DE3511678A1 - Photographic recording materials - Google Patents

Abstract

A photographic recording material with a base and at least one image-receiving layer applied thereto contains, in the image-receiving layer or in a layer adjoining the image-receiving layer, a coordination compound which is formed from a ligand of the general formula (I) given below and a metal ion: A-(L)n-Y in which A is a sulphonic acid group or carboxylic acid group or a salt of the acid, Y is a group which can provide quadridentate coordination with a polyvalent metal ion, L is a divalent organic group and n is the number 1 or 0. e

Description

Photographic recording materials

The invention relates to a photographic recording material, it particularly relates to a photographic material of the so-called Post-chelation type in which in an image receiving layer using a Dye ligands or a compound releasing a dye ligand, the (which) can form a metal chelate, a metal chelate dye is formed.

It is known that in photographic recording materials, particularly in color diffusion transfer photographic recording materials dye image-forming materials are typically used.

In this case, the stability, especially the lightfastness of the dye images formed, one of the serious problems.

To improve the lightfastness of dye images is it is known to use metal chelate dyes.

One method using a metal chelate dye is for example, in U.S. Patent 3,196,014. In a color diffusion transfer process, in which dyes are used that have previously been converted into metal chelate dyes the molecular weight of the metal chelate dye becomes huge, what has the disadvantage that the diffusion rate of the dye is delayed in the photographic material after exposure and development the images appear slow and require a long period of time until the formation of the images is finished.

To overcome this disadvantage, a post-chelation system is already in place become known in which a metal ion in an image receiving layer or in the Is fixed near the image receiving layer; a dye ligand (which was previously not metal chelate) as a result of development imagewise diffuses into the image receiving layer; and forming a metal chelate dye by a complex formation reaction between the metal ion and the dye ligand.

To improve the lightfastness of dye images using of the post-chelation system described above requires that in the image-receiving layer or in the vicinity of the image-receiving layer is available, which delivers a metal ion by a complex formation reaction can form a metal chelate dye with the dye ligand. The requirements, which are placed on the material supplying a metal ion are that of the material can easily be made that the material is essentially colorless that the material does not adversely affect the photographic Recording materials exercises that the material in the manufacture of the photographic recording material and not transferred in the processing of the photographic material will or will not migrate and that the material quickly becomes a metal ion to the dye ligand provides. The development of materials that provide a metal ion, which meet the above requirements is therefore very desirable.

Examples of metal ion donating materials include a high molecular weight Complex consisting of a polymer ligand with multiple ligand groups in the same Molecule and a metal ion is formed, such as in the Japanese OPI Patent Applications Nos. 48 210/80 and 129 346/80 (the one used herein The abbreviation "OPI" stands for a published, unexamined Japanese patent application).

The use of a chelated polymer ligand for Fixing a metal, however, brings about that the viscosity of a coating liquid when coating the layer containing the polymer as a function of the viscosity of the polymer fluctuates, making it difficult to obtain a photographic material with an exact and uniform layer thickness. When a cationic Polymer is used as a mordant and an anionic polymer is used as the polymer ligand is used, an insoluble polyion complex is formed and this leads to the formation of aggregates unsuitable for the formation of a smooth applied layer are, making it very difficult to mix the cationic polymer and the anionic Use polymers in the same layer. To avoid these difficulties, has already been proposed, the cationic polymer mordant and the polymer ligand to be used in the form of separate layers. But also in this case it is Formation of a polyion complex at the interface between the two Layers inevitable and this leads to a visible clouding (a so-called grinder), which reduces the commercial value. To avoid the above disruption It can also be considered adding an additional layer between the one dye ligand or a layer containing a dye ligand releasing compound and to provide the mordant layer to fix an imagewise released dye ligand, however, by arranging this additional layer, the distance between both layers increased, thereby helping to achieve a finished image after the Exposure and time required after development is extended what greatly reduces the commercial value of the photographic material, in which is the time required for images to appear and be complete, should be kept as short as possible.

It is also already known to have a low molecular weight ligand and an organic metal complex formed as a metal ion donor To use material for the production of a photographic recording material however, with a high commercial value, it is important to have both sufficient metal ion fixing ability as well as rapid metal chelation of a dye ligand.

That is, when a metal ion fixing ability is sufficient, the However, metal chelation reaction with the transferred dye is slow to proceed, becomes the wavelength of the absorption maximum of the dye ligand due to metal chelation shifted, whereby the tint of the color images formed increases as the color progresses Metal chilling reaction gradually changes. It is easy to understand that the change in the tint of the color images affects the commercial value of the photographic material greatly diminishes.

Even when the metal chelation reaction of a dye ligand rapidly advances (elapses), but the metal ion fixing ability is insufficient is, the metal ion diffuses into one or more layers when the Layer containing metal ions and the further photographic layer or Layers or the dye ligand diffuses beforehand at the start of development in an image-receiving layer and, if the metal ion, the light-sensitive silver halide emulsion layer reached, the metal ion produces a deleterious photographic effect. Even then, when the metal ion does not reach the photosensitive layer, a becomes Metal chelate dye formed before the dye ligand released after development the image-receiving layer reaches when the metal ion is divided into several types of layers diffuses between the image-receiving layer and the photosensitive emulsion layer. These phenomena cause an undesirable increase in the image transmission time and a undesirable reduction in image density. These disadvantages make the Commercial value of photographic recording materials within a short Period of time should deliver high quality images, especially in the case of color photographic images Instant materials or color diffusion transfer photographic materials, greatly reduced.

To prevent these harmful effects from occurring, it must be Metal ion in a specific layer in the image receiving material is sufficient be fixed.

However, if a dye ligand after exposure and development is released and reaches the image-receiving layer, that contained in the layer must Metal ion rapidly with the dye ligand after a ligand exchange reaction react.

In Japanese OPI Patent Application No. 38955/83, 105 146/83 and 129 429/83 are water-insoluble organic metal complexes as metal ions supplying compounds described. In the case of using one insoluble in water Metal complex as a metal ion supplying compound, however, the complex is in usually dispersed in a water-immiscible high-boiling bl, causing the formation of a metal chelate dye by ligand exchange reaction with a water-soluble dye ligands is delayed. Also, if such a in Water-insoluble metal complex compound is applied in the form of a layer, a high-boiling oil that does not participate in the photographic properties, can be used to disperse the compound because the compound is insoluble in water is what leads to undesirable defects as commercial products such as an increase the thickness of the photographic layers.

Also in Japanese Patent Application OPI No. 126 529/83 is Use of a water-soluble organic metal complex as a metal ion-donor Material described. In the case of using these metal complexes, it is generally it is very important to appropriately select the complex stability constant thereof.

That is, if the complex stability constant is too large, that is Fixing ability for metal ions is sufficient, the metal chelation reaction of a Dye ligand, however, is delayed while when the complex stability constant is too small, the metal chelation reaction of a dye ligand is high, however, the metal ion fixing ability becomes insufficient.

Especially in the case of using a bidentate ligand or of a tridentate ligand as disclosed in Japanese OPI Patent Application No. 126 529/83 described, it is difficult to have both sufficient metal fixability as well as a rapid metal chelating ability for a dye ligand to achieve, even if the amount of metal ion and ligand, to be fixed is changed. For example, diffuses in the case the use of the comparative compound given in Example 1 described below (ii) as an example of the above ligand even when a metal complex as a metal ion donating material using a ligand in a equivalent amount to a metal ion to be fixed is formed, the metal ion to another layer due to insufficient metal ion fixability. Even an attempt to improve the lack of metal ion fixing ability through education a metal complex using an excessive amount of a ligand leads to the disadvantage that the metal chelation reaction with a dye ligand is greatly delayed. Even if a metal complex using a ligand is formed in an amount twice that of a metal ion is, in the case of using the in the example given below 1 Comparative compound (iii) described above, the metal ion fixing ability is insufficient.

The object of the present invention is therefore to provide a photographic Recording material with an improved stability of the dye images in relation to to create lightfastness and the like. The aim of the invention is also to provide a photographic material having a high transfer speed to create the dye ligands. The aim of the invention is also to provide a photographic To provide recording material having a metal ion fixing layer which has an excellent Fixing ability for metal ions and a rapid ligand exchange reaction with one Has dye ligands. Another object of the invention is to provide a photographic A recording material having a metal ion fixing layer using a Ligands for fixation of metal ions to create that is cheap and can be easily manufactured. Another aim of the invention is to a photographic material having a metal ion fixing layer create with fewer coating defects, such as less formation aggregates, the formation of streaks and the like, occur during coating. target Finally, of the invention is a color diffusion transfer photographic recording material to create a new metal coordination compound.

After extensive research, it has now been found that the above various objects of the invention by the invention described below can be achieved effectively.

The invention relates to a photographic recording material, that in an image-receiving layer or in one adjacent to the image-receiving layer (adjacent) layer as a metal ion-supplying material a metal coordination compound contains, wherein as a ligand that builds up the metal coordination compound, a Compound of the general formula is used: AtL t Y (I) wherein mean: A a sulfonic acid group, a carboxylic acid group or a salt of the acid; Y a group, which can be tetradentate coordinated to a polyvalent metal ion; L is a bivalent organic group; and n is the number 0 or 1.

The present invention is explained in detail below.

As polyvalent metal ions associated with the ligand of the above general formula (I) are to be combined are transition metal ions, such as e.g.

Nu2 +, 2+ Zn2 +, pt2 + pd2 +, Co2 + and the like 6 preferred and among them Ni and Cu2 + are particularly preferred.

As the metal ion source for these metal ions is preferably a Solution (e.g. a solution in water, methanol, ethanol, dimethylformamide and the like. or a mixture thereof) a metal salt such as a hydrochloride, a sulfate, a nitrate and the like.

of the corresponding metal is preferably used.

As the group A in the general formula (I) is an alkali metal salt or an ammonium salt of sulfonic acid or a carboxylic acid preferred and below Of these salts, a sodium salt and a potassium salt are particularly preferred.

When n = 1, L in the general formula (I) represents, for example, an alkylene group, an arylene group, a composite group thereof or a divalent organic group formed by the composition of at least one of these groups and the divalent group of a carbonamido or sulfonamido group will. In particular, L stands for -CH2-, -CH2CH2-, (cm2) 3 r However, according to the invention, L is in no way restricted to these groups.

These divalent organic groups may be substituted, for example through a halogen atom (e.g., a chlorine atom and the like), a hydroxy group, an alkoxy group having 1 to 30 carbon atoms (e.g. a methoxy group, a dodecyloxy group and the like), an amino group, a carbamoyl group, a sulfamoyl group, a carboxy group, a sulfo group, an alkyl group having 1 to 30 carbon atoms (e.g. a methyl group, a t-butyl group, a t-amyl group, a t-octyl group, a dodecyl group, a Octadecyl group and the like), an aryl group having 6 to 30 carbon atoms (e.g. a phenyl group, a naphthyl group and the like), an aralkyl group of 7 to 30 Carbon atoms such as a benzyl group, a phenethyl group and the like) and the like.

Among these substituents, the alkyl group, the aryl group and the aralkyl group may be further substituted by a halogen atom (e.g. a chlorine atom and the like), a hydroxy group, an alkoxy group having 1 to 30 carbon atoms (e.g. a methoxy group, a dodecyloxy group and the like), a carboxy group, a Sulfo group and the like.

The group represented by Y in the general formula (I) is a group capable of tetradentate coordination to a metal ion, and examples of the group are: In the above formulas, a and b each represent an integer from 1 to 3; p and q each represent an integer from 0 to 2; u is an integer from 2 to 4; R1, R2 and R3 each represent a hydrogen atom, an alkyl group (e.g. a straight or branched chain alkyl group having 1 to 6 carbon atoms) or an aralkyl group (e.g. a benzyl group, a phenethyl group, and the like); and Z represents a nonmetal atom group necessary to form a 5- or 6-membered ring structure, which ring may be a saturated or unsaturated ring, or a carbon ring or a heterocyclic ring, or the ring may be further with another ring (as the ring described above) may be condensed. Specific examples of the ring are aromatic hydrocarbon rings such as benzene ring, naphthalene ring and the like, and nitrogen-containing heterocyclic rings such as

a pyridine ring, an imidazole ring, a quinoline ring and the like. In addition These rings may have a substituent such as those used as substituents for the groups represented by L have been given.

Preferred examples for Y are: in which R1 and R2 have the meanings given above.

Below are specific examples of the general Formula (I) shown ligands indicated.

Connection 1 Connection 2 Synthesis examples of the compounds represented by the general formula (I) are described below.

Synthesis Example 1 (Synthesis of Compound 5) Synthesis of N-methylaspartic acid After refluxing 196 g of maleic anhydride in 500 ml of water for 1 hour the solution was cooled to room temperature and after the slow The addition of 500 g of an aqueous 40-paste methylamine solution became mixture 3 Heated to 1200C for h in an autoclave with stirring. After getting the reaction mixture Allowed to cool, 160 g of sodium hydroxide was slowly added and then volatile materials were distilled off under reduced pressure. After that were Add 200 ml of water and 330 ml of concentrated hydrochloric acid to the residue, then it was cooled and the crystals precipitated were collected by filtration collected and dried to give 256 g of the desired compound. the chemical structure was determined by infrared absorption spectra and nuclear magnetic resonance spectra confirmed.

Synthesis of sodium 4-t-butylphenol-2-sulfonate To a solution of 53.3 g of 4-t-butylphenol in 400 ml of methylene chloride became a solution of 29.3 g of sulfuric anhydride added dropwise in 50 ml of methylene chloride at 25 to 30 ° C. over a period of 1 h.

After stirring the reaction mixture for 0.5 hour at room temperature the solvent was distilled off under reduced pressure. Then 100 ml of water and 300 ml of an aqueous saturated sodium chloride solution are added, the precipitated crystals were collected by filtration. The so collected Crystals were obtained from a mixed solvent of 500 ml of ethanol and 250 ml of water recrystallized to give 59.1 g of the desired compound. The chemical Structure of the product was determined by infrared absorption spectrum and nuclear magnetic resonance spectrum confirmed.

Synthesis of Compound 5 To a mixture of 8.8 g of N-methylaspartic acid, 2.2 g of an aqueous 37% formaldehyde solution and 100 ml of ethanol became a solution of 4.8 g of sodium hydroxide in 20 ml of water was added and then 13.5 g of sodium 4-t-butylphenol-2-sulfonate were added added to the mixture.

After stirring the resulting mixture at 80 ° C. for 10 hours the reaction mixture was allowed to cool, the precipitated crystals were through Filtering, collected, dried and dissolved in 60 ml of water with heating and it 220 ml of ethanol was added to the mixture with heating. After you get the Had the reaction mixture allowed to cool, the precipitated crystals were through Filtration collected and dried to give 18.5 g of compound 5 in which two carboxy groups were present in the form of the sodium salt. The melting point (F) was above 2500C. The chemical structure thereof was determined by infrared absorption spectrum and nuclear magnetic resonance spectrum confirmed.

Synthesis Example 2 (Synthesis of Compound 6) While cooling with ice, were 40 ml of a 1 N aqueous sodium hydroxide solution were added to 2.66 g of iminodiacetic acid and after adding 4.6 g of sodium 1-naphthol-4-sulfonate, 1.8 ml of a aqueous 37% formaldehyde solution was slowly added to the mixture. after the The resulting mixture was stirred for 1.5 hours under ice-cooling, became 6.25 ml of 6.4N hydrochloric acid was added to the mixture and the resulting mixture was left to stand in a refrigerator overnight. The precipitated crystals were collected by filtration and dried to give 4.26 g of the compound 6 with a melting point of 1250C (dec.). The chemical structure was through the infrared absorption spectrum and the nuclear magnetic Resonance spectrum confirmed.

Synthesis Example 3 (Synthesis of Compound 7) While cooling with ice, were 40 ml of a 1N aqueous sodium hydroxide solution and then 4.6 g of sodium 2-naphthol-6-sulfonate to 2.94 g of N-methylaspartic acid were added and then 1.8 ml of an aqueous 37% formaldehyde solution was slowly added to the mixture. After 1.5 hours Then, while stirring the mixture under ice-cooling, 6.25 ml of 6.4N hydrochloric acid became was added to the reaction mixture and the resulting mixture was allowed to stand overnight left standing in a refrigerator. The crystal precipitated was collected by filtration collected and dried, giving 5.27 g of compound 7 having a melting point from 1500C (dec.). The chemical structure was determined by the infrared absorption spectrum and confirmed the nuclear magnetic resonance spectrum.

Further compounds of the general formula given above (I) can also be prepared by the methods described above.

The appropriate complex stabilization constant (stabilization constant for metal ions) of the coordination compound used according to the invention 108 to 1022, preferably about 1012 to 1020. The stabilization constant can can be easily determined according to the edited in Kagehira Uesugi, Chelate Chemistry (6), Pp. 20-63 (1975).

The coordination compound used according to the invention can be used in a Image receiving layer of the photographic recording material according to the invention or in a layer adjoining (adjacent) to the image receiving layer (in a layer which is closely adjacent to the image receiving layer or in a layer, those to the image receiving layer via one or two or three layers quite is adjacent).

When the coordination compound used according to the invention in one Solvent (e.g. in water or in an organic solvent such as methanol, Ethanol, acetone, dimethylformamide, ethyl acetate and the like or a mixture thereof) is soluble, the compound can be made without using a binder or with any desired conventional binder can be applied in the form of a layer. If the coordination compound is insoluble in these solvents, you can the layer containing the metal ion source and the layer containing the ligand of the general Layer containing formula (I) can be formed as separate layers. Even if the coordination compound is soluble in a solvent can do the above called coating processes are used. The mordant layer can be used as a layer separate from said layers can be formed. A pickling agent can also in the layer containing the metal ion source or in the ligand of the general formula (I) containing layer are incorporated. With another Coating system can include the pickling agent, the ligand of the general formula (I) and the metal ion can also be incorporated into the same layer. If the the Layer containing metal ion source and the ligand of the general formula (I) containing layer are prepared separately from each other, it is also preferred the layer containing the ligand of the general formula (I) closer to one light-sensitive silver halide emulsion layer as that of the metal ion source containing layer to prevent diffusion of metal ions into the photosensitive Silver halide emulsion layer and into one a dye ligand or one To prevent dye ligand releasing compound containing layer.

If a binder is used, the mixing ratio is (Weight ratio) between the coordination compound used in the present invention and the binder about 20/1 to about 0.05 / 1, preferably about 5/1 to 0.2 / 1. The coating amount of the coordination compound is expediently about 0.05 up to about 20 g / m 2, preferably about 0.5 to 5 g / m 2.

When the layer containing the metal ion source and the ligand the layer containing the general formula (I) are formed separately from one another, is the ratio between the ligand of the general formula (I) and the Binder (ligand / binder) expediently about 20/1 to 0.05 / 1, preferably about 4/1 to 0.2 / 1. The coating amount of the metal ions is generally about 10 to about 10 1 mol / m2.

As a binder, which is used if necessary for the Coordination compound-containing layer for the layer containing the metal ion source Layer, for the layer containing the ligand of the general formula (I) and one or more further layer (s) of the photographic recording material according to the invention, can for example be used hydrophilic colloids, such as gelatin, poly (acrylamide), Poly (vinyl alcohol), poly (vinyl pyrrolidone), hydroxyethyl cellulose, copolymers thereof and graft copolymers thereof.

The photographic recording material according to the invention has at least an image-receiving layer applied to a support and the inventive Photographic material may or may not contain a silver halide emulsion layer and a dye ligand or a compound releasing a dye ligand, associated with the silver halide emulsion layer. When the photographic material does not contain these layers, becomes the photographic of the present invention Recording material used together with a photosensitive material, which has another support to which is applied at least one silver halide emulsion layer, associated with a dye ligand or a dye ligand releasing agent Link.

The photographic material according to the invention can be used in a heat generation type system as used in Japanese OPI Patent Application No. 58,543/83, but is particularly preferred used in a wet type color diffusion transfer process.

In the case of the use of the photographic recording material according to the invention in a wet type dye diffusion process, between the support and the The image-receiving layer of the photographic material has a neutralization rate controlling layer (timer layer) and a neutralization layer are provided be.

The photosensitive silver halide emulsion used in the present invention is a dispersion of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, Silver chloride iodobromide or a mixture thereof in a hydrophilic colloid. The halide composition of the silver halide emulsion is selected accordingly the use and processing conditions for the photographic Recording material, silver bromide, silver iodobromide or silver chloride iodobromide with an iodide content of less than 10 mol% and a chloride content of less however, more than 30 mol-t is particularly preferred.

The silver halide emulsion can be negative working Emulsion, which forms surface latent images, or a direct positive silver halide emulsion be. As the latter type of silver halide emulsion, direct positive ones are used Internal latent image type silver halide emulsion and one previously fogged direct positive silver halide emulsion is advantageous.

Among the silver halide emulsions, there can be a direct positive emulsion internal latent image type can be used with advantage and examples of silver halide emulsion of this type are silver halide emulsions of the conversion type, silver halide emulsions of the core / shell type, silver halide emulsions, the various kinds of metals and the like, such as in U.S. Patents 2,592,250; 3,206,313; 3,447 927, 3 761 276 and 3 935 014.

The silver halide emulsions used in the present invention can be used if desired have increased color sensitivities due to spectral sensitizing dyes. As the spectral sensitizing dyes, cyanine dyes, merocyanine dyes can suitably be used and the like. Can be used.

A dye ligand (the term dye "as used herein includes also the precursor thereof) or a compound releasing a dye ligand is a compound that develops as a result of heat or an alkaline Developer solution to form a diffusible dye ligand imagewise or can release, and any desired compound that undergoes a ligand exchange reaction with the above metal fixation coordination compound, can be used as such a compound. A preferred connection is a dye which forms a chelate compound with the above metal ion and particularly preferred are azo dyes and azomethine dyes.

Examples of azo dyes are dihydroxyazo dyes, pyridylhydroxyazo dyes, Aminohydroxyazo dyes, pyridylsulfonamidoazo dyes, hydroxyisopyridylazo dyes and the like. Specific examples of the dye ligand include dye developers with a chelating group.

One of the preferred dye ligand releasing compounds is also a non-diffusible redox compound (DRR compound) that is a Release diffusible dye component with a chelating group can. Examples of these compounds are, for example, in U.S. Patents 4,142,891, 4,248,956, 4,250,238, 4,195,994, 4,204,993, 4,148,641, 4,207,104, 4,147,544, 4,148,642, 4,148 643, 4,287,292, 4,346,155, 4,346,161, 4,357,410, 4,357,411, 4,368,153, 4,368,248, 4,357,412, 4,366,218, and 4,368,154, in Japanese OPI Patent Application No. 15448/84, 208 551/84, 164553/84 and 149362/84 and in Japanese patent application No. 146099/83 indicated.

Specific examples of DRR compounds that can be used in the present invention are given below.

In the case of the use according to the invention, the DRR compound can any silver halide developing agent that crosses the DRR compound oxidize can be used. Such a silver halide developing agent can be in an alkaline treatment or. Treatment composition or developing element) or in a suitable layer of the photosensitive Materials to be incorporated.

Examples of developer compounds used in the present invention are hydroquinones, aminophenols (e.g. N-methylaminophenol), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone, 1-phenyl-4, 4-dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like), phenylenediamines (e.g. N, N-diethyl-p-phenylenediamine, 3-methyl-N, N-diethyl-p-phenylenediamine, 3-methoxy-N-ethoxyp-phenylenediamine and the like.) and the like.

Among these developing agents is a black and white developing agent, which has the property of forming color stains in the image-receiving layer generally reduce, particularly preferred.

According to the invention, a mordant such as e.g., a poly-4-vinylpyridine latex (especially in polyvinyl alcohol), as in US Pat U.S. Patent 3,148,061; Polyvinyl pyrrolidone as described in U.S. Patent 3,003,872; or a polymer containing a quaternary ammonium salt or a phosphonium salt, as in U.S. Patents 3,239,337, 3,547,649, 3,709,690, 3,958,995, 3,770,439, 3,898,088, In DE-OS 22 64 073 and the like. Described, used with advantage. In these materials is to immobilize the metal coordination compound used according to the invention a polymer mordant containing a quaternary ammonium salt in the molecule, the having the acid group represented by A in the above general formula (I) can form an ionic bond, is preferred.

As a carrier for the photographic recording material according to the invention, for a photosensitive material to be used together with the photographic recording material is used, or a carrier can be used for a coating film, such as it is usually used in photography, and the one used according to the invention Support can be transparent or opaque (opaque).

Reference Example 1 Fixation of Nickel Ions A test film was prepared, by placing the following in succession on a transparent polyethylene terephthalate support Layers (1) to (3) have been applied: (1) A mordant layer, Contains 3 g / m2 of polydivinylbenzene-co-styrene-co-N-benzyl-N, N-dimethyl-N-vinylbenzylammonium chloride (Polymerization ratio 1: 49.5: 49.5), 3 g / m2 gelatin, 4 mmol / m2 of the following indicated compound (5) and 2 mmol / m2 nickel acetate; (2) a white reflective one Layer containing 20 g / m2 titanium dioxide and 3 g / m2 gelatin; (3) a layer containing 3 g / m2 of gelatin, in which is dispersed a solution of 0.48 g / m2 of the following indicated compound (i), dissolved in 0.24 g / m2 triphenyl phosphate.

The test film thus prepared was referred to as test film (A) and for comparison, a test film (B) was produced by the same method as above, which, however, did not contain the compound (5) in the layer (1).

Comparison compound (i) Compound According to the Invention (5) The test films (A) and (B) described above were left to stand at 45 ° C. and 60 ° C. relative humidity (RH) for 3 days. In the case of the test film (A) containing the compound of the present invention, the color of the layer (3) did not change, and in the case of the test film (B) in which the color tone changed even immediately after coating, the color tone changed completely from yellow to red-orange of the nickel chelate when the test film was allowed to stand under the above-mentioned conditions. By analyzing the absorption spectra, the conversion ratio of the compound (i) in the layer (3) into the nickel chelate was determined; the result obtained is shown in Table I below.

Table I Conversion ratio of compound (i) in the layer (3) in nickel chelate test film (A) 0% test film (B) 100% from the test results of the It can be seen from the above table that in the comparative test film (B), those shown in FIG Nickel ions contained in the pickling agent layer (1) have been transferred into the layer (3), to a complete Chelate compound (i) while forming in the test film (A) containing the compound (5) of the present invention, a change the color tint could be prevented by transferring the nickel ions.

Example 1 A photographic material (A) was prepared by successively placing the applied the following layers: (1) One layer (mordant layer), which was the same as layer (1) in Reference Example 1; (2) one layer (white reflective layer) which was the same as the layer (2) in the reference example 1; (3) a light shielding layer containing 0.75 g / m 2 of gelatin and 1.5 g / m 2 Soot; (4) a layer that was the same as layer (3) in the reference example 1; (5) A photosensitive layer containing 1.9 g / m 2 of a direct positive Silver bromide emulsion of the latent internal image type, 0.022 g / m2 2-methyl-3- (2-formylethyl) benzothiazolium bromide, 2 g / m2 gelatin and 0.13 g / m2 5-octadecylhydroquinone-2-sulfonic acid; (6) a coating layer, containing 2 g / m2 gelatin.

Also, a photographic one was made in the manner described above Comparative recording material (B) which does not contain a compound (5) according to the invention contained in the layer (1), a photographic recording material (C) which 4 mmol / m 2 of the known compound (ii) described in Japanese Patent Application OPI No. 126 529/83 contained in the layer (1) in place of the compound (5), a photographic one Recording material (D) containing 2 mmol / m2 of compound (ii) in layer (1) contained, and a photographic Recording material (E), the 4 mmol / m2 of the known compound (iii) described in Japanese Patent Application OPI No. 126 529/83.

A cover sheet was made by resting on a polyethylene terephthalate support successively applied the following layers (7) and (8): (7) a neutralization layer, containing polyacrylic acid; (8) a timer layer composed of a mixture made of cellulose acetate and poly (styrene-co-maleic anhydride).

After exposing each of the photographic materials to light (A), (B), (C), (D) and (E) the above-described coversheet was applied to each Material placed and between the elements was a treatment or. Developing fluid distributed with the following composition: treatment or development composition KOH (28%) 71 g Na2SO3 2.0 g 5-methylbenzotriazole 3.0 g 4-hydroxymethyl-4-methyl- 1-phenyl-3-pyrazolidon 5.0 g KBr 20 g carboxymethyl cellulose 44 g water ad 1 1 3 minutes after the treatment or development, the reflection spectrum in the Dmax portion of the transferred dye image is determined and analyzed of the spectrum became the chelation ratio of the transmitted diffusible Dye ligands (hereinafter referred to as "dye") determined, the obtained Results are given in Table II below are.

Table II Chelation ratio and optical density of the transferred dye photographic ligand ligand / Ni chelation optical density record- ing ratio (Dmax) material (%) material (A) Compound (5) 2 93 1.51 (B ) - 0 95 0.62 (C) comparative compound (ii) 2 40 1.31 (D) "1 93 0.73 (E) comparative compound (iii) 2 95 0.65 comparative compound (ii) Comparison compound (iii) As can be seen from the results in Table II, the photographic material (A) in which the compound (5) of the present invention was used had a high chelation ratio of the transferred dye and a high optical density thereof. This shows, since the compound (5) strongly fixes Ni2 + ions, that the dye was not chelated until the dye was transferred to the mordant layer, and therefore that the transfer of a dye was not disturbed and that after the dye was pickled, the compound (5) rapidly released Ni ions to the dye, thereby forming the chelate dye image.

On the other hand, the photographic material (B) had the did not contain a metal fixing ligand as the compound (5) contained a high chelation ratio of the transferred dye, the optical density of the resulting color image however, it was very low. This is because, since the photographic The recording material contained no Ni-ion-fixing compound, the Ni-ions diffused from layer (1) into another layer before the dye in the mordant layer (1) has been transferred to form a chelate compound of the dye, and that the transmission rate of the chelate compound des Of the dye formed thereby was very low.

Also in the photographic material (C) in which the Comparative compound (ii) was tridentate coordinated that of the invention Compound (5) is different, the optical density of the color images was high, however the chelation ratio of the transferred dye was very low. this shows that chelation of the dye did not occur until the dye in the pickling agent layer had been transferred, however, since the speed or Rate of Metal chelation reaction of the dye was low, no Ni ions were released to the dye, even after the dye had been pickled.

Also the photographic material (D) in which the comparative compound (ii) in a smaller amount, i.e. in one of that of the Ni ions equivalent Amount to decrease the rate of the metal chelation reaction had been used had a high chelation ratio of the transferred dye however, the optical density of the dye was low. This is due to, that the fixability for Ni ions was insufficient and therefore the dye in a chelate has been converted before the dye transfers to the mordant layer had been, whereby the transfer of the dye was severely hindered, as in Case of the photographic material (Bi in which no metal fixing ligand was used.

When the comparative compound (ii) in an equivalent 2+ amount was used to the Ni ions, the metal chelating ability was insufficient and even when the compound (ii) was used in an amount 2+ double corresponded to the amount of Ni ions, was the metal chelation reaction of the dye delayed.

Therefore, in the case of the comparative compound (ii) used, it was difficult to both sufficient metal fixability and rapid metal chelation to achieve the dye.

In addition, the photographic material (E) in comparative compound (iii) had the same tendency as that Photographic material (B) in which no metal fixing ligand is used that is, it showed a high chelation ratio of the transferred dye, However a low optical density of the color images. From this it can be seen that even when the comparative compound (iii) is used in an amount corresponding to the Twice that of Ni2 ions corresponds to the fixing ability of the metal ions is low and the dye is chelated before the dye is transferred into the mordant layer, whereby the transfer of the dye is disturbed.

As described above, the metal ion fixing ligand of the present invention excels compared to conventional ligands, such as the comparison compounds (ii) and (iii) in particular in that it has both a sufficient metal fixability as well as a rapid metal chelating ability of the dye can be achieved, what has so far never been achieved by conventional methods, through use a group that is tetradentate coordinated with respect to a metal ion.

In addition, according to the present invention, the metal ion fixing layer can be included less coating defects, such as

less formation of aggregates, less occurrence of strips and the like, and transferred dye images can also be used having excellent stability, such as particularly excellent Lightfastness and the like., Can be obtained.

The invention has been described above with reference to specific preferred embodiments explained in more detail, but it is self-evident for the person skilled in the art that it is by no means restricted to this, but that it is in many respects altered and modified without departing from the scope of the present Invention is abandoned.

Claims (11)

Claims 1. Photographic recording material, characterized by a carrier and at least one image-receiving layer applied thereon, that in the image-receiving layer or in an adjacent to the image-receiving layer Layer contains a coordination compound selected from a ligand of the following given general formula (I) and a metal ion is formed: A- (L) -nY (I) wherein: A is a sulfonic acid group, a carboxylic acid group or a salt of Acid; Y is a group which coordinates in a tetradentate manner with respect to a polyvalent metal ion can be; L is a divalent organic group; and n is the number 1 or 0. 2. Photographic recording material according to claim 1, characterized characterized in that the metal ion is Ni2 +, Cu2 +, Zn2 +, Pt2 +, Pd 2+ or Co 2+ 3. Photographic recording material according to claim 2, characterized characterized in that the metal ion 2+ or 2+ is Ni or Cu. 4. Photographic recording material according to at least one of Claims 1 to 3, characterized in that in the general formula (I) n the Number 1 and L represent an alkylene group, meaning arylene group, a composite group thereof or a divalent organic group formed by the composition of at least one these groups with the divalent group of a carbonamido or Sulfonamido group is formed, mean. 5. Photographic recording material according to claim 4, characterized in that L denotes -CH2-, -CH2CH2-, 6. Photographic recording material according to at least one of Claims 1 to 5, characterized in that the divalent organic represented by L Group is substituted by a halogen atom, a hydroxyl group, an alkoxy group having 1 to 30 carbon atoms, an amino group, a carbamoyl group, a sulfamoyl group, a carboxy group, a sulfo group, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms; or an aralkyl group having 7 to 30 carbon atoms. 7. Photographic recording material according to claim 6, characterized characterized in that the alkyl, aryl and aralkyl groups are each further substituted are through a Halogen atom, a hydroxy group, an alkoxy group having 1 to 30 carbon atoms, a carboxy group or a sulfo group. 8. Photographic recording material according to at least one of claims 1 to 7, characterized in that Y means: wherein: a and b each represent an integer from 1 to 3; p and q are each an integer from 0 to 2; u is an integer from 2 to 4; R¹, R and R³ each represent a hydrogen atom, an alkyl group or an aralkyl group; and Z is a non-metal atom group necessary to form a 5- or 6-membered ring structure. 9. Photographic recording material according to claim 8, characterized in that Y is wherein R1 and R2 have the meanings given in claim 9. 10. Photographic recording material according to at least one of Claims 1 to 9, characterized in that the coordination compound is a Complex 8 has 22 stabilization constants of 10 to 10. 11. Photographic recording material according to claim 10, characterized characterized in that the coordination compound has a complex stabilization constant 20 from 1012 to 1.