DE19705691A1 - Metallocene-sensitised colour photographic material avoiding deterioration during storage - Google Patents

Abstract

A colour photographic silver halide (AgX) material has a base and AgX emulsion layer(s). The AgX emulsion contains a transition metal aromatic complex (I), spectral sensitiser(s) (II) and an alkyne compound of formula R1-C?=C-R2 (III), where R1, R2 = optionally substituted alkyl or (het)aryl and at least one of R1 and R2 contains polar, preferably hydrophilic group(s).

Description

The invention relates to a color photographic silver halide material with ver better sensitivity and lower haze.

It is known from US 5 457 022, the sensitivity of silver halide emul to improve sions by adding metallocenes. Metallocenes are over transition metal complexes of cyclopentadiene and its derivatives with iron, titanium, Vanadium, chromium, cobalt, nickel, ruthenium, osmium or palladium. Of the Iron (II) cyclopentadiene complex (ferrocene) is stated to be preferred.

At the same time, these connections create an undesirable veil increase after storage at higher temperatures and an undesirable Decrease in sensitivity found on storage.

The object of the invention was to avoid this disadvantage.

On the other hand, it is known that an addition of certain heterocyclic amines with an alkyne group improves the latent image stability (EP 658 803) and in some Cases also increased sensitivity.

Surprisingly, it is found that a combination of both additives Stabilization of the increased sensitivity when stored in the unexposed area stand occurs.

The invention relates to a color photographic silver halide material with a support and at least one silver halide emulsion layer applied thereon, characterized in that the silver halide emulsion layer contains a transition metal aromatic complex, at least one spectral sensitizer and a compound of the formula I:

R ₁ -C∼CR ₂ (I)

wherein
R ₁ and R ₂ independently of one another denote unsubstituted or substituted alkyl, unsubstituted or substituted aryl or unsubstituted or substituted hetaryl, at least one of the radicals R ₁ and R ₂ containing at least one polar, preferably hydrophilic group.

Preferred compounds of the formula (I) corresponding to the formula (II):

wherein
R _{3 is} unsubstituted or substituted alkyl or unsubstituted or substituted aryl
R ₄ and R ₅ independently of one another are hydrogen, alkyl or aryl or together the remaining members of a carbo- or heterocyclic, aromatic or non-aromatic ring and
X means O, S, Se or Te.

Preferably, R _{3 is} methyl or phenyl, X is oxygen and R ₄ and R _{5 are} hydrogen or C ₁ - to C ₄ -alkyl.

Suitable connections are:

The abovementioned compounds are suitable as transition metal aromatic complexes fertilize. However, aromatic complexes with a transition metal are preferred central atom that is present in a valency level that is not the one for the the metal in question is the highest possible, and the at least one non-aroma table complex ligands included.

Suitable transition metals are vanadium, chromium, manganese, iron, cobalt, Nickel, molybdenum, rhenium, ruthenium, rhodium, tungsten, osmium and Iridium.

In the preferred complexes the binding state corresponds to the transition metal central atom preferably a valence level that is at least one Unit is lower than in the lower-value inorganic salts of be appropriate transition metal.

The complexes according to the invention meet in terms of the electron balance Formula of the so-called 18-electron rule, as used by Mitchell and Parish in Journal of Chemical Education 46, 811-814 (1969) for transition metal complexes is fixed. According to this, all complexes according to the invention are in one reducing state.

As aromatics come z. B. those with 6 or 10 π-electrons into consideration preferably the cyclopentadienyl anion, the indenyl anion, pyrrole, thiophene and Benzene and their substituted derivatives, especially cyclopenta dienyl anion, optionally substituted by alkyl, aryl, carboxyl and carboxyl derivatives can be substituted.

Suitable non-aromatic complex ligands are, for example, CO, R-N = C and NO, with CO being preferred and R being alkyl or aryl.

Preference is also given to transition metal complexes with 2 cyclopentadienide Ligands, especially ferrocene and ferrocene derivatives, ruthenocene and rutheno cene derivatives, titanocene and titanocene derivatives, vanadocene and vanadocene derivatives, with titanium and vanadium as the central atom, additional non-aromatic ones Ligands may be present to fill the valence electron shell, e.g. B. Halogen, CO, NO, NS, SR and carbanionic radicals.

The preferred complexes are referred to below as s-complexes. The π complexes of formally zero to monovalent iron are particularly valuable of zero or monovalent manganese, of zero valent chromium. Particularly Cyclopentadienyl manganese carbonyls and cyclopentadienyl iron carbonyls are preferred, which do not have any electronegative ligands, in particular no halogen Contain ligands, but also aryl chromium carbonyls, aryl molybdenum carbonyls and Aryl tungsten carbonyls.

Cyclopentadienyl manganese tricarbonyl and im are particularly preferred Cyclopentadien ring substituted derivatives of cyclopentadienyl manganese tricarbo nyls, especially the methylcyclopentadienyl manganese (II) tricarbonyl and the aryl cyclopentadienyl manganese (II) tricarbonyls. The compounds are used in the chemi usually referred to as Cymantrene in the literature.

Cyclopentadienyl manganese or cyclopentadienrhe are also preferred nium dicarbonyls with another ligand on the metal atom. As ligands especially phosphines, phosphorus trifluoride, isocyanides, nitriles, ylides, etc. in question, but also carbene radicals, in particular via a heteroatom on directly bonded carbon atom have. The bond of the metal atom to one additional ligand can also be a double or triple bond.

The following are examples of cymantrene and other suitable complexes listed, with the five-membered carbocycle for the cyclopentadienyl anion stands.

Information on the preparation and properties of the low-valent transition metal complexes usable according to the invention can be found in particular in:

• 1) Angew. Chem. 86: 651-663 [1974]
• 2) Elscherbroich, Salzer: Organometallchemie, Teubner, Stuttgart 1993
• 3) Pauson, P.L. in: Houben-Weyl; Methods of organic chemistry, Volume E18, 1-450, G. Thieme, Stuttgart 1986.

Cymantren is known from
Piper, Cotton, Wilkinson; J. inorg. nucl. Chem. 1 (1955) 165, 175;
Cotton, Leto; Chemistry and Industry, Oct. 18, 1958.

Derivatives of cymantren are described at
Plesske; Angew. Chem. 74, 301-336 (1962);
Coffield, Ihrmann; J. Am. Chem. Soc. 82: 1251 (1956);
Riemschneider, Kassahn; Chem. Ber. 92: 3208 (1959);
Riemschneider, Petzold; Z. Naturforsch, 15b, 627 (1960);
Kozikowski, Maginn; J. Am. Chem. Soc. 81: 2995 (1959);
Cais, Kozikowski; J. Am. Chem. Soc. 82: 5667 (1960);
Cais et al .; Chemistry and Industry 1960, 202.

The spectrum of possible conversions on the cymantrene molecule is with the cited literature only indicated, but not delimited. So can for Example the carbonyl compounds of cymantren into the known derivatives such as Oximes, hydrazones, semicarbazones etc. are converted.

Examples of ferrocenes are listed below, with the five-membered carbocycle represents the cyclopentadienyl anion.

An older overview of the preparative possibilities in the synthesis of Ferrocene derivatives and derivatives of other stable ferrocenes, e.g. B. the ruthenocene and the osmocene is found in Bublitz and Rinehart in Org. Reactions 17, 1-154 (1969).

More recent literature is listed in Houben-Weyl, Methods of Organic Chemie, Volume 13 / 9a, pages 176-669 and in Lukehart, Fundamental Transition Metal Organometallic Chemistry, Brookes / Cole, Monterey Ca, 1985, pp 85-118 and in Lemenowski Fedin; Uspekhi Khim. 1986, Russ. Chem. Rev. 55, pp 127-142.

The alkynyl compound is the silver halide emulsion concerned in particular in an amount of 2. 10 ^-6 to 2. 10 ^-4 mol / mol Ag added. The time of addition is not critical and can be between the end of the precipitation and the pouring of the support.

The alkynyl compound is preferably added together with the spectral compound Sensitizer to the silver halide emulsion.

The transition metal aromatic complex is the silver halide emulsion concerned in particular in an amount of 10 ^-6 to 10 ^-2 mol / mol Ag, preferably 5. 10 ^-5 to 5. 10 ^-3 mol / mol Ag added.

The transition metal aromatic complex is preferably used together with the Spectral sensitizer added to the silver halide emulsion.

Spectral sensitizing dyes that can be used to advantage can be found in all common sensitizer classes, for example in the series the cyanine dyes, the merocyanine dyes, the rhodacyanine dyes, the Hemicyanine dyes, the benzylidene dyes, the xanthene dyes. Examples for these dyes are described in Th. James, The Theory of the Photographic Process, 3rd Edition (Macmillan 1966), pp. 198-228. Preferred are polymethine cyanines.

The dyes can be silver halide for the entire range of the visible Sensitize the spectrum and also for the infrared range. Particularly preferred dyes are mono-, tri- and pentamethine cyanines Benoxazole, benzimidazole, benzthiazole or benzoselenazole series, each in the benzene rings further substituents or further rings or ring systems fused, among the pentamethine cyanines again those whose Methine part is part of a partially unsaturated ring. The dyes can be cationic, uncharged in the form of betaines or sulfobetaines, or be anionic. The amounts of dye can be in the presence of the oversensitive bilizing cymantrene should be chosen higher than usual.

The silver halide used can be selected from silver chloride, silver bromide, silver chloride ridbromide, silver bromide iodide and silver bromide chloride iodide exist. The Kri Stalls can be homogeneous or inhomogeneous in zones, there can be a multiple crystals or single or multiple twinned crystals. The Emui Sions can consist of predominantly compact or predominantly leaflet form moderate crystals exist. In the case of lamellar crystals, those are with an aspect ratio above 3: 1 is preferred, especially hexagonal flakes with an adjacent edge ratio close to 1.

The emulsion crystals can also be doped with certain foreign ions, e.g. B. with polyvalent transition metal cations, preferably with noble metal cations, which have an octahedral ligand environment, e.g. B. with ruthenium, Rhodium, osmium or iridium ions, the function of the foreign metal ions doping essentially goes beyond that of a pure lattice disruption and on aims to incorporate so-called shallow electron traps.

The emulsions can be monodisperse or polydisperse, they can be demented Speaking through conventional precipitation, through one to multiple double inlets or with the micratum solution method.

The emulsions can be chemically sensitized in a conventional manner, e.g. B. through sulfur ripening, selenium ripening, ripening with sulfur and gold (I) - Compounds, as well as with so-called reducing ripening agents. the Reduction ripening can also occur in the course of the precipitation of the emulsion crystals in the Depth of the crystal can be built up, with the reduction maturation nuclei in the white teren growth of the crystals are covered. As a reducing ripening agent can divalent tin compounds, phosphane tellurides, salts of formamidine-C-sulfine acid and boranates can be used to advantage. Organically soluble, rapidly and Reduction ripening agents which can be fully adsorbed on the silver halide are preferred.

The oversensitization of spectrally sensitized emulsions with cymantren or Cymantren derivatives in combination with the stabilization by palladium (II) - Connections particularly advantageous.

Examples of color photographic materials are color negative films, color reversal films, color positive films, color photographic paper, color reversal photographic paper, color-sensitive materials for the color diffusion transfer process or the Sil Over-color bleaching process.

The photographic materials consist of a support on which at least one light-sensitive silver halide emulsion layer is applied. As a carrier own Thin films and foils are particularly suitable. An overview of carrier materials lien and auxiliary layers applied to their front and back is in rese arch Disclosure 37254, Part 1 (1995), p. 285.

The color photographic materials usually contain at least one red each sensitive green-sensitive and blue-sensitive silver halide emulsions layer and optionally intermediate layers and protective layers.

Depending on the type of photographic material, these layers can be different be arranged. This is shown for the most important products:

Color photographic films such as color negative films and color reversal films have in the order given below on carrier 2 or 3 sensitive to red liche, blue-green coupling silver halide emulsion layers, 2 or 3 green temp sensitive, purple coupling silver halide emulsion layers and 2 or 3 blue sensitive, yellow coupling silver halide emulsion layers. The layers same spectral sensitivity differ in their photographic emp sensitivity, with the less sensitive sub-layers usually closer are arranged to the carrier than the more sensitive sub-layers.

Between the green sensitive and blue sensitive layers is more common wisely applied a yellow filter sheet that prevents blue light from entering the layers underneath.

The possibilities of the different layer arrangements and their options effects on the photographic properties are in J. Inf. Rec. Mats., 1994, Vol. 22, pages 183-193.

Color photographic paper, which is generally much less sensitive to light as a color photographic film, exhibits in the order given below usually a blue-sensitive, yellow-coupling silver halo on each support genide emulsion layer, a green sensitive, purple coupling silver halide emulsion layer and a red-sensitive, blue-green coupling silver halide emulsion layer on; the yellow filter layer can be omitted.

There may be deviations in the number and arrangement of the light-sensitive layers to achieve certain results. For example can all highly sensitive layers in a layer package and all low sensitivity other layers in a photographic film be summarized in order to increase the sensitivity (DE 25 30 645).

The essential components of the photographic emulsion layers are binders, Silver halide grains and color couplers.

Information on suitable binders can be found in Research Disclosure 37254, Part 2 (1995), p. 286.

Information on suitable silver halide emulsions, their production, ripening, Stabilization and spectral sensitization including appropriate spectral signals sensitizers can be found in Research Disclosure 37254, Part 3 (1995), p. 286 and in Research Disclosure 37038, Part XV (1995), p. 89.

Photographic materials with camera sensitivity usually contain Sil berbromidiodide emulsions, which may also contain small amounts of silver chloride may contain. Photographic copy materials contain either silver chloride bromide emulsions with up to 80 mol% AgBr or silver chloride bromide emulsions with over 95 mol% AgCl.

Information on the color couplers can be found in Research Disclosure 37254, Part 4 (1995), p. 288 and in Research Disclosure 37038, Part II (1995), p. 80. The maximum absorption from the couplers and the color developer oxide The dyestuff formed by the product is preferably in the following ranges: Yellow coupler 430 to 460 nm, magenta coupler 540 to 560 nm, cyan coupler 630 up to 700 nm.

In color photographic films, to improve sensitivity, Graininess, sharpness and color separation are often used in the compounds Reaction with the developer oxidation product releases compounds which photo are graphically effective, e.g. B. DIR couplers, which act as a development inhibitor columns.

Information on such compounds, especially couplers, can be found in Research Disclosure 37254, Part 5 (1995), p. 290 and in Research Disclosure 37038, Part XIV (1995), p. 86.

The mostly hydrophobic color couplers, but also other hydrophobic components of the layers are usually in high-boiling organic solvents dissolved or dispersed. These solutions or dispersions are then in a aqueous binder solution (usually gelatin solution) emulsified and lie after drying the layers as fine droplets (0.05 to 0.8 µm diameter knife) in the layers.

Suitable high-boiling organic solvents, methods of incorporation into the layers of a photographic material and other methods, chemical Introducing compounds into photographic layers can be found in Research Disclosure 37254, Part 6 (1995), p. 292.

Usually between layers of different spectral sensitivity arranged non-photosensitive intermediate layers may contain agents the unwanted diffusion of developer oxidation products from a photosensitive in another photosensitive layer with different prevent spectral sensitization.

Suitable compounds (white couplers, scavengers or EOP catchers) can be found in Research Disclosure 37254, Part 7 (1995), p. 292 and in Research Disclosure 37038, Part III (1995), p. 84.

The photographic material can also contain UV light absorbing compounds, whiteners, spacers, filter _{dyes, formalin scavengers, light stabilizers, antioxidants, D Min} dyes, additives to improve the dye, coupler and whiteness stability and to reduce color haze, plasticizers (latices), Contain biocides and others.

Suitable compounds can be found in Research Disclosure 37254, Part 8 (1995), P. 292 and in Research Disclosure 37038, Parts IV, V, VI, VII, X, XI and XIII (1995), p. 84 ff.

The layers of color photographic materials are usually hardened; H., the binder used, preferably gelatin, is by suitable cross-linked chemical processes.

Suitable hardener substances can be found in Research Disclosure 37254, Part 9 (1995), p. 294 and in Research Disclosure 37038, Part XII (1995), p. 86.

After imagewise exposure, color photographic materials become their character ter processed according to different procedures. Details of the Procedures and the chemicals required for them are in Research Disclosure 37254, part 10 (1995), p. 294 and in Research Disclosure 37038, parts XVI to XXIII (1995), pp. 95 ff. Published together with exemplary materials.

example 1

A tabular silver bromide iodide emulsion with 9 mol% AgI, an average grain diameter of 1, matured to optimum sensitivity with tetrachloroauric acid (2 µmol per mol AgNO ₃ ), potassium thiocyanate (250 µmol per mol AgNO ₃ ) and sodium thiosulfate (10 µmol per mol AgNO ₃₎ 5 μm, corresponding to the mean diameter of the circle of equal area and an aspect ratio of 7.5, 50 mg per mol of Ag of a transition metal complex (0.5 g each dissolved in 100 ml of acetone) are added, followed by 300 mg of a mixture each time the red sensitizers RS-1, RS-2 and RS-3 in a weight ratio of 3: 6: 1. For some samples, an alkynyl compound is added in the amount (mg / mol Ag) given in the table together with transition metal complex and sensitizer mixture.

The sensitized emulsions are after the addition of a color coupler emulsified with the following jobs on a 120 µm thick subbed carrier Cellulose triacetate applied.

Cyan Coupler C-1 0.3 g / m ² Tricresyl phosphate 0.45 g / m ² gelatin 0.7 g / m ² Silver halide emulsion 0.85 g AgNO ₃ / m ²

A protective layer of the following composition was applied to this:

Hardener H-1 0.02 g / m ² gelatin 0.01 g / m ²

The individual samples were exposed to daylight both behind a blue filter and behind an orange filter and each with a graduated gray wedge and then processed according to the process described in "The British Journal of Photography" 1974, p. 597. The sensitivity E is determined after densitometric measurement at a density of 0.2 over fog (D _min ) in relative DIN units.

ΔE and ΔD _min mean the change in sensitivity and fog after storage of the unexposed material at 60 ° C. for 14 days.

The results are shown in Table 1 below:

Table 1

Samples 10 to 15 and 18 to 23 according to the invention are distinguished by ver improved sensitivity, low fog, and diminished changes in Sensitivity and haze off when stored in a heating cabinet.

Cyan coupler C-1 has the formula

Hardener H-1 has the formula

The sensitizers correspond to the formula

RS-1: R ₁ , R ₂ = CH ₃ ; R ₃ , R ₅ = H; R ₄ = (CH ₂ ) ₄ SO ₃ Na; R6 = phenyl; X = O; n = 2;
RS-2: R ₁ , R ₃ , R ₅ = H; R ₂ , R ₆ = Cl; R ₄ = C ₂ H ₅ X = S; n = 3;
RS-3: R ₁ = H; R ₂ and R ₃ together and R ₅ and R ₆ together in each case -CH = CH-CH = CH-, R ₄ = (CH ₂ ) ₃ SO ₃ Na; X = S; n = 3.

Claims (11)

1. Color photographic silver halide material with a support and at least one silver halide emulsion layer applied thereon, characterized in that the silver halide emulsion layer contains a transition metal aromatic complex, at least one spectral sensitizer and a compound of the formula I:
R ₁ -C∼CR ₂ (I)
wherein
R ₁ and R ₂ independently of one another denote unsubstituted or substituted alkyl, unsubstituted or substituted aryl or unsubstituted or substituted hetaryl, at least one of the radicals R ₁ and R ₂ containing at least one polar, preferably hydrophilic group. 2. Color photographic silver halide material according to claim 1, characterized in that the compounds of the formula I correspond to the formula II:
wherein
R _{3 is} unsubstituted or substituted alkyl or unsubstituted or substituted aryl
R ₄ and R ₅ independently of one another are hydrogen, alkyl or aryl or together the remaining members of a carbocyclic or heterocyclic, aromatic or nonaromatic ring and
X means O, S, Se or Te. 3. Color photographic silver halide material according to claim 1, characterized characterized in that as a transition metal complex aromatic complexes with a central atom can be used, which is in a level of importance is present that is not the highest possible for the metal in question, and which contain at least one non-aromatic complex ligand. 4. Color photographic silver halide material according to claim 3, characterized characterized that the transition metal vanadium, chromium, manganese, Iron, cobalt, nickel, molybdenum, rhenium, ruthenium, rhodium, Is tungsten, osmium or iridium. 5. Color photographic silver halide material according to claim 3, characterized characterized in that the aromatic complex is cyclopenta as aromatic dienyl anion, the indenyl anion, pyrrole, thiophene or benzene and as not aromatic complex ligands CO, C = N-R or NO, where R is Alkyl or aryl. 6. Color photographic silver halide material according to claim 1, characterized characterized in that as a transition metal complex or unsubstituted substituted cyclopentadienyl manganese tricarbonyl is used. 7. Color photographic silver halide material according to claim 1, characterized ge indicates that as a transition metal complex complexes with two Cyclo pentadienide ligands can be used. 8. Color photographic silver halide material according to claim 2, characterized in that R _{3 is} methyl or phenyl and R ₄ and R _{5 are} hydrogen or C ₁ -C ₄ -alkyl. 9. color photographic silver halide material according to claim 1, characterized in that the transition metal ^{aromatic complex} in an amount of 10 -6 to 10 ^-2 mol / mol Ag and the compound of formula I in an amount of 2. 10 ^-6 to 2. 10 ^-4 mol / mol Ag are added. 10. Color photographic silver halide material according to claim 1, characterized characterized in that transition metal aromatic complex and compound of Formula I of the silver halide emulsion together with the spectral sensitizer can be added. 11. Color photographic silver halide material according to claim 1, characterized ge indicates that the spectral sensitizer belongs to the class of polymethine cyanine heard.