) an optionally substituted amino radical, e.g. a dimethylamine, methylethylamino or methylphenylamino radical and

Z the atoms required to complete a 5-, 6- or 7-membered heterocyclic nucleus with up to 2 nitrogen heteroatoms including substituted 5-, 6- or 7-membered heterocyclic nuclei, the substituents, for example, from alkyl radicals having 1 to 25 carbon atoms , Aryl radicals with 6 to 25 carbon atoms, including substituted aryl radicals, amino radicals, including amino radicals substituted by alkyl and / or aryl radicals, optionally substituted carbonamido radicals, substituted sulfonamido radicals, substituted carbonyloxy radicals, oxo radicals (= 0), imino radicals C = NH), including substituted imino radicals , for example of the formula «NR ¹ , in which R ^{1 is} an alkyl radical as indicated, can also consist of hydroxy radicals or an oxygen atom.

For the production of nitroxy compounds which can be used for the production of polymers which can be used according to the invention, a wide variety of known synthesis methods can be used, as described, for example, in the book by EG Rozantsev, "Free Nitroxyl Radicals", Plenum Press, New York, 1970. A large number of stable nitroxyl compounds or nitroxyl radicals can be prepared from heterocyclic amines which do not have a hydrogen atom on the carbon atom in the α-position to the nitrogen atom, for example from di-t-alkylamines and t-alkylarylamines. Such amines are oxidized with hydrogen peroxide in the presence of (1) phosphotungstic acid or (2) a salt of vanadium, molybdenum or tungsten. Diarylamines are converted into the corresponding diarylnitroxy compounds with per-

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benzoic acid oxidized ^{at O 0 C.} Heterocyclic nitroxyl radicals or nitroxyls with more than one heteroatom, for example porphyrexide, and processes for their preparation are also known. Binitroxyls and conjugated biradicals are also known (reference is made, for example, to Forrester and co-workers "Organic Chemistry of Stable Free Radicals").

The term "stable" as used here in connection with the nitroxyl radicals or Nitroxylreste used \ tfird to the invention Polymeric oxidizing agents used are bound, says that these compounds are free radicals without decomposition exist for at least such a period of time until the image generation process is completed or at least substantially completed.

The nitroxyl radicals or nitroxyl groups used according to the invention containing polymers of the invention may be colored, provided that the color of the oxidizing agent corresponds to the quality of the image to be produced is not adversely affected.

In a recording material in which the oxidizing agent is behind an opaque layer remains so that it is not visible, the coloring of the oxidizing agent does not affect the quality of the image. Of course, colorless or practically colorless or slightly colored nitroxyl radical-containing polymers are particularly advantageous cause at most only a slight increase in the D-min values, since such compounds are particularly versatile. A colorless oxidizing agent or a practically colorless oxidizing agent can be used, for example, in a recording material or a recording unit such as is used for performing diffusion transfer processes any place that can also accommodate a colored oxidizing agent. In addition, however, a colorless or practically colorless oxidizing agent or one with only a slight inherent color, for example in an image receiving element or an image receiving material where it is not hidden from the viewer. Because of their more versatile Polymers with nitroxyl radicals or have proven useful

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NitroxyIres th of the formula (7) proved to be particularly advantageous, if in the given formula:

R, R, R and R each individually represent a short-chain alkyl radical having 1 to 5 carbon atoms;

R and R or R and R together with the carbon atom which they sit, the carbon atoms that make up a 5- or 6-membered cycloalkyl or cycloalkenyl nucleus are required and

Z is the carbon atoms necessary to complete an optional substituted 5- or o-membered heterocyclic Kernes are required, where the nuclei can be substituted e.g. by alkyl radicals with preferably 1 to 5 carbon atoms, Acyl radicals with 1 to 25 carbon atoms, optionally substituted amino radicals, optionally substituted Carbonamido, optionally substituted sulfonamido, optionally substituted carbonyloxy, üxo - (= 0) or Hydroxy radicals. Is the heterocyclic one completed by Z Core a substituted 6-membered core, then there is typically the covalent bond (the bond that connects the nitroxyl radical with the R.est of the polymer) in the 4- or para-position with respect to the nitrogen atom of the formula

The polymers containing nitroxyl radicals used according to the invention can be produced by various processes. One of these methods is similar to the method that, for example in Research Disclosure, Item 2578, December 1973 will. This process relies on the alkylation of a tertiary amine with an alkylating agent. ^ after this procedure will a polymer with repeating tertiary amine residues or functional alkylating radicals with a monofunctional alkyl ■ · lierungsmittel or a tertiary Amiη to produce a Ammonium salt implemented. This is advantageous for the production! The method used by the polymers which can be used according to the invention differs from the aforementioned method in that the 5 0 9 8 19/1023

monofunctional reaction component a nitroxyl radical or has a nitroxyl radical as a substituent. This means that an advantageously applicable method for Production of polymers which can be used according to the invention can be reproduced as follows:

A. The starting polymer is a tertiary amine:

polymer

R R

NHCCH ₂ Cl

(NIOX)

Polymer _n I γ

R-NT-CH 'cNH- (NIOX)

I ²

Cl ⁰

B. Starting polymer is an alkylating agent:

1. Polymer

CH ₂ Cl

or

2. Polymer +

CH ₂ Cl

0
NHCCH ₂ N (R) ₂ -

(NIOX)

NHC-N

(NIOX)

polymer

CH ₀ N-CH ₀ C-NH 2 | 2 j

(NIOX)

he

polymer

R j - _v "CH ₀ -N, .NC-NH

CI

(NIOX)

50981 9/1023

wherein each R represents, for example, an alkyl radical having 1 to 10 carbon atoms.

Another suitable method for producing according to the invention Usable polymers is based on the reaction of a primary amine containing a nitroxyl radical with a copolymer Maleic anhydride with the production of an N-substituted polyimide according to the following reaction equation:

- (CH ₀ CH-CHCH) - ^v 2 2 | ι 'n

, C C

NH,

CNIOX)

O = C C = O

ohI

NH (NIOX)

Ak

ONO (NIOX)

In the case of this last-described reaction, a sufficient one remains Number of carboxy residues unreacted, so that the polymer has the desired Has solubility in water.

According to the invention usable polymeric oxidizing agents with recurring Units of the specified formula, in which η = 1 and Q represents a simple alkylene or arylene radical, leave from the corresponding polymeric acid chlorides or esters with an amine containing a nitroxyl radical according to the following Create reaction scheme:

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Polymer CH ₉ CH
C = O Cl

or polymer

CH ₇

CH

C = O

t R

(NIOX)

polymer

CH _n »^

CH ₉ C = O

(NIOX)

In a corresponding manner, polymeric oxidizing agents with recurring units of the formula given, in which Q a simple carbonyloxyalkyl radical or a carbonyloxyaryl radical is obtained from the corresponding polymeric acid chlorides or acid esters and an amine containing a nitroxyl group.

The polymers used according to the invention can be made from homopolymers or copolymers. In the case of copolymers, these exist from recurring units of the formula given and recurring units from another for addition polymerization capable polymerizable monomers. Examples of copolymerizable comonomers are olefins, e.g. ethylene, Styrene, acrylic compounds, including acrylic acid and methacrylic acid esters, also acrylic acids, e.g. acrylic acid and methacrylic acid and the corresponding amides, also maleic acid, maleimide, methyl vinyl ether, Acrylonitrile, phenyl acrylate, isopropyl acrylate, N-vinyl-2-pyrrolidone, 2-acetoacetoxyethyl methacrylate, also active Monomers containing methylene groups which are curable by means of conventional photographic hardening agents, such as, for example from US Pat. Nos. 3,459,290 and 3,488,708, as well as sulfonic monomers, e.g. 3-acryloyloxypropane-i-sulfonic acid, sodium salt

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- 17 or 3-methacryloyloxypropane-i-sulfonic acid, sodium salt.

Regardless of whether the polymers are homopolymers or copolymers, the polymer should advantageously be a have a comparatively high molecular weight, preferably of over 500. Furthermore, the nitroxyl radicals or ftitroxylreste having recurring units of the specified Formula make up at least 40 LIo 1 -% of the total polymer in order to give it the desired oxidizing properties.

The use of polymers has proven to be particularly advantageous, which consist of more than 50 mol% of recurring nitroxyl radicals having units of the formula given exist. As already stated, the polymers used according to the invention should at least 5 I-iol- ° & consist of recurring units, which have a water-soluble residue. These are water-soluble Recurring units having a remainder can be identical to the recurring units having a nitroxyl radical Units or be different from these. In particular, such polymers are special from a manufacturing standpoint advantageous in which the water-solubilizing residues present in the same repeating units as the nitroxyl radicals or nitroxyl radicals.

Lde nitroxyl-containing polymers can be used for the production of various types of photographic materials can be used, among a photographic material the known photographic recording units or felt units are also understood here, which are used for carrying out Color diffusion transfer methods can be used. In advantageous In some cases, the polymers according to the invention are grounded as oxidizing agents used for the synthesis of color dyes. Thus, the nitroxyl radicals or nitroxyl radicals according to the invention Polymers used to make color developing agents to oxidize, whereupon the oxidized color developer compounds with the color couplers to produce ßildfarbstoffen react. On the other hand, the poly used according to the invention can

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lyinereii can also be used to make compounds directly to image dyes to oxidize, for example in the case of the use of leuco dyes, for example leucoindoanilines, Leucoindophenols and leukotriaryl methanes or other than so-called Dye precursors are known compounds.

The polymers used according to the invention can be used in a particularly advantageous manner for the production of photographic recording materials for color diffusion transfer processes, e.g. those processes in which unreacted color formers are used in undeveloped or partially developed areas of a photographic recording material image by image after color development The layers of the exposed layers diffuse in one Image receiving layer in which the color formers react with oxidized color developing agent to produce in imagewise Distribution of existing dyes. By accommodating a polymeric oxidizing agent used according to the invention in the image-receiving layer or in a layer adjacent to it, dyes can image-wise as a result of the reaction of oxidizing agents, Color developing agent and diffused color former are generated. Process of this type, as well as recording materials for carrying out such processes, for the production of which the polymeric oxidizing agents used according to the invention are used are described in more detail, for example, in GB-PS 926,462.

Examples of processes and recording materials suitable for this purpose, in which a dye image is obtained by oxidation of transferred color developing agents and color couplers known for example from US-PS 2,559,293 and 2,698,798. Even The recording materials according to the invention can be such as are disclosed, for example, in the two US patents 2 89 2 710 and 2 69 8 79 8 are known, the leucoanthraquinones and contain other dye precursor compounds which can be converted into dyes by oxidation or which are based on use are based on developer compounds which, when oxidized, are subject to self-coupling with the production of dyes.

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Finally, the oxidizing agents used according to the invention can also be used in the context of color diffusion transfer processes in which so-called leuco developer compounds may be used, as is known, for example, from the two US Pat. Nos. 2,992,105 and 2,909,430.

According to a further embodiment of the invention, they are grounded according to the invention used polymers for the production of recording materials, in which the developer part of a Dye developing agent is oxidized, i.e. a compound which have both a silver halide developer moiety and a special further R.est has, which is the chromophore of a Has ßildfarerstoffes.

The nitroxyl radical or the nitroxyl radical of the polymers must have an oxidation potential which is sufficient to cause the developer part of the molecule, e.g. the developer part consisting of a hydroquinone residue. In this embodiment of the invention, the nitroxyl radicals or nitroxyl radicals can be used of the polymeric oxidizing agent serve to form the dye developing agent to immobilize, e.g. when it diffuses into the image-receiving layer, e.g. by forming the corresponding quinone or quinonimides of the developer residue, \\ relches generally in is insoluble in an alkaline developing solution.

According to a further advantageous embodiment of the invention, the nitroxyl radicals or nitroxyl radicals can be used to to stabilize preformed image dyes. For example, the nitroxyl radicals can be used to improve stability of azo dyes to increase which in an image receiving layer have been transferred.

According to another advantageous embodiment of the invention, can a photographic recording material is treated with one of the oxidizing agents used according to the invention in such a way that that an imagewise distribution of the oxidizing agent is achieved. The recording material can then come into contact with a material

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which can be oxidized with generation an image recording in the recording material. For example in this embodiment of the invention a photographic recording material with at least one silver halide emulsion layer and an adjacent layer with the non-diffusing oxidizing agent containing nitroxyl radicals be developed with a silver halide developing agent. In the places where the silver halide does not develop the oxidizing agent is reduced. The recording material can then with a solution of a color coupler and a color developing agent are brought into contact, the present in imagewise distribution having nitroxyl radicals Connection with the color coupler and. the color developing agent reacts to form an image dye.

The polymeric oxidizing agents used according to the invention are suitable is particularly advantageous as an oxidizing agent for the production of photographic recording materials and film units, which contain oxichromogenic compounds of the type, for example, from BL-PS 792 598 and DT-OS 2 2G0 194 are known.

Particularly advantageous oxichromogenic compounds are those which undergo chromogenic oxidation to produce a photographic Subject to image dye.

According to a particularly advantageous embodiment of the invention, the photographic recording materials of the invention have at least one oxichromogenic compound of the following formula:

T- (Kupp) -N-Ar-J

where mean:

(Kupp) a photographic color coupler residue attached to the nitrogen atom is bonded via a carbon atom in the coupling position, for example the remainder of a phenolic coupler, a

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nes pyrazolone coupler, a pyrazolotriazole coupler or one Coupler with open-chain ketomethylene residues;

Ar is an arylene radical having 6 to 20 carbon atoms, which is optionally can be substituted or have fused residues;

J is an optionally substituted amino radical or a Ilydroxylrest or a radical of the formula:

where R is a radical having 1 to 12 carbon atoms, for example an optionally substituted alkyl or optionally substituted aryl radical;

R is a hydrogen atom or a radical of the formula:

wherein R has the meaning given and preferably one is polyhalogenated alkyl radical and

T is a residue that is (1) the residue of a silver halide developing agent and preferably consists of an aromatic radical which is substituted by hydroxy radicals and / or optionally substituted Amino radicals is polysubstituted or (2) an oxidizable one Remainder (oxidizable releasing group), i.e. a remainder, i ^ elcher by oxidation facilitates the subsequent cleavage of a residue, or a residue which can be oxidized and the normal splitting off of a residue under the development conditions prevented.

If T is a residue of a silver halide developer compound, then the resulting compound is preferably originally mobile. If T has the meaning of an oxidizable residue of the Oe-

5 0 9 819/1023 BAD original

of the type written, the resulting compound is preferred originally immobile.

The oxidizing agents containing nitroxyl radicals used according to the invention can also be used in a developing liquid used for photographic processing Recording materials and recording units for the diffusion transfer process is used. In a particularly advantageous manner, however, the oxidizing agents ground in the image-receiving layer or in a layer adjacent thereto of a recording unit intended for the fusion transfer method used. The recording units can have a structure as they are, for example, from DS-PS 2 543 181, 2 983 606, 3 227 550, 3 227 552, 3 415 644, 3 415 645, 3 415 and 3 635 707 as well as CA-PS 674 082 and BE-PS 757 959 and 75 7 960 is known.

The oxidizing agents used according to the invention are for example in the developing liquid of photographic recording units used for the diffusion transfer process, the oxidizing agents are advantageously used in about 0.01 to about 0.1 molar concentrations.

If the oxidizing agents are not accommodated in the developing liquid, they are contained in at least one layer of the recording material or the recording unit, which typically contains a conventional binder, for example gelatin or polyvinyl alcohol. The polymers containing nitroxyl radicals can, however, also be part of several constituents of a specific layer. This means that in the case of recording units for the color diffusion transfer process, the polymers used according to the invention can be contained, for example, in a mordant layer. Advantageously, the polymers in layer thicknesses of from about 4 to to 55 mg per 0,0929 m ^above substrate surface is used, depending on the ililliäquivalenten of nitroxyl radicals or radicals in the polymer. The amount of oxidizing agent and nitroxyl-

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; - 23 -

residues in the oxidizing agent depends of course on the amount and the type of compound used to be oxidized, for example the amount and type of oxichromogenic present Connection off.

According to a particularly advantageous embodiment of the invention, a recording material according to the invention consists of a Recording unit for the color diffusion transfer process, which is developed with a developing liquid and in the positive image obtained can be viewed through a transparent support against an opaque background can; preferably all of the silver halide recording layers and the image-receiving layer is laminated between two dimensionally stable substrates after the development process stay.

In a particularly advantageous manner, there is one according to the invention Recording unit, for example, from:

1. a light-sensitive recording part made from a layer carrier having coated thereon at least one silver halide emulsion layer which is an image dye-forming compound or is in contact with a layer having such a compound, the recording part preferably has at least three such layers or layer units, one layer consisting of a blue-sensitive silver halide emulsion layer consists of a layer of a green-sensitive silver halide emulsion layer and a layer of a red-sensitive silver halide emulsion layer, all of the layers being an image dye-forming layer Contain compound or are in contact with corresponding layers;

2. an image receiving layer, which is on a special support can be arranged, which rests on the light-sensitive recording part or can be placed on this part or preferably in the recording part on the same

. "BO9819 / 1023

Layer support is arranged and that adjacent to the photosensitive Silver halide solution layers and

3. a rupturable container with an alkaline developing liquid, which is arranged so that its contents into the Can eject the recording unit.

In those cases where the image-receiving layer is on the same support as the light-sensitive silver halide emulsion layers is arranged, the support preferably consists of a transparent support, preferably one opaque layer is disposed between the image-receiving layer and the light-sensitive silver halide emulsion layers. the alkaline developing liquid preferably contains an opacifying substance such as carbon or soot, or a pH indicator dye, which is in the recording unit between a dimensionally stable support or a cover sheet and the photosensitive recording part is ejected. In particular Cases may be the cover sheet on the photosensitive recording part rest or be of such a nature that it can be applied to the photosensitive recording part. The image receiving layer can optionally be applied to the cover sheet. Advantageously, in those cases where the Image receiving layer is part of the photosensitive recording part, a neutralizing layer is arranged on the cover sheet be.

The container with the alkaline developing liquid has the usual known construction, that is, it is in the recording unit arranged to have his content in the recording unit can eject 'when the recording unit is passed through the gap formed by a pair of pressure rollers. Instead of one If necessary, other means can be provided to divert the developing liquid into the recording unit introduce, for example, hypodermic syringes and the like.

509819/1023

The usual known silver halide emulsions can be used to produce the recording materials, as described in more detail, for example, in the journal "Product Licensing Index", Volume 92 of December 1971, Publication 9232 on page 107 in § 1 under the heading "Emulsion Types". The emulsions can be chemically and spectrally sensitized in a conventional manner, as described in more detail on pages 107 to 109 of the cited literature in the paragraphs "Chemical sensitization" and "Spectral sensitization". The emulsions can furthermore be protected against the occurrence of fog and stabilized against a loss of sensitivity, as is known, for example, from the cited literature reference, page 107, §V, "Antifoggants and Stabilizers". Finally, the emulsions can contain customary known development modifiers, hardeners and coating auxiliaries, such as are known, for example, from pages 107 to 103 of the cited literature (cf. §IV "development modifiers", §VII "hardening agents" and §XII "coating agents"). The emulsion layers and other layers of a recording material according to the invention can furthermore contain plasticizers, binders and filter dyes, as they are for example on page 103 in §XI under the heading "Plasticizers and lubricants" and in §VIII under the heading "Lindmittel" and on page 109 in §XVI under the heading "absorption dyes and FiI-te-r dyes" are described in more detail.

The individual additives can be added to the silver halide emulsion layers and other layers of photographic recording material are incorporated according to the invention by customary known methods, for example methods such as those on page 109 in §XVII are described in more detail under the heading "Methods of addition". Finally, you can distribute the recording materials Usual known coating methods can be used, such as for example, on page 109 in JXVIII of the cited reference are described under the heading "Coating Process".

5 0 9 8 19/1023 _BAD original

The image-receiving layers are conventional image-receiving layers, that is, the usual known compounds can be used to form the layers so long they are only able to ueizen or otherwise fix the transferred image dyes. The structure of the individual The image-receiving layers used naturally depend on the dyes to be stained. It applies acidic dyes too pickling, so the image receiving layers can using basic polymeric mordants, e.g. using polymers of aminoguanidine derivatives of vinyl methyl ketones, as they are known, for example, from LS-PS 2,882,156 and of basic polymeric mordants such as, for example from US Pat. No. 3,709,690.

Other suitable mordants are cationic mordants, e.g. polymeric compounds made from polymers with quaternary nitrogen atoms and at least two aromatic nuclei per quaternary nitrogen atom in the polymer cation, i.e. for each positively charged one At least two aromatic nuclei are present in nitrogen atoms, with polymeric mordants of this type having no or practically none Have carboxy residues. Typical suitable mordants of this type are made up of recurring units of the following formula, which are ethylenically unsaturated with units of at least one other Monomers are copolymerized:

CH

* - R ^lü -

, 15

\ vorin mean:

509819/1023

1 ^
R and R each represent a hydrogen atom or a short-chain alkyl radical preferably having 1 to 6 carbon atoms, with the proviso that. R can additionally be a radical with at least one aromatic nucleus, for example a phenyl, naphthyl or tolyl radical;

Q ¹ ". A divalent alkylene radical with preferably 1 to 6 carbon atoms, a divalent arylene radical, a divalent aralkylene radical, a divalent arylene-alkylene radical or radicals of the formulas:

0 0 0

Il ι 7 H 1 7 H 17 17

-C-OR-, -OC-R ¹ - or -C-NH-R ¹ -, in which R ¹ 'is an alkylene radical or Q ¹ can together with R form a radical of the following formula

N-R -, where R has the meaning given;

R ¹⁴ , R ¹⁵ and R ^{16 are} short-chain alkyl or aryl radicals, where the following applies

that R. and R and the nitrogen atom on which they are attached, together with Q ¹ , can represent the atoms and bonds which are necessary for the formation of a heterocyclic ring having a quaternary nitrogen atom and

a monovalent negative salt-forming radical or a corresponding monovalent atom in ionic relationship with the positive salt-forming residue.

The rule here is that the polymer is free or practically free from carboxy radicals and that the positive, salt-forming radical of the polymer is at least two aryl radicals for each quaternary nitrogen atom in the

5 09819/1023

should have lymer. Such advantageous polymeric cationic Pickling agents are known, for example, from US Pat. No. 3,709,690.

Further suitable mordants which are suitable for the production of photographic recording materials according to the invention are, for example, poly-4-vinylpyridine, and also the hetiio-p-toluene sulfonates of polymeric 2-vinylpyridines and other compounds such as those from IiS-PS 2 484 430 are known and also, for example, trimethylammonium bromide. Advantageous mordant compositions for producing image-receiving layers are further described, for example, in US Pat. No. 3,271,148 and in US Pat. No. 3,271,147. Finally, the polymers containing nitroxyl radicals used according to the invention, many of which have a quaternary nitrogen atom or a quaternary amine center, can also be used as mordants for acidic dyes, in which case the need to use other mordants is eliminated. This means that the polymeric oxidizing agents used according to the invention may not only perform the function of an oxidizing agent, but rather can also perform the function of a pickling agent for image dyes.

In the following, the production of some according to the invention will begin usable oxidizing agent are described.

Manufacturing process 1

Production of poly / il, N-dimethyl-N- (2-ethyl methacryl) -N- (1 - (N- (2,2,6,6-tetramethyl-4-piperidine-1-oxyl) acetamido)) ammonium chloride7 der Formula: _{Λ,. τ}

Ln,

C = O iI_C Cii_

I όι ^ S j

0 CH ₇ 0 j lc

1 I ₊ ³ Il / \

(CH ₂ ) ₂ N -CH ₂ CNH- ^ NO

CH

\ /
3 W- _C

CH ₃

^CH 3

509819/102 3

A solution of 3.18 g (0.0202.! Oils) of poly (2-dimethylaminoätliylmetiiacrylat) / N7P ■ = G, 40 (sämtlicne here specified viscosities are inherent viscosities were determined at 25 ⁰ C at a concentration of 0.25 g / jeciliter of a solution of the specified solvent) and 5.0 g (O, O2C2 ^ iole) 4- (a-Chloracetaniiuo) -2,2,6, S-tetramethy! piperidin-1-oxyl in 30 ml of K, N- dimethylformamide was heated on the steam bath under nitrogen for three hours. The polymer obtained was isolated by precipitation in ether and filtering off. Thereupon it was again in 30 mi; [ethanol dissolved. It was then again precipitated from the solution using ether, filtered off and dissolved in 30 ml of water while still moist.The solution was then placed in a rotary evaporator to remove excess traces of ether, leaving an aqueous solution of the polymeric oxidizing agent 1 with 18 % solid components.

The blemeiitar analysis of the compound of the _empirical formula 0 1π ίί _{? Γ} λ ^: -, 0.01 resulted in the following values:

Calculated: C: 56.4; II: 8.7; N: 10.4; Cl: 5.8 Found: C: 5ό.4; Π: 8.6; N: 10.4; Cl: 3.2

Manufacturing process 2

Preparation of poly {λ '- / 3- (1,1-dimethylpropylacrylamido) 7 ~ ^, N-dimethyl-N- / T- (N- (2,2,6,6-tetramethyl-4-piperidine-1- oxyl) acetamido]) ammonium chloride} of the formula:

C = O ".- _r,.

j bl Cii ~ ρ,

J «

H ₃ CC-CH ₃ CH ₃ O y ^

(Ch ₀ ) "-H -CK ₉ CNIM i) -O

ClI

BATH ORIGINAL 509819/1023

The procedure described under "Preparation Method 1" was repeated using 3.72 g (0.0202 moles) of poly / N- (3-dimethylamino-1,1-dimethylpropyl) acrylamide. 7 and 5.0 g (0, 0202 moles) 4- (a-chloroacetamido) -2,2,6,6-tetramethylpiperadine-i-oxyl, with the exception that the reaction product was isolated by precipitation from acetone. Jas precipitated polymer was dissolved in 70 ml of water. A clear solution with 9.9 % solids was obtained. The elementary analysis for the compound with the empirical formula O ₃ resulted in the following values:

Calculated: C: 58.4; K: 9.3; N: 13.0; Cl: 8.2 Found: C: 5 4.9; H: 9.0; Ii: 16.2; Cl: 6.9.

Letting process 3

Preparation of poly {N- / 3-propylacrylamido7 ~ N, N-dimethyl-N- ^ 7- (N- (2, 2,6, G-tetrar, iethyl-4-piperidin-1-o3cyl) acetamido} 7aninionium chloride} the formula:

-fCH ₂ -CH) - _{n C1} - ^

N - CIi ₂ CNH- ^ ß-0-

A \ / Pi!

CH ₃
d

₃
The preparation was carried out starting from 3,15g (0.0202 moles) of poly-ZN (3-dimethylamino _P ropyl) acrylamid7 l \? _H} ^ - _mmG ^ yI formamide = 0.28 and 5.0 g (C, Ü2O2 moles) 4- (a-chloroacetamido) -2,2,6,6-tetraiaethylpiperidin-1-oxyl in the under "Preparation process 1 "be described manner with the exception, however, that the reaction product was first isolated by precipitation in acetone, whereupon it was dissolved in 30 ml of methanol and precipitated by means of ether. The polymer was then dissolved in 35 ml of water, a clear solution with a solids content of 19% being obtained.

50981 9/1023

Calculated: C: 56.4; H: 8.9; N: 13.9; Cl: 8.8 Found: C: 56.5; H: 9.6; N: 13.8; Cl: 8.2.

Manufacturing process 4

Production of poly / styrene-co-N- (3-propylamidoacryl) -N, I \ idiraethyl-N- {4-acetamido-2,2,6,6-tetramethyl-piperidin-1-oxyl) -ammonium chloride7 the formula:

-KjH ₀ -CH-CI-I ₀ -CIiV
^v 2 ι 2 ι ^; n

C _r H _c C = O "

6 5 ι

"T ₊ ^ ³ Si

HCN * -CH ₀ CNH

CH
CH ₃

The polymer was produced as described under "Preparation process 1" using 2.62 g (0.0101 hole) poly / styrene-co-N- (3-dimethylaminopropyl) acrylamide / (ratio of monomers: 1: 1 ) and 5.0 g (0.0202 moles) 4- (α - Ch Io race t ami do) -2,2, -6,6-tetramethylpiperidin-i-oxyl with the exception that the solution is on the steam bath 5 Has been heated for hours. The reaction product obtained was dissolved in 30 ml of water. A clear solution with a solids content of 9.9 % was obtained. The theoretical values, calculated for C ₂₇ Il ₄₄ ClN, 0_ and the actually determined values were:

Calculated: C: 63.8; H: 8.7; Cl: 7.0; N: 11.0 Found: C: 66.8; H: 8.2; Cl: 5.3; K: 10.0

Manufacturing process 5

Production of polyivinylbenzyl chloride-co-N-vinylbenzyl-Ν, Ν-dimethyl-N- / 2-ethyl-4- (2,2,6,6-tetramethylpiperidin-1-oxy) urea7ammonium chloride} of the following formula:

50981 9/1023

-6CII ₂ -CH)

Cl

CH,
U ³

CK ₀ N "(CIi,) - KHCNf
2 j ^v 2 ^ 2

CH ₃

CH- CH, ο 3

A solution of 3.10 g (0.0203 moles) poly (vinylbenzyl chloride) / ~ r) 7 _benzene = 0.42 and 3.0 g (0.0102 hole) N- (2-dimethylaminoethyl) -N '- ( 2,2,6,6-tetramethyl-4-piperidine-1-oxyl) urea in 30 ml Methoxyätnanol was heated for three hours at 100 ⁰ C. The polymer obtained was then precipitated in acetone, filtered off and dissolved in 30 ml of methanol. The polymer was then precipitated by means of ether, filtered off and dissolved in 50 ml of water while it was still moist. The aqueous solution was placed in a rotary evaporator to remove traces of ether still adhering to it, an aqueous solution having a test substance content of 10.8% being obtained. The theoretical values calculated for CJi ₄₇ Cl ₂ N ₄ O ₂ and the actually determined values are:

Calculated: C: 05.1; H: 8.0; N: 9.5; Cl: 12.0 Found: C: 62.4; H: 8.2; N: 8.0; Cl: 11.6.

Manufacturing process 6

Production of poly / N-vinylbenzyl-NjN-dimethyl-N- (4-acetamido-2,2,6,6-tetramethy! Piperidin-1-oxyl) ammonium chlorate of the formula:

Cl

CH,

₀ -N -CIl ₀ CNH
2 ι 2

CH ₃

509819/1023

The polymer was prepared as described under "Preparation 5" using 3.82 g (0.0205 moles) of poly (vinylbenzyl chloride) Z ~ ^r 17 _benzene = 0.42 and 7.0 g, (0.02 73; iole) 4- (α-Dimethylaminoacetamido) -2, 2, 6, 6-tetramethylpiperidin-1-oxyl. The final product was dissolved in 60 ml of water. A clear solution with a solids content of 11.3 % was obtained. The theoretical values calculated for C-Ji-Jn 0 Cl and the actually determined values were:

Calculated: C: 64.6; H: 8.6; N: 10.3; Cl: 8.7 Found: G: 64.3; H: 8, D; N: 10.1; Cl: 7.9.

Manufacturing process 7

Production of copoly / styrene-N-vinylbenzyl-x \ ', N-dimethyl-N- (4-acetamido-2,2, G, ö-tetramethylpiperidine-1-oxyl) ammonium chloride 7 the formula:

A solution of G, 4 g (0.025 moles) of a copolymer of styrene

and vinylbenzyl chloride in a molar ratio of 1: 1 / ~ r \ 7, - _λΤ r, · * ι τ £ -j ^JJL - ' > j, N-dimethylformamide

= 0.75 and 7.0 g (0.0273 moles) of 4- (α-dimethylaminoacetamido) -2,2, -6,6-tetramethylpiperidin-1-oxyl in 75 ml of benzyl alcohol was left on under nitrogen for three hours Heated 1ÜO ° C. The polymer was isolated by precipitation in acetone and filtering off. Ls was then dissolved in -50 ml of methanol. The reaction product precipitated again in ether, filtered off and dissolved in 90 ml of water while still moist. The solution was then briefly placed in a flotation evaporator to evaporate traces of ether. An aqueous solution with a solids content of 0.4% remained. The theoretical values calculated for C _{3 QiU 3} KO ₂ Cl and the actual

509819/1023

BAD OBiSSNAL

actually determined values were:

Calculated: C: 70.2; H: 8.5; N: 8.2; Cl: 7.0 Found: C: 69.8; Ii: 8.2; N: 7.9; Cl: 5.1.

manufacturing process p

Production of poly / ethylene-co-N- (2,2,5,5-tetramethyl-3-pyrro lidin- 1-oxyl) maleimide / of the formula:

~ CIU

Line solution of 3, b5 g (0.029 moles) of a copolymer of ethylene and maleic anhydride in; Mole ratio 1: 1 and 5.0 g (0.029 Hole) 3-amino-2,2,5,5-tetramethylpyrrolidine-1-oxyl in 30 ml of N, N-Oime thy formamide 30 minutes, heated to 100 ⁰ C for! . The polymer was precipitated in ether, filtered off and dissolved in 50 ml of water while it was still moist. The solution was then briefly placed in a rotary evaporator to evaporate any traces of ether that were still present. An aqueous solution with a solids content of 10 % was obtained. The theoretical values calculated for C ₁₁ K ₀ -NaO ₁ and the actual values were:

Calculated: C: 59.3; H: 8.2; N: 9.9
Found: C: 56.9; H: 8.8; N: 10.4.

Manufacturing process 9

Production of copoly / ethylene-N- (2,2,6,6-tetramethyl-4-piperidin-1-oxyl) maleiiuid7 the formula:

5 0 9 8 19/1023

A solution of 3.55 g (0.029 mol) of a copolymer of ethylene and ilaleic anhydride in a molar ratio of 1: 1 and 7.0 g (0.041 mol) of 4-amino-2,2,6, o-tetramethylpiperidin-1-oxyl in 35 ml of N, N-dimethylformamide was added for 30 minutes at 130 ⁰ C erhitzt..Das polymer was then precipitated into ether, and dissolved in 50 ml methanol and precipitated again in ether. The polymer obtained was then filtered off and washed in 80 ml of water while it was still moist. The solution was placed on a rotary evaporator for a short period of time to remove traces of ether present. An aqueous solution with a solids content of 8.6 % remained. The theoretical values calculated for -C _{11 -H 71} -N ₂ O. and the actual values determined by analysis were:

Calculated: C: 60.7; K: 8.4; N: 9.8
Found: C: 58.7; H: 9.2; N: 9.3.

• The following examples are intended to illustrate the invention in more detail.

The oxychromogenic compounds mentioned in the following examples corresponded to the formulas listed in Table 1 below:

50981 9/1023

- 36 table

link

formula

. 0 0

ii ii

CCK.) - C-C-CIi-C-KK

OJ ι

KiI

Cl

OC-CH, OH

BgCCH ₂ J ₄

OH

, 011

JH

Cl
OCOCH

OH

)H

F F

NHCO

,) ₄ coNr y ff

KCOCF,

Cl

Cl

OH

609819/1023

- 37 -

OK

Cl

OCCF.

ti

The concentration data given in the following examples

each refer to a substrate area of 0.0929 m.

example 1

The oxidizing agents listed in Table 2 below were used tested in the following way:

First of all, matrix elements consisting of a transparent layer support and a gelatin layer with 125 mg of gelatin and 50 mg of one of the listed oxichromogenic substances applied to it
Compounds dissolved in 75 mg of diethyl lauramide, divided into different groups. the
Matrix elements were then brought into contact with an image-receiving element in the presence of an alkaline developing liquid. The alkaline developing liquid was placed between the matrix element and the silk receiving element.

5 0 9 819/1023

The image-receiving element consisted of a transparent support with a first layer of 200 mg of an oxidizing agent, manufactured according to one of the specified manufacturing processes, in 100 ng gelatin and a second layer of 2000 ng titanium dioxide in 200 mg gelatin arranged over the first.

The development fluid consisted of a 7.5 "proprietary potassium hydroxide solution with a content of 2.5 % hydroxyethyl cellulose as a thickener. The oxichromogenic compound was then oxidized by the polymeric mordant to the corresponding dye, which was visible through the transparent support against the white background of the titanium dioxide layer.

The following Table 2 shows the oxichromogenic compounds used in the individual cases, the oxidizing agents, the colors of the dyes produced and the density of the dyes in the image-receiving layers.

5098 19/1023

Table 2

Oxidizing agent Oxichromo contact dye according to Hei'stellungs- gen duration in in image processes IYr. binding seconds eiupfan ^ s-

s ch icht

Max

1 - A. 60 yellow 1.3 1 B. 60 purple 1.7 1 C. 60 blue green 1.7 2 ϊ) 60 If 1.5 CSl C. 60 II 1.2 2 B. 60 purple 2.1 2 A. 60 yellow 1.7 3 A. 60 yellow 1.4 3 B. 60 purple 2.2 3 D. 60 blue green 1.5 4th A. 60 yellow 1.5 4th B. 60 purple 2.3 4th D. 60 blue green 1.8 5 A. 60 yellow 1.3 5 B. 60 purple 2.4 5 D. 60 blue green 1.6 6th A. 60 yellow 1.2 6th B. 60 purple 1.3 6th D. 60 blue green 1.3 7th A. 60 yellow 1.5 7th B. 60 purple 2.1 7th D. 60 blue green 1.5 Example 2

The procedure described in Example 1 was repeated using the oxidizing agent prepared according to Preparation 8. This oxidizing agent does not contain a quaternary nitrogen atom, which is why between the oxidizing agent layer and Layer support was arranged a mordant layer, which was composed of 200 mg of copoly / styrene-N, N-dimethyl-N-benzyl-N (3-male- -imidopropyl) ammonium chloride7 in 100 mg gelatin.

509819/1023

Contact of the liatrix element and the image receiving element in the presence of the developing liquid (duration of contact oO seconds) the oxichromogenic compound A produced a yellow dye with a density of 0.7. Lei use of the oxichromogenic compound & became a purple dye with a density of 2.4 generated.

Example 5

ifs became a photographic material for the color diffusion transfer process manufactured with an integrated express train station. The recording material consisted of a transparent one Polyethylene terephthalate support on which the layers indicated below in the order indicated below were applied:

1.) a dye-mordant-oxidizing agent not of 100 mg Gelatin and 200 mg of the oxidizing agent according to the manufacturing process No. 4;

2.) a layer of 2000 mg titanium dioxide and 200 mg gelatin; 3.) a soot from 20 mg kiss and 156 mg gelatin;

4.) a layer of 75 mg gelatin, 70 mg 2,5-di-sec-dodecylhydroquinone and 23 mg tricresyl phosphate;

5.) a red-sensitive silver bromide iodide emulsion layer with 70 mg of silver, 230 mg of gelatin, 42 mg of the oxichromogenic compound H, dispersed in 73 mg of diethyllauramide, 5 mg of 5- (2-cyanoethylthio) -1-phenyltetrazole, dispersed in 15 mg tricresyl phosphate and 10 mg 5,6,7,8-tetrahydro-5, S-methano-1,4-naphthalenediol;

6.) a layer of 300 mg gelatin, 70 mg 2,5-di-sec-dodecylhydroquinone and 30 mg of a purple filter dye dissolved in 50 mg of diethyl lauramide;

BATH O.

50 9819/1023

7.) cine * green-insensitive silver broriiidjodidaruulsiousscnicht with 70 kg of silver, 230 mg of gelatin, 54 mg of the oxichroi: ogene compound L ·, dispersed in 64 i. g liäthyllauramid, 5 iiig 5- (2-CyaüOätnylthio) -1-phenyltotrazole, dispersed in tricresyl phosphate and 10 mg 5, 6, 7, 8 - Tetrahydro-5, 8 - ::: ethano-1, 4-napVithaliiidioi ;

0.) a layer of 300 rag gelatin, 70 mg 2.5 pi-sec. -dodecyihydroquinone and 100 my of a yellow filter dye, dispersed in 2 2 ing ciatliyllauramide;

. 3.) a jlau-e ^ roi pfiudliciie Silberb; idjodidu; .iuls ionssciiic.it} .ut 70 K ^ silver, 21Π r :: g Golatine, C'L wg the oxichron'Ogenen compound Λ, - üisporgiort in 10ο _α oi wtnyllauranid, 5 vg S- (2-L / anoätnylthio) -1-p3ien> ^r ltctrazole, dispersed in 15: i; g Tricresylp.ioS'ihat and 1ü-i: ig 5, ö, 7 , 3- ^r fctra; iyaro-5, G-methano-1,4-riaph.thalenediol;

10.) an ociiiciit made from SC ag gelatine.

The recording material described is transparent Jecxülätt dadurCii Jiergestell t that on a transparent Polyätnylentereputhalatscjiicbtträger were applied:

1.) a layer of DOO \ i ₆ gelatin, i "UEU r.ig t'ol / acrylic acid una 7o0 L! G Iiiiid

.) A Scniciit from 1140:;: _ü Oelluloseacetac and GO mg of a Copol / i.ieren from styrene and ^ alcinsüureanh / tlriu.

The phutographic recordings produced by Jasmine a viehrfarb testoi: ject jäit graduated degrees of light exposed, whereupon the transparent leaking sheet on the Aufzeicnnungsiumaterial applied xvurde. Between the recording material and the cover sheet became a splittable container with an opaque developing liquid gebraclit. Record material, splittable container

5 0 9 8 19/1023 ^ßAD ORIGINAL

and cover sheet were then stacked by the two i'i'alzen formed gap With a gap width of 0.20 mm guided. In the process, the splittable container was split open, as a result of which its Iimalt was distributed between the recording material and the cover sheet became.

The winding liquid had the following composition:

g / l

potassium hydroxide 51

liydroxyätnylcellulose 30

Ka 1 i UiTib ro mid 40

oi-lenzyl picolinium bromide 15 5,6, 7,8-tetrahydro-5, 8-ynethano-1, 4-naph-

thalindiol 15

I: uss 40

^T iit Water to make 1 liter

I was able to pass through the transparent substrate for about 1 to 2 minutes the integral linearity a well-defined color image with excellent color rendering can be observed.

BAD ORfSIMAL 509 8 1 9/1023

Claims (1)

Claims 1. Photographic recording material composed of a layer support and at least one layer applied thereon with an oxidizing agent and one or more photosensitive SiI overhalide emulsion layers and / or an image-receiving layer, characterized in that it contains a water-soluble polymer as the oxidizing agent, which is at least 40 Iiol- ^? o from recurring units of the following formula: - CH C - ¹ I ' R ¹ C = O 2 I. ρ ^ώ M (NIOX) in which: a divalent radical of the formula: -R ³ - (L) -CR ⁴ ) - in which R and R are alkylene, arylene or alkarylene radicals and R is also a radical of one of the formulas: 0 OR ² -COR ^{5 T} " or -C-N-R ° can be, in which R is defined in the same way like R and in which the carbonyl group is directly on the polymer framework sits, and m and ρ are each = 0 or 1; η = 0 or 1; L is an onium salt residue; 509819/1023 Iv is a hydrogen atom: i or an alkyl rust; U is a hydrogen atom or a carboxy substituent or 2
_ü c) iieiiisaiii iait "a caruonyluindeglied; I ^ a i'.assers toffatojii or an alkyl radical or ge together with ? ■. a carbonyl residue and (WIOX) a stable free 'Ai trox / lrest, and to at least 5 Iiol-'ό from iriederke ^ renden with one, ..water-soluble, raaciienden remainder. 2. Photographical recording material according to Claim 1, dadurcii marked, that it is a polymer lüit recurring as an oxidizing agent Contains linlicitcn of the formula given, in the (i \ I0X) is a heterocyclic xitroxyl radical. 5. PIiotograpliisciies recording material according to claims 1 and 2, dadurcii characterized that it is a polymer as an oxidizing agent with recurring lines from the above mentioned Fonuel, v.'orin η and m are each = 1 and L represents an ammonium salt residue. 4. Photographic recording material according to claims 1 to 3, dadurcii characterized that it is a polymer as an oxidizing agent with recurring lines of the specified formula as one . Contains a molecular weight greater than 5000. 5. Püotographic recording material according to claims 1 to 4 consisting of a photographic recording device the end a) a light-sensitive recording part made up of a layer support and at least one light-sensitive silver halide emulsion layer applied thereto, which contains a compound which produces an image dye or which is in contact with a rail containing such a compound; b) an image receiving layer and BAD ORIQiNAL 509819/1023 Hh c) an au Ts ^ aI t ^ aren container with an alkaline lungs Elassi ^ Kei t, i ^ ekennzeiciuie t, JaiTi die Auf zeiciinuukscinhoit as uxida ioiisiai ttel a in Uasser i-Jsiicues i ^J oiyi.icr the aii £ ej., eijeiit.n ^ iisciiös Aursoic.i-iaii ^ si.iatoricii. »ac»; , \ iis-rucu 5, uäuiircii ii;: oiε, ua; o it contains the UxiJatiüiis.ii ttel iii uor Jilüüji;) fan ^ sschiciit or in a kier.i.it Lu i-.oaLakt sLoiiCiideii Scniclit 7. ? Holo ^ la ^ iLis c / itii on 2cieiiüuiigs, .iateriai nau. Ans ^ ruci. 1>, ^ uke.mzciciincL, uaii ü3 das Oxidatiuji3j: »l tt- ^ i iji _u or alkalisc i_.iit.v ic.vlLiIi ^ j LLuSS i ^ JvOχ" ü enCj-ex 1 c. JAiOtügrapjiiscacs AuLSuicliiiuii ^ shiatdriai nacii / “ils;.! 'Those 1 uis 7, thereby ^ ekciiiizeic ^ iiioL, da;.; it as CxiaaLiüns ... i ttel a i'vjI / i.iüi-.r.it .iieucrkoiireiiaen i.inaeiten dor an ^ e ^ euenen iür.; iul entiidlt, woriu (i.I'Yes) a nuterocyclisciicr Aitroxylrost uer rol>; enüeu Foriuei is: -.10 S ^χ · „ι "in which each: Γ. °, R "'. Ί' 'uau -i each individually a short-chain alkyl rest; reiter.iin Γ. "And 'ι or V." ujid -. ^u an imino rest or together with the carbon atom j on which they sit, the koulenstoffatome, which to complete a 5-- or ö- ^ liedri ^ cn Cycloalkyl or Lycloalkenylrin ^ it are necessary, uüo weiteruin one of the radicals R 'or R together with Z forms a link in the cyclic one formed by Z BATH ORIGINAL 50981 9/1023 Nucleus, in which case R or R " ¹ represent (1) an aryl radical or (2) an amino radical and Z to complete a 5-, ü- or 7-membered heterocyclic ring required non-metallic atoms. . A photographic recording material according to claim 8, characterized characterized in that it is a polymer with repeating as the oxidizing agent Contains linearities of the formula given, ivorine (aIGX is a heterocyclic metroxyl radical of the following formula: / Z \ ivorin mean: s C 1Π 11 Γ, R, R ^w and Γ individually each a short-chain alkyl radical, R ^u and R or W and?. together with the carbon atom where they sit, the carbon atoms, those to complete a 5- or o-membered cycloalkyl or üycloalkenylringes are required and d Z to complete a 5- or ΰ-membered heterocyclic ring required atoms. 0. Photographischos recording material according to claims S and 9, characterized in that it contains a polymer with recurring linear units of the formula given as the oxidizing agent, in the (NiOX) is a heterocyclic i \ itroxylrcs t of the following formula is: BATH ORIGINAL 509819/1023 10 ο · η ^ IQ 1-1 ViOrin R, ΓΓ \, K and Γ. each a short-chain alkyl radical represent. 11. Photographic recording material in the form of a recording unit according to claim 5, characterized in that the light-sensitive Recording part a) ordered from a layer carrier with a red-sensitive silver halide emulsion layer applied on top, which contains a blue-green silu dye-forming compound or has a layer with such a compound Compound is in contact, a ^ green-sensitive silver halide emulsion layer, which contains a magenta image dye-forming compound or has a layer thereof Connection is in contact and a blue-er. Sensitive Si / overhalide emulsion layer, containing a yellow image dye-forming compound or having a layer with a such connection is in contact. 12. Photographic recording material according to claims 5 to 11, characterized in that there is at least one image dye generating compound that consists of an oxichromogenic compound T) it tent. 13. Photographic recording material according to claim 12, characterized characterized in that there is at least one oxichromogcnc compound contains the following formula: T- (KUPP) -N-Ar-J where mean: (KUPP) a photographic color coupler residue attached to the nitrogen atom is bound via a carbon atom in the coupling position • ■; OF ?? Q! _NAL 50981 9/1023 - * Wed Ar is an arylene radical; J is an amino or dydroxyl radical or a radical of Formula: -o-c-r "· wherein R * ^{1 is} an alkyl or aryl radical; R is a hydrogen atom or a radical of the formula: 0 -ü-C-R ^ wherein R ^ has the meaning given and T is the remainder of a silver halide developer compound or an oxidizable releasing group (oxidizable releasing group). 14. Photograpliisdies recording material according to claims 1 to 13, characterized in that it contains, as the oxidizing agent, a polymer with recurring units of the formula given, in which η and m jexieils = 1 and L represents an iminium salt residue. 15. Photographic recording material according to claims 1 to 14, characterized in that it contains a water-soluble polymer as the oxidizing agent, which is at least 40 2iol- $ from recurring Units of the following formula: R I R ¹ H • · R ¹ - eat - R ' _Ä I ⁴ C = O R ² - (NIOX) SAD 0r ?? 3! NAL 50 9819/1023 in which (NICX) has the meaning given and in which further οinterpret: R and R "each represent a hydrogen atom or an alkyl radical ..lit 1 to 6 carbon atoms, ■ ?. a hydrogen atom or a carboxy radical; 4 ^r
R and R ° each represent an alkylene radical having 1 to 6 carbon atoms and
R 'each represents an alkyl radical with 1 to 10 carbon atoms and
X ~ an anion. Photo graph is cii the recording material according to claims 1 to 14, characterized in that it removes a water-soluble polymer as the oxidizing agent, of which at least 40 ilol- ^ from re-teaching Lines of the following formula: I ₁ t R ¹ C = O _T U C = O
2 · (NIOX) in which (NIOX) has the meaning given and in which also mean: R and R ⁴ "each have a hydrogen atom or an alkyl radical having 1 to G carbon atoms; R represents a hydrogen atom or a carboxy radical; Λ i- R and R ^J each represent an alkylene radical having 1 to 6 carbon atoms; BATH ORIGINAL 50981 9/1023 each is an alkyl radical having 1 to 10 carbon atoms and λ "is an anion. 7. Photographic recording material according to claims 1 to 14, characterized in that it contains, as the oxidizing agent, a polymer which consists of at least 40% by volume of recurring units of the following formula: R I - cn - c— 4 'R ³ ρ »I γ © C = O - N (NOX) where (iNIOX) has the meaning given and also mean: 2
R and R each have a hydrogen atom or an alkyl radical 1 to 6 carbon atoms; R represents a hydrogen atom or a carboxy radical; R is an alkarylene radical having 7 to 12 carbon atoms; R ^{1 is} an alkyl radical having 1 to 10 carbon atoms and an anion. 50981 9/1023