JPS616651A - Image accepting element for dye diffusion transfer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a dye diffusion transfer method (dye diffv, 5i
The present invention relates to an image receptor element for producing color photographic images by an ontransfer process, in which the dyes used to produce the color images are primarily diffusible dyes capable of post-metalization.

According to the invention, the image receptor element consists of a combination of layers arranged on a layer support, several combinations of which can be dyed with a diffusible organic dye and polymerized as a mordant for the image dye. repeating cations having a (meth)acrylic ester structure, (meth)acrylamide structure or maleimide structure in the form of It consists of a layer containing a polymer with structural structural units and an adjoining hydrophilic binder layer containing a metallizing agent in the form of a dispersion of a water-insoluble organic copper compound or a nickel complex.

In image receptor layers for photographic dye diffusion transfer processes, the use of polyvalent, especially complex-forming metal cations is of particular importance. As is known, the dye diffusion transfer method is particularly important for instant color photography, and it involves several silver halide emulsion layers of different spectral sensitivities and the color-providing compounds associated with these layers. It uses a photosensitive recording material. The color-providing compounds used can be, for example, chromophore-containing initially diffusible compounds and in the course of development fixing the compounds imagewise, or so-called "1-dye developers", which contain chromophores and fixing the compounds imagewise, or can be a non-diffusible color-providing compound (dye release agent) containing a chromophore that is imaged released as a dye precursor.If the dye developer is not If suitable as a ligand for forming complexes with cations, the formation of complexes can be effected or fixed in the color tone of the image dye transferred to the image receptor layer and stabilized against light. The formation of the complex is preferably carried out after dye transfer has taken place.
It is possible to treat the image receptor material with a solution of complex-forming polyvalent metal cations, for example in the form of a solution of the corresponding salt, or to add polyvalent metal ions to the image receptor material.
Alternatively, this can be achieved by incorporating them into further layers so that they readily react and undergo complex formation with the dyes that diffuse into these layers during the development process.

Polymers containing polyvalent metal cations bound in complexed form and their use in image receptor layers of color photographic materials for dye transfer processes are disclosed in Research Disclosure.
) IG, 18534 (September 1979); however, the polymers described there have only a limited ability to absorb polyvalent metal cations.

European Patent Publication Specification-1=EP-A) No. 0009411
It is known from No. 1 that cationic nickel- or copper(II)-complexes of polyvinylpyridine or polyvinylimidazole can be used as metallating agents for image dyes, which in turn allows the formation of complexes. There is. Although these complex compounds have little color of their own when pIi is neutral, in alkaline processing media they undergo rapid darkening and this dark discoloration occurs very gradually, if at all. It only disappears after a while, and during that time the image becomes less visible.

It is also known from the above-mentioned European Patent Application that polymeric metal complexes containing iminodiacetic acid units may also be used as metalizing agents. These metallating agents are difficult to handle in polymer chemistry methods and are susceptible to agglomeration, especially in the case of latex polymers.

U.S. Pat. No. 4,284,305 describes an image receiver element having a double layer structure consisting of a metal donor layer and a dye absorbing layer arranged thereon. The metallating agents mentioned include aqueous solutions of metal salts such as nickel sulfate. The dye-absorbing layer contains a polymeric mordant of a polymer having heterocyclic tertiary-amino groups, such as polyvinylimidazole. Even when using any bilayer arrangement, difficulties arise in casting these layers due to the reaction of the copper (I or nickel) ions with the polyvinylimidazole.Moreover, if the copper salt is If used as a colorizing agent, such an image receptor element cannot be used since even amounts of 5 mmol/mmol/millimeter or less have the undesirable effect of producing an inhibiting discoloration of the image brightness.

German Patent Publication (DE-A) No. 3.220°43
No. 5 has a layer which can be dyed with a diffusible dye and contains a mordant for the diffusible dye, and adjacent thereto,
A double layer image receptor element is described comprising a dye followed by a hydrophilic binder layer containing a metallating agent in the form of a dispersion of a water-insoluble organocopper (II) or nickel complex for metallization. . The mordant contained in the dye-absorbing layer to mordant the diffusible dye has a heterocyclic amino functional group,
Polymers containing structural units, optionally in protonated or quaternized form. It has been found that the light fastness of the mordanted image dye in this image receptor layer leaves room for improvement.

It was also found that the mordanted image dyes suffered from a shortwave shift in absorption maximum, which was particularly troublesome in the case of cyan dyes, which appeared entirely as blue.

It is an object of the present invention to provide a dual-layer image receptor element having a water-insoluble metallating agent incorporated in a hydrophilic binder layer adjacent to a dye-absorbing layer, which image receptor element is further improved in lightfastness. and ensure that the shortwave shift of the absorption maximum of the cyan dye described above does not occur or occurs only to a very small extent? ::hru.

Double-layer image receptor elements meeting the above requirements can be prepared if a water-insoluble organo-nickel or copper(I) complex compound is used as metallizing agent and in the form of an aqueous dispersion, optionally with the addition of an oil-forming agent, the adjacent If added to the casting solution for the hydrophilic binder layer, and if, in addition, the dye-absorbing layer contains quaternized tertiary-amino groups as a mordant for the diffusible imaging dye. It has been found that this can be obtained if the polymeric mordant contains a polymeric mordant having structural units containing it in a protonated form or in a protonated form.

The present invention comprises a hydrophilic layer arranged on a layer support and capable of absorbing a diffusible organic dye, and adjacent to this layer a metallating agent in the form of a dispersion of a water-insoluble organic copper(n) or nickel complex compound. an image-receiving element for a dye diffusion transfer process, comprising a dye-absorbing layer comprising a (meth)acrylic ester, (meth)acrylamide or has maleic acid imide structure and is acyclic but saturated cyclic tertiary
It relates to an element characterized in that it contains a polymer having repeating cationic structural units containing amino groups in protonated or quaternized form.

Suitable metallating agents that can be used in the hydrophilic binder layer adjacent to the dye-absorbing layer according to the invention are listed below.

Nickel and copper complexes of imino-bis-methylene-phosphinic acid or monophosphonic acid (formula I) or iminodiacetic acid (2): (I) (II) 2,2'-thio-bisphenol, Nickel complex compounds of 2,2-sulfinyl-bisphenol or 2,2'-sulfonylbisphenol (2■ and 2■): The symbols in formulas (I) to (II/) have the following meanings: 2R1
represents a hydrocarbon radical having up to 30 carbon atoms, optionally interrupted by -〇-;
alkyl, cycloalkyl, having up to 4 carbon atoms;
Aralkyl or aryl of 6 to 10 carbon atoms; R8, Rh' is alkyl or alkoxy of 1 to 4 carbon atoms, aralkyl or OH; ↑ X is -S-1-S-1 or - Hail SO,-;R
4 is a hydrocarbon group having up to 18 carbon atoms and is bonded directly or via -0-; halogen or a group R6
R11 is hydrogen, halogen, alkyl or alkoxy having up to 18 carbon atoms, alkenyl, a group completing a fused benzene ring; or R6, provided that R4 does not include R6; ;-NH-CO-R1,
Or hail -NH-S O, -RIO; R? represents alkyl, aralkyl or 7-chloroalkyl of up to 8 carbon atoms; R8, RI represents R1 and 7? or other groups that together complete a 5-, 16- or 7-membered cyclic amine group (pyrrolidine, piperidine, perhydroazepine, morpholine); R9 is alkyl, aralkyl, aryl; , -OR'is.

The radicals RL-R6 in formulas (I) to (l) are those which function inter alia as ballast groups, i.e. when all the radicals of the compound are taken together they represent the nickel and/or copper formed from the compound. It is of a size that ensures that the (II)-complex compound is incorporated with rapid diffusion into the photographic layer.

The hydrocarbon groups represented by RI and R4 can be, for example, alkyl, aralkyl, cycloalkyl or aryl groups. Ethyl, n-butyl, 2-ethylhexyl, n-dodecyl, n-octadecyl, benzyl, phenylethyl, phenyl, 4-dodecylphenyl and hiscyclohexyl are specific examples. The hydrocarbon radical interrupted by -〇- can be, for example, an alkoxyalkyl group or an alloxyalkyl group +4-(2,4-bis-t
-amyl-phenoxy)-butyl group is an example of such a group.

Examples of alkyl groups represented by RτR9 or RIo in RζR include methyl, ethyl, n-propyl, n-
Included are butyl, isobutyl and n-heptadecyl.

Phenyl and naphthyl are examples of Bt, Be and 7-10 aryl groups, and these may also be used, for example, for hydroxyl, methoxy, t-butyl or groups having the character of a ballast group, such as n-dodecylthio or n
- can be substituted with a hexadecyloxy group.

Examples of compounds corresponding to formulas (I) to (IV) are shown below: υ Compound 3 CH, -COOH CHs (CH2) st-A' CH, -000H Compound 5 Compound 6 Compound 8 Compound 9 Formula (+, Examples of nickel and copper(II)-complexes (chelate compounds) of compounds corresponding to ) to (IV) are shown below: Chelate 1 (Cu-1 chelate compound of compound 1), probably corresponding to the formula Do: Chelate 2 (nickel-chelate compound of compound 1),
Probably corresponds to the formula: Chelate 3 (Ni-chelate compound of compound 3), probably corresponds to the formula: 202. The water-insoluble nickel chelate compounds of 2'-thio-bisphenol, 2,2'-sulfinyl-bisphenol and 2j 2'-sulfonyl-bisphenol are 0.2'-thio-bisphenol, 2'-sulfinyl-bisphenol and 2'-sulfonyl-bisphenol per mole of bisphenol (III, F/). 5-1
．． 5 mol of nickel; those chelate compounds of bisphenol ■ correspond, for example, to formula (V), (■), (■) or (■), in which the radicals shown have the meanings given above, and L' represents a colorless, neutral (L) or anionic (L) foreign ligand introduced during the production process of the complex compound.

The following are examples of foreign ligands L that can be formed in nickel chelate compounds: preferably tertiary monoamines or diamines or amidines, such as ethyl-diisopropylamine, bis-2-hydroxyethyl-cyclohexylamine, pyridine, Diazabicyclo[2,2,2]-octane, 1,8-diazabicyclo(
[+4+0]-undecene and 1,5-diazabicyclo(4,3,0)-non-5-ene, di- or tri-esters of phosphoric acid, such as tributyl phosphite, aliphatic, cycloaliphatic or araliphatic alcohols, Glycol monoethyl or equivalent anion.

Chelate 5 (Ni-chelate compound of compound 4) LI
L' Chelate 6 (Ni-chelate compound of compound 4) -Pr "Chelate 7 (Ni-chelate compound of compound 4) Formula (I
) to (IV) and the nickel and copper(I) complexes obtained therefrom are disclosed in German Patent No. 3.
．． No. 220.435, which provides references still mentioned herein.

It is known that anionic image dyes suffer a significant loss of lightfastness when fixed on cationic mordants. The loss in lightfastness is highly dependent on the structure of the cationic mordant and the form in which it is incorporated; it is also related to the composition of the immobilized image dye, although this is difficult to predict.

To improve the lightfastness of image dyes immobilized on cationic mordants, German Patent Publication No. 40.7
No. 19 proposes that these dyes are then metalized with transition metal ions, which according to the invention is carried out adjacent to the dye-absorbing layer and in which the CtL-(I)-straddling Ni ions are water-insoluble. So-called "dispersed in the form of organic complex compounds"
This is done by using these metal ions which are supplied from a "metal donor layer" to a dye absorbing layer.

The use of nickel chelate compounds to stabilize color photographic images has been described many times in the past. For example, German Patent Application No. 2,85:(,826) describes the use of nickel chelate compounds of thioamides of the picolinic or quinaldic acid type to stabilize dyes against light.

However, the considerable self-pigmentation of the nickel chelate compounds described therein causes a prohibitive discoloration of the image brightness even when present in amounts of only 5 tnmol O per m' of image receptor layer; however, dye diffusion transfer methods Copper and nickel complexes used in image receptor elements for
0mmol/lr? Even when used in amounts of 0.0, the density measured behind the blue, green or red filter is
It must not cause discoloration of the dye absorbing layer of 07 or higher.

The copper or nickel complexes used according to the invention to incorporate copper(II) or nickel ions in a rapidly diffusive form into the layer can be introduced by various methods without loss in reactivity with the complexing dyes. I can do it.

Thus, for example, the complex compounds can be mixed with binders such as gelatin, polyvinyl alcohol, cellulose derivatives or polyacrylamide, and can be used in the form of such mixtures to create transparent layers.

The Cu-(II) or Ni complexes mentioned above have a uniform or image-like distribution of color therein due to the reaction of the complex-bound metal ions with other organic colorless or colored color-providing complex-forming agents. It is particularly suitable as a metal donor for incorporation into the photographic layer to be produced.

In contrast to the water-soluble metal salts used according to U.S. Pat. No. 4,282,305, the metallating agents used according to the present invention are more or less water-insoluble compounds;
The liquid is added to the layer in the form of a dispersion and then forms a separate phase therein due to its water insolubility. Water-insoluble Cu (
In order to incorporate II) or Ni complex compounds into a hydrophilic binder layer, in most cases they are first dissolved in a low-boiling solvent, such as diethyl carbonate or ethyl acetate, and this solution is then incorporated into a hydrophilic binder layer. Preferably, an oil-forming agent is added and dispersed into the casting composition for use.

These oil formers are generally substances that boil at temperatures above 180 DEG C. and are good solvents for the water-insoluble organic copper(I) or nickel complexes to be dispersed. The substances used as such oil formers are preferably glutaric acid, adipic acid, phthalic acid, cepatic acid, succinic acid, maleic acid, fumaric acid, isophthalic acid,
esters of terephthalic acid or phosphoric acid or esters of glycerol or paraffins or fluorinated paraffins, which is why these compounds are chemically stable and readily available, easy to handle and dispersions suitable for photographic purposes. This is because it does not have any harmful effect on photosensitive materials when used. According to the invention, the following are particularly preferred oil-forming agents: nitricresyl phosphate, triphenyl phosphate, dibutyl phthalate, di-n-octyl phthalate,
Di-2-ethyl-hexyl phthalate, glycerol tributyrate, glycerol tripropionate, dioctyl sepacate, paraffins and fluorinated paraffins. Monoesters of long chain alkylated succinic acids have also proven to be suitable oil formers. Compounds of this type are described in US Pat. No. 3,689,271.

The amount of oil former is preferably between 10 and 200% based on the total weight of Cm(II) or Ni chelate used.
%.

According to the present invention, the water-insoluble ('1L (I1) and nickel chelate compounds used as metallating agents) are used as metallizing agents in a hydrophilic layer adjacent to a dye-absorbing layer that can be colored by a diffusible dye in an image-receiving element. Contained in the binder layer.

This spatial arrangement ensures that the metallizing agent has no deleterious effects on the dye-absorbing layer, such as causing undesirable discoloration, and also ensures that if the dye is The metal ions can diffuse into the dye-absorbing layer with turbulence that allows the formation of complexes of the image dye in the dye-absorbing layer. The metallizing agent is preferably applied in one layer arranged on the side of the dye-absorbing layer facing away from the photosensitive element in the image-receiving element, for example between the layer support of the image-receiving element and the dye-absorbing layer. included in the intervening layer.

The polymer present as mordant for the diffusible anionic dye in the dye-absorbing layer of the image receptor element according to the invention contains in particular repeating cationic structural units corresponding to the following formulas (l and/or (X): R'-4-CH-C
H+- 1II where RA is hydrogen or methyl; RB, f are the same or different and represent an optionally substituted alkyl, aryl, cycloalkyl or aralkyl group having up to 12 carbon atoms; Hail, or BB and Ro together together with nitrogen atoms saturate 5-16-
or a group forming a ring of a 7-membered cyclic amino group, such as a piperidine group; B, D are hydrogen or groups as defined in RB and Ro; L' is -CO-0-(CH or -co-NH-(
CH, )-, which are directly bonded to the carbon atoms of the polymer chain via a carbonyl group; L2 represents an alkylene group of 2 to 12 carbon atoms; ? and m and n have values from 2 to 4.

RD preferably represents an alkyl group of the alkylating quaternizing agent, for example the following are particularly preferred: H -CHt-CH-CH, -CI OH -CH, -CH-CH, -OH, and L' The polymeric mordant according to the invention preferably has a binder corresponding to one of the following formulas: Co-0-CH, -CH, and -Co-NH-CH2-CH, -0. or (X
), or copolymers containing at least one of these elements. The structural elements of the formulas (l and (X)) preferably have an amount of at least 5 moles of the total polymer.The polymer mordant according to the invention preferably corresponds to the following formula (l: (,-,4-) , (-Jf- ~ (-V-),
(X+), where A represents a cationic structural element corresponding to formula (l or (X)); M has one copolymerizable ethylenically unsaturated group;
represents the residue of a polymerized comonomer; V represents the residue of a polymerized comonomer having at least two copolymerizable ethylenically unsaturated groups, such as vinyl groups;
And Z, y, and 2 are the following molar fractions of structural units derived from comonomers participating in the polymer, where X is a value of 0.05 to 1, V is a value of θ to 0.95, and 2 has a value of θ~0.18 (Z+M+z=1).

To produce the group represented by M, various copolymerizable monoethylenically unsaturated monomers can be used, including monomers containing conjugated ethylenically unsaturated bonds.

The following are examples of representative monomers suitable for producing residues of M: ethylene; propylene; 1-butene; 4-nor-1-lupentene-1; styrene, α-methylstyrene; fats. Monoethylenically unsaturated esters of group acids, such as vinyl acetate, isopropenyl acetate, allyl acetate and esters of di-carboxylic acids, such as methyl methacrylate, ethyl acrylate, glycidyl acrylate, glycidyl methacrylate, butyl acrylate and unsubstituted or substituted (meth)acrylamides; other monomerically unsaturated compounds such as acrylonitrile, methacrylonitrile, allyl cyanide, vinyl chloride, vinylidene chloride and N-vinylpyrrolidone; and conjugated dienes consisting of butadiene, isoprene and 2.3-Dimethyl-butadiene.

Monomers (crosslinking monomers) that can be used to produce the residues formed by (2) are mainly compounds corresponding to the following formula ()I): where n is an integer greater than 1;
Preferably 2.3 or 4; RE represents hydrogen or methyl; and RF represents 9-
Hail the attached organic group.

The following are examples of monomers suitable for producing the residue represented by V: Nidivinylbenzene; Allyl acrylate; Allyl methacrylate IN-allyl-methacrylamide; 4 H4
'-isoworopylidene-diphenyl diacrylate; 1
, 3-butylene diacrylate; 1,3-butylene-
Dimethacrylate; t,4-cyclohexylene-dimethylene-dimethacrylate; cyethylene glycol-dimeryl+)V-); diisopropylene glycol-dimethacrylate; ethylene-diacrylate; ethylene-
Dimethacrylate ethylidene diacrylate; 1.
6-Diacrylamidohexane; 116-hexamethylene-diacrylate; 1,6-hexamethylene-dimethacrylate, N,Nξmethylene-bis-acrylamide; neopentyl glycol-dimethacrylate; tetraethylene glycol-dimethacrylate; tetramethylene- diacrylate; tetramethylene-dimethacrylate; triethylene glycol-diacrylate; triethylene glycol-dimethacrylate; ethylidene-trimethacrylate;
1?2,4-vinyl-cyclohexane; and tetraallyl-oxyethane.

Trivinyl-cyclohexane, divinyl-benzene, tetraallyl-oxyethane and 1,4-butylene-dimethacrylate are particularly suitable monomers for producing the V-grouped residue.

Two or more of the above monomers can be used to form the units r of the polymer according to the invention.

Styrene and acrylonitrile are particularly suitable comonomers, especially those described in EP-A-00330
Suitable when used in the proportions given in No. 64. The composition of the monomer mixture disclosed in this document ensures that the copolymer has a chemically substantially uniform structure. This also ensures good solubility in aqueous systems with little clouding or phase separation.

The polymer can be used as an aqueous solution or as a latex (optionally crosslinked).

Examples of polymers that are suitable mordants include:

Polymer 1 Copolymers can be made by solution polymerization, precipitation polymerization or emulsion polymerization methods well known to those skilled in the art. They can be made batchwise or continuously or by flow mode. I can do it.

Preferred basic comonomers are N,N-trimethylaminoethyl-(meth)acrylate and N.

The incorporation of N-trimethylaminoethyl-(meth)acrylamide into a copolymer is preferably carried out with the aid of a free radical generating 1 initiator. For further details on the preparation of such copolymers, reference may be made to the following patent publications: U.S. Pat. The image receptor element according to the invention can form a composite component of a multilayered light-sensitive color photographic recording material, in which case it remains attached to the first light-sensitive element after development, or it remains attached to this element after development. can be separated from Alternatively, the image receptor element can initially exist as a separate photosensitive recording material, which is brought into contact with the photosensitive recording material for the first time during the photographic processing process and then separated therefrom. It is possible.

The image receptor element according to the invention is distinguished by significant advantages, in particular with regard to the high level of lightfastness and vivid shade of the transferred dyestuffs, in particular when the image dyestuffs used contain groups which can be chelated. That's the case when you are.

The image receptor element can be hardened in conventional manner to increase its scratch resistance and limit liquid absorption when processed in alkaline media.

The stability of dispersed copper(n) and nickel chelate compounds combined in the form of a dispersion is such that upon long-term storage, ions of copper(III) or nickel migrate into the hydrophilic binder layer and release the dye from there. Possibility of diffusion into agents (
These are sufficient to reduce the loss in diffusivity and photographic speed.

The image receptor elements of the present invention are characterized in that the image receptor element together with the layer of photosensitive element forms part of a complete layer unit--wherein the image receptor element is optionally optically The photosensitive element'b by an opacifying layer for separation into
- Particularly suitable for making a composite monosheet or single sheet material that may only be separated.

The image receptor element of the present invention comprising a hydrophilic binder layer containing a chelating compound as described above and a dye-absorbing layer adjacent to the binder layer comprises a diffusible image dye or a diffusible dye-forming material containing a substituent capable of forming a chelate. It is a suitable image receptor material for various diffusion transfer processes in which an agent (imaging dye precursor) is used or imagewise released and transferred to the image receptor layer. After this transfer, the image receptor layer of such a photographic material contains an imagewise distribution of this or more dye in the form of the corresponding dye-metal complex.

÷fi CIIIJsmall+≦1夷−malt r1? a! of
In addition to the image receptor element of the invention containing the (hydrophobic) copper(II) or nickel tin compound described above, the fungicidal material preferably contains at least one acid dye or a corresponding precursor compound. The photosensitive element can contain a photosensitive element in the form of a layer unit comprising one layer and at least one photosensitive layer, particularly a photosensitive silver halide emulsion layer. The dyes and dye precursor compounds mentioned above are all referred to below as color-providing compounds.

Such recording materials also advantageously contain spectral sensitivity in addition to other light-insensitive layers such as interlayers, overlays and other functional layers of the type commonly used in multilayer color photographic recording materials. It also contains several different light-sensitive silver halide emulsion layers.

Photographic materials comprising an image receptor element comprising a copper(n) or nickel complex according to the invention and a mordant according to the invention, i.e. the image receptor material itself, and also composites with such image receptor elements. Color photographic recording materials which contain as a part additionally an acid layer and a so-called "retardation layer"
(“rgtard-ing Lαygr”), which together form a so-called “combined neutralizing system” (Comhi-ned, neutralizat
ion system”).

Such a neutralizing system can be located in a known manner between the layer support and the image receptor layer disposed on this support, and it can also be located elsewhere in the layer combination, e.g. It can be placed above the layers, ie on the side of these photosensitive layers remote from the image receptor layer. The neutralizing system is normally arranged so that the retardation layer is located between the acid layer and the point where the alkaline developer or block paste enters the operation. Such a neutralization layer consisting of an acid layer, a retardation layer or both of these layers is
For example, U.S. Pat. No. 2,584,030, 2.983
゜606, No. 5,362,819, No. 3.562.
No. 821, German Patent Publication Specification Letter 2.455.762
No. 2.601,653, No. 2,652.464, No. 2.716.505, and No. 2.816.878. Such neutralizing systems can include two or more retardation layers in a known manner.

According to one particular embodiment, the photographic material can also contain one or more opaque pigmented layers that are transparent to aqueous liquids. These layers can serve two functions. Firstly, they can prevent the access of unwanted light to the photosensitive layer and secondly, especially when they contain bright or white pigments such as T i O, they can reduce the color produced. An aesthetically pleasing playground for images can be formed. Composite color photographic recording materials comprising layers of such pigments are known, for example, from US Pat. No. 2,543.181 and German Patent Publication No. 1.924.430.

Instead of including a preformed opaque layer, the photographic material can have means for generating such a layer during the development process. According to the dual function of the opaque layer mentioned above, such a pigment layer can consist of two or more partial layers, one of which contains e.g. a white pigment, while the other layer contains a dark color, e.g. carbon black. of light-absorbing pigments.

According to a particularly preferred embodiment of the invention, the photographic material is a composite color photographic recording material for carrying out a dye diffusion transfer process, for example consisting of the following layer elements: +l) a transparent layer support (2) Water-insoluble organic nickel or CL according to the present invention
(Hydrophilic binder layer containing a dispersion of a Hl complex compound; (3) Dye-absorbing layer containing a cationic mordant according to the invention; 14) Light-opaque layer (pigment layer); 15+ At least one photosensitive layer (6) a retardation layer; (7) a single layer of acid polymer; (8) a transparent layer support.

This material consists of two distinct parts separated from each other: the photosensitive part (layer elements 1-5) and the covering sheet (layer elements 6-8;
The two parts can be arranged so that their active surfaces contact and coalesce and optionally a space for receiving a precisely measured amount of developer is provided between the two parts. Place the spacer pieces in the middle so that they are left in between. - the layer elements 6 and 7 which together constitute the neutralizing system can also be arranged between the layer support and the image receptor layer of the photosensitive part, in which case they are arranged in the reverse order; be done.

Means for introducing a developer solution between two adjacent layers of the composite recording material may be provided, which is arranged laterally, for example in the form of a container and which is torn open by mechanical force to release its contents into the recording material. between two adjacent layers, in the case of the present invention between the photosensitive layer and the covering sheet.

When used in single-dye transfer processes, the photosensitive element contains a light-sensitive silver halide emulsion layer and associated color-providing compounds. In this case the color-providing compound can be located in a layer adjacent to the silver halide emulsion layer or in the silver halide emulsion layer itself. In the latter case, the color of the image dye is preferably selected such that the main absorption region of the color-providing compound does not coincide with the main sensitivity region of the silver halide emulsion layer. On the other hand, in order to produce a multicolor transfer image of pristine colors, the photosensitive element generally has a four-dimensional sensitivity region in the silver halide emulsion layer in which the absorption region of the image dye produced from the color-providing compound is associated. contains three associations of color-providing compounds, photosensitivity, and) silver rhodanide emulsion layers, substantially similar to the above. In that case, however, in order to achieve the highest possible sensitivity, the color-providing compound must be placed behind the silver halide emulsion layer (jf! looking in the direction of the output incident light) in a separate layer of binder #/C. or a color-providing compound having an absorption different from that of the image dye (U.S. Pat. No. 3,854.9).
No. 45 °transferred imaging dye” (“rhif-tmr
It is advantageous to use L irnagg dyLz ” l l.

A transition in absorption is generally obtained, if dyes with chelatable substituents are used, by complexation with copper (III or nickel ions) contained therein in the image receptor layer.

The color-providing compound can be a colored compound which is itself diffusible and which begins to diffuse when the layer is treated with an alkaline processing liquid and which is fixed only in the lighted areas by development.

Color-providing compounds, on the other hand, resist diffusion and can also liberate diffusible dyes during development. In this regard, most of the important known color supply systems are described by ArLggw-Charn.
) 95, 厖3. Please refer to the comprehensive explanation on pages 165-184.

When using the image receptor element according to the invention, it is preferred to use dye-releasing agents in which the dye residues contain substituents capable of forming complexes. Compounds of particular interest for this purpose are azo dyes having chelating substituents such as -OH, -NHR, and the ring nitrogen atom adjacent to the azo bond. Color-providing compounds containing dye residues such as
osurePublications 1461738
4 (September I978) and 1618022 (I979
April 2013) and U.S. Patent No. 3.081.167, German Patent Publication No. 2.740,719, No.
．． 540, No. 3,115.648, No. 3.117.
No. 245, U.S. Pat. No. 4,418,131, No. 4,3
No. 46,161, European Patent Publication No. 0095127
No. 0095524.

However, it has surprisingly been found that a stabilizing effect is also obtained when the dye liberating agents used do not then give rise to complexable dyes.

Example 1 Image receptor sheets according to the invention and image receptor sheets not according to the invention were prepared by applying the following layers in sequence to a polyethylene-backed paper support (amounts per layer): 1: 2.7F gelatin 1.3t chelate 2 (Ni1 1.7F+7) tricresyl phosphate 0.03f saponin layer 2: 51 polymer 25 gelatin 0.029 saponin CE.

(C parrot)! 0.2v of 2.5-sooctyluonoidoquinone 0.49 tricresyl phosphate 0, 02 f saponin #4: 0.9f gelatin 0.5f dimethylol urea.

The image receptor sheet was stored for 48 hours at 40° C. and 57% relative humidity before use.

Image receptor sheet 2 Same as image receptor sheet 1, except layer 1 had the following composition: 2.7t gelatin 1.22 chelate 3 (Ni1 1.6f tricresyl phosphate and H003f saponin) Same as image receptor sheet 1, but layer 1 had the following composition: 2.7F gelatin 0.8f chelate 5 (Ni 1 1.12 tricresyl phosphate and 0.05t
saponin image receptor sheet 4 Same as image receptor sheet 1, but with the following layers: 2.72 gelatin 1.2 to chelate 7 (Ni) 1.6 f tricresyl phosphate and 03 r
saponin image receptor sheet 1, except that layer 2 had the following composition: 52 polymer 1 52 gelatin 0,029 saponin image receptor sheets 1 to 5 were used, in each case a smooth A light-margined image receptor layer with a surface was obtained. The optical density measured behind the red filter was in no case greater than 0.05.

Same as image receptor sheet 1, except layer 1 had the following composition: 2.71 gelatin 1.12 tricresyl phosphate 1 ((I'tL1 2.22 tricresyl phosphate and 0.3
Same as image receptor sheet 1, except layer 1 had the following composition: 2.7 f gelatin 1.12 chelate 4 (Cu1 2.22 tricresyl phosphate and 0.032 saponin) Same as image receptor sheet 1, but layer 211 had the following composition: 52 Polymer 3 52 gelatin 0.02 f saponin Same as image receptor sheet 8, but layer 1 had the following composition: Chelate 1 (CtL) of gelatin 1.1 f of 2.72 tricresyl phosphate of 2.22 and 0,03 f
The image receptor layers obtained using saponin image receptor sheets 6 to 9 all have smooth surfaces, but image receptor sheets 6 to 9 have smooth surfaces.
．． The image receptor layers obtained in the cases of Nos. 7 and 9 have a light blue color, and in the case of the image receptor sheet 8 a light edge color. The optical density measured behind the red and blue filters is in each case less than 0.05.

Image receptor sheets were prepared by sequentially applying the following layers to a polyethylene-backed paper support according to conventional techniques (amounts are 1-per-inch):

Layer 1 5.5v gelatin 3.02 cationic polyurethane (German patent no.
631,521) 0.059 saponin layer 2 Same as image receptor sheet 10 layer 6.

Layer 3 Same as image receptor sheet 10 layer 4.

Image receptor sheet 11 (not according to the invention) Another image receptor sheet according to the prior art is image receptor sheet 1
0, except that layer 1 was prepared with the following composition: 5. Of gelatin 5. Of mordant B. layer quaternization) 0.52 saponin image receptor sheet 12 (not according to the invention) another image receptor sheet according to the prior art image receptor sheet 4
was prepared in the same manner as above, but with the same composition as layer 1 of image receptor sheet 11.

A 0.03 molar solution was prepared from the following post-complexable image dyes and the solution was made alkaline using 1T NaOH.

Dye A Dye B Dye C 5o, IVH.

Dye E Dye F Dye G Immerse a piece of each of image receptor sheets 1.4.5.8 and 12 into these solutions until a density of 1.5 is obtained, measured behind the extra color filter. did. Pieces of image receptor sheet 10 and 110 were soaked in nickel dithiacetate solution until a 30 second post-treatment gave a density of 1.5.

Each month was then post-treated for 1 minute with a 2% sodium succinate solution adjusted to pH 6 and dried.

The results show that the desired color tints can be obtained with virtually no delay in the image receptor sheets of the present invention compared to the prior art, and that the tints of image receptor sheets 1, 4, 5, 8 and 12 are the same as those of the image receptor sheets. 10 and 11 are similar to the shade obtained when post-treated with nickel acetate;
shows. No brown discoloration occurs. Complex formation is instantaneous and no gradual color change is observed. Image receptor sheets 11 and 12 (polyvinylimidazole-containing mordant il)
The hypsochromic effect of the shift of the maximum absorption of the cyan dyes E and F (as Keckel complexes) which occurs in the image receptor sheets 1.4.5 and 8 according to the invention is not observed in the image receptor sheets 1.4.5 and 8.

Table 1 1663 (5551665 (5601650<5661
4663 (5551665 (5601650<566)
1264B<540) 645(546) 635(5
50) The numbers in parentheses (λHBFKj) indicate the wavelength of the shortwave half-band flank.

To test the lightfastness, image receptor sheets 4.10.
A piece of each sample containing dyes A-G transferred to 11 and 12, respectively, was placed in a Xeno (Xt3o) test apparatus for 150 min.
Subjected to high intensity exposure for hours.

The nocucentage based on the initial density of 1.5 for the density loss found after 15, oxio'lux hours is summarized in Table 2 below.

Table 2 (according to the invention) Results show that the lightfastness of transferred colors obtained from post-complexable anionic image dyes is improved by metallization with hydrophobic nickel chelate compounds according to the invention. I accept the conclusion that it is true.

Example 2 A piece of each of image receptor sheets 6.7 and 9 was immersed in a dye solution until a density of 1.5 was obtained as measured behind the extra color filter. The polished pieces of image receptor sheets 10 and 11 were post-treated for 30 seconds with a 2% copper acetate solution until a density of 1.5 was given.
Soaked.

Each month was then 7) post-treated with a 2% sodium sulfur solution adjusted to H6 for 1 minute and dried.

The results show that the desired color tone can be obtained with virtually no delay compared to the prior art and that image receptor sheets 6.7 and 90
It is shown that the tint is similar to that obtained when tinted image receptor sheets 10 and 11 are post-treated with steel acetate. No brown discoloration occurs.

Complex formation is instantaneous and no gradual color change is observed.

To test lightfastness, a piece of each sample containing transfers of dyes A and G to image receptor sheets 6.10 and 11, respectively, was subjected to high intensity exposure in a xeno tester for 150 hours. The density loss found after exposure to 1.5OX10' hours is summarized in Table 3K based on the initial density of 1.5.

Table 3 The results show that the lightfastness of colors transferred from post-complexable anionic image dyes is higher than that of hydrophobic steels according to the invention (
Allows the conclusion that it can be improved by metalation using III chelate compounds.

Practical Application Example 3 The procedure was the same as in Practical Application Example 1, but with the following imaging dyes for which no post-complexation was possible: Dye H Dye IO Dye L n ( L'1ish Dye M Dye N Dye Q To test light fastness, image receptor sheets 4 and 11
A piece of each sample containing color transfers of dyes H and Q, respectively, was subjected to high intensity exposure [150 hours] in a xeno tester. The percentage of density loss found after exposure for 15.0 x 10' lux hours based on the initial density of 1.5 is summarized in Table 4K below.

Table 4 (according to the invention) The results allow the conclusion that the lightfastness of color transfers obtained from anionic image dyes which are not capable of post-complexation is also improved by the hydrophobic nickel chelate compounds according to the invention. .

Claims (1)

[Scope of Claims] 1. A dye-absorbing layer dyeable with a diffusible organic dye arranged on a layer support and a metalizing agent adjacent to this layer arranged on a water-insoluble organic copper(II) or nickel complex. The dye-absorbing layer consists of a hydrophilic binder layer containing the compound in the form of a dispersion, the dye-absorbing layer containing a polymerized (meth)acrylic ester, (meth)acrylamide or maleimide as a mordant for the diffusible dye. characterized in that it contains a polymer having repeating cationic structural units in which acyclic or saturated cyclic tertiary amino groups are contained in protonated or quaternized form. image receptor element for dye diffusion transfer methods. 2. At least one nickel or copper(II) compound corresponding to one of the formulas (I), (II), (III) and (IV) as a metallizing agent in the layer adjacent to the dye-absorbing layer. Complex compounds: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ Mathematical formulas, chemical formulas, tables, etc. ▼(IV) (where R^1 has up to 30 carbon atoms and can be -
represents a hydrocarbon radical, interrupted by O-; R^2, R^2' represents hydrogen, alkyl having up to 5 carbon atoms, cycloalkyl, aralkyl or aryl having 6 to 10 carbon atoms; , R^3, R^3' represents alkyl or alkoxy, aralkyl or OH having up to 4 carbon atoms; X represents -S-, ▲There are numerical formulas, chemical formulas, tables, etc.▼ or -SO_2- ; R^4 is a hydrocarbon group of up to 18 carbon atoms bonded directly or via -O-; or halogen or a group R
^6; R^5 represents hydrogen, halogen, alkyl or alkoxy having up to 18 carbon atoms, alkenyl, a group for completing a condensed benzene ring; or a group R^6;
However, in this case, R^4 does not represent the group R^6; R^6 is -CO-O-R^7, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc. ▼, -NH-CO-R
^9_9 or -NH-SO_2-R^1^0; R^7 represents alkyl, aralkyl, or cycloalkyl having up to 8 carbon atoms; R^8, R^8' represents R^2 and R^2', or the two together represent a group such as 5-, 6- or 7-
Represents a group for completing a membered cyclic amino group; R^9 is alkyl, aralkyl, aryl, -OR^7
or ▲ represents a mathematical formula, chemical formula, table, etc.; R^1^0 represents alkyl, aryl, or ▲ represents a mathematical formula, chemical formula, table, etc.) Image receptor element according to item 1. 3. Polymers whose dye-absorbing layer has repeating cationic structural units corresponding to formulas (IX) and/or (X) as mordants for diffusible anionic dyes: ▲Mathematical formulas, chemical formulas, tables, etc.▼(IX )▲There are mathematical formulas, chemical formulas, tables, etc.▼(X) (In the formula, R^A represents hydrogen or methyl; R^B
, R^C are the same or different and represent an optionally substituted alkyl, aryl, cycloalkyl or aralkyl group having up to 12 carbon atoms, or R^D and R^C taken together 5- along with the nitrogen atom
, represents a group forming a 6- or 7-membered cyclic amino group; R^D represents hydrogen or a group defined for R^B and R^C; L^1 represents -CO-O- (CH_2)_m- or -CO
-NH-(CH_2)_n-, these groups are directly bonded to the carbon atoms of the polymer chain via a carbonyl group; L^2 represents an alkylene group having 2 to 12 carbon atoms; 3 represents an anion; and m and n each represent a number from 2 to 4). 4. The polymer contained as a mordant in the dye-absorbing layer has a repeating structural unit corresponding to the following formula (X I ): (-A-)_
x(-M-)_y(-V-)_z(X I ) (wherein, A
is the formula (IX) defined in claim 3 or (
represents a cationic structural unit corresponding to X); M represents a residue of a polymerized comonomer having one copolymerizable ethylenically unsaturated group; represents the residue of a polymerized comonomer having a saturated group; x, y, z represent the molar fraction (x+y+z=1) of structural units derived from the comonomer that participated in the polymer; x is 0.05 to 1; y has a value of 0 to 0.95, and z has a value of 0 to 0.18). Receptor element. 5. Claims 1 to 4 are characterized in that they constitute a component part of a multilayer light-sensitive color photographic recording material containing at least one silver halide emulsion layer and a color-providing compound associated with this layer. An image receptor element according to any of Clauses.