DE3835467A1 - COLOR PHOTOGRAPHIC SILVER HALOGENIDE MATERIAL - Google Patents

Description

The invention relates to a color photographic silver halide recording material, especially one with reflective pad that provides higher color densities.

From EP-A 02 43 199 are color photographic materials known, in particular color negative paper, in at least a photosensitive layer, a silver halide containing at least 80 mole% of chloride containing a Layer with a UV light absorbing agent, the have liquid at room temperature, and with Hardened a vinyl sulfone hardener. With this color negative paper can in the so-called short-term process, at the development time is 45 seconds, color images getting produced. The material is drawing results from reduced pressure desensitization but still no really satisfying maximum densities, although it is opposite to materials used in Room temperature solid UV absorber included, advantageous is.  

From EP-A 02 71 005 is a color photographic silver halide material known with improved image quality, on the one hand certain cyan coupler and on the other hand requires a layer with a UV absorber, wherein this at least to 30 wt .-% of a Room temperature liquid UV absorber exists and in addition a solvent (oil former) with a dielectric constant (DK) needed from 6.0.

Apart from that so far usual and proven, at Room temperature solid UV absorber only in small Shares can be used, suffers the material at unsatisfactory maximum densities.

The object of the invention was therefore to find means which provides a satisfactory protection against UV light under use provide at room temperature solid UV absorber and nevertheless deliver high color densities.

It has now surprisingly been found that solve this problem by that at room temperature solid, UV-absorbing compounds used dissolved in special oil formers.

The invention is therefore a color photographic Silver halide material with a support, preferably a reflective support, at least one photosensitive silver halide emulsion layer and at least one UV light absorbing, at room temperature solid medium containing layer whose UV Absorber dissolved in an oil painting and the solution in the  Layer is emulsified, characterized in that as Oil former at least one liquid at room temperature, organic compound is used, the following Conditions fulfilled:

• a) she is saturated,
  b) it contains wenigstgens an ester or amide group,
  c) it is electrically neutral,
  d) their carbon number is 14 to 40.

The oil former may act as additional functional groups Halogen atoms, ether groups and other ester groups included and preferably has no further addition functional groups. The saturated radicals are in particular aliphatic and cycloaliphatic Residues. The carbon number of the oil formers is preferably 18 to 28.

Particularly advantageous are monocarboxylic acid esters, dicarboxylic acid esters and doubly esterified with monocarboxylic acids Diols, as further functional groups exclusively up to 10 halogen atoms and / or up to Have 4 ether groups.

The boiling points of the oil formers should in particular <150 ° C.

Examples of such oil formers are:  

The oil formers according to the invention can also with the customary oil formers, z. Phthalic, phosphoric, Be mixed with citric and benzoic esters, wherein the blend at least 30 wt .-%, preferably at least 50% by weight of the oil formers according to the invention should contain.

Preferred room temperature solid UV absorbers correspond the formula

wherein

R₁ and R₂ are alkyl, aryl, alkoxy or aryloxy and
R₃ is hydrogen, halogen, alkyl, aryl, alkoxy, aryloxy, alkenyl, nitro or hydroxy

mean.  

Its melting point is higher than 30 ° C, preferably higher than 50 ° C. The alkyl and alkoxy groups have in particular 1 to 20 carbon atoms and can, for. By chlorine, bromine, Methoxy or phenyl substituted. The alkenyl groups in particular have 2 to 10 C atoms, aryl and aryloxy groups have 6 to 10 ring carbon atoms and can also C₁-C₄-alkyl, C₁-C₄-alkoxy, chloro or bromo be substituted.

Suitable UV absorbers are in the table below listed.  

Part of the UV absorber can also be liquid but preferably not more than 25% by weight of the total amount on UV absorbers. Suitable liquid UV absorbers are known from EP-A 2 71 005, z. B. UV-20 with R₁ = t-C₄H₉, R₂ = - (CH₂) ₂COOC₈H₁₇ (n + iso), R₃ = Cl.

The 2- (2-hydroxyphenyl) benzotriazole compounds are known and for example in US 37 54 919, 42 20 711 and 45 18 686 described.

The UV absorbers (total amount) are preferably in in an amount of 0.01 to 5 g / m², especially 0.05 to 2 g / m² used, especially over all photosensitive Layers in the farthest from the wearer non-photosensitive layer. But it can also be beneficial, the total amount of UV absorber divide up a part in the top, not photosensitive Protective layer and a part in one non-photosensitive intermediate layer, in particular over the purple layer, or in a light-sensitive Apply layer over the purple layer.

The photographic material according to the invention contains in particular at least one blue-sensitive layer, the at least one yellow coupler is associated, at least a green-sensitive layer containing at least one magenta coupler is assigned and at least one red sensitive Layer containing at least a cyan coupler assigned. Preferably, of the photosensitive Layers that are at least one blue-sensitive Layer closest to the wearer and the at least one red sensitive layer most distant from the wearer.  

Preferably, the silver halides of all photosensitive Layers at least 80 mole% chloride, in particular 95 to 100 mol% chloride, 0 to 5 mol% Bromide and 0 to 1 mole% iodide.

The silver halide may be predominantly compact Crystals act, the z. B. regular cubic or octahedral or may have transitional forms. Preferably, however, platelet-shaped crystals can also be used whose average ratio of Diameter to thickness preferably at least 5: 1, wherein the diameter of a grain is defined as the Diameter of a circle with a circle content accordingly the projected area of the grain. The layers but can also be tabular silver halide crystals in which the ratio of diameter to Thickness greater than 5: 1, z. From 12: 1 to 30: 1.

The silver halide grains may also be multi-layered Have grain structure, in the simplest case with an inner and an outer grain area (core / shell), wherein the halide composition and / or other modifications, such. B. doping of the individual Grain areas are different. The middle Grain size of the emulsion is preferably between 0.2 μm and 2.0 μm, the particle size distribution can be both homo- as well as heterodisperse. The emulsions can in addition to the silver halide, organic silver salts included, for. B. silver benzotriazolate or silver behenate.  

Two or more kinds of silver halide emulsions, which are manufactured separately as Mixture be used.

The photographic emulsions can be prepared by various methods [e.g. BP Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967); GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966); VL Zelikman et al., Making and Coating Photographic Emulsion, The Focal Press, London (1966) ] from soluble silver salts and soluble halides.

The precipitation of the silver halide is preferably carried out in Presence of the binder, e.g. As the gelatin, and can carried out in acidic, neutral or alkaline pH range preferably silver halide complexing agents additionally used. To the latter belong z. As ammonia, thioether, imidazole, ammonium thiocyanate or excess halide. The merge the water-soluble silver salts and the halides takes place one after the other after the single- jet or simultaneously using the double-jet method or by any combination of both methods.  

Preferably, the dosage with increasing inflow rates, the "critical" feed rate at which just no new germs arise, not exceeded should be. The pAg area may be during the Precipitation vary within wide limits, preferably the so-called pAg-controlled method is used, in which a certain pAg value is kept constant or on pass through the defined pAg profile during the precipitation becomes. In addition to the preferred precipitation with halide excess but is also the so-called inverse precipitation at Silver ion excess possible. Except by precipitation The silver halide crystals can also be replaced by physical Maturation (Ostwald ripening) in the presence of excess halide and / or silver halide complexing agent to grow. The growth of the emulsion grains can even be overwhelmingly due to Ostwald ripening take place, preferably a fine-grained, so-called Lippmann emulsion with a sparingly soluble Emulsion is mixed and redissolved on the latter.

During precipitation and / or physical ripening The silver halide grains may also be salts or Complexes of metals, such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe, be present.

Furthermore, the precipitation may also be in the presence of sensitizing dyes respectively. complexing and / or dyes can be added to any Make ineffective, eg. B. by changing the pH Value or by an oxidative treatment.  

The binder used is preferably gelatin. However, this can be done in whole or in part by others synthetic, semi-synthetic or naturally occurring Be replaced polymers. Synthetic gelatin substitutes For example, polyvinyl alcohol, poly- N-vinylpyrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers. Well-known gelatin substitutes are, for example other proteins such as albumin or casein, Cellulose, sugar, starch or alginates. semi-synthetic Gelatine substitutes are usually modified Natural products. Cellulose derivatives such as hydroxyalkyl cellulose, Carboxymethyl cellulose and phthalyl cellulose and gelatin derivatives obtained by reaction with alkylating or acylating agents or by Grafting of polymerizable monomers obtained are examples of this.

The binders should be over a sufficient amount functional groups, so that by implementation sufficiently resistant with suitable curing agents Layers can be generated. Such functional Groups are especially amino groups, as well Carboxyl groups, hydroxyl groups and active methylene groups.

The gelatin preferably used can be acidic or alkaline digestion. The production such gelatins is described, for example, in The Science and Technology of Gelatine, published by A.G. Ward and A. Courts, Academic Press 1977, p  295 ff., Described. The gelatine used in each case should have the lowest possible content of photographic contain active impurities (inert gelatin). Gelatins with high viscosity and low swelling are particularly advantageous. The gelatin can partially or completely oxidized.

After completed crystal formation or already too at an earlier point in time, the soluble salts become the emulsion removed, z. By noodles and washing, by flocculation and washing, by ultrafiltration or by ion exchanger.

The photographic emulsions may be compounds for Prevention of fogging or stabilization the photographic function during production, the Storage or photographic processing included.

Particularly suitable are azaindenes, preferably tetracenes and pentaazaindenes, in particular those containing hydroxyl or amino groups are substituted. such Connections are z. B. von Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Next can as Antifogg salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as Benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, (subst.) benzotriazoles or benzthiazolium salts. Especially suitable are mercapto-containing heterocycles, z. Mercaptobenzothiazoles, mercaptobenzimidazoles,  Mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, these mercaptoazoles also being a water-solubilizing Group, e.g. B. a carboxyl group or Sulfo group, may contain. Other suitable compounds are in Research Disclosure No. 17643 (1978), Section VI, published.

The stabilizers can be added to the silver halide emulsions be added before, during or after their maturation. Of course you can do the connections as well other photographic layers containing a silver halide layer zugerodnet are, enforce.

It is also possible to use mixtures of two or more of these Connections are used.

The silver halide emulsions usually become chemically matured, for example, by the action of Gold compounds or compounds of the bivalent Sulfur.

The photographic emulsion layers or other hydrophilic Colloid layers of the invention produced Photosensitive material can be surface-active Containing agents for various purposes, such as coating aids, to prevent electrical charging, to Improvement of gliding properties, to emulsify the Dispersion, to prevent adhesion and to improve it Photographic Characteristics (eg development acceleration, high contrast, sensitization etc.).  

The photographic emulsions can be made using of methine dyes or other dyes spectrally be sensitized. Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex ones Merocyanine.

Color couplers for forming the cyan partial color image are usually phenol or α -naphthol type couplers; suitable examples are known in the literature.

Color couplers for producing the yellow partial color image are usually couplers with an open-chain ketomethylene group, in particular couplers of the α- acylacetamide type; suitable examples thereof are α -benzoylacetanilide couplers and α- pivaloylacetanilide couplers, which are also known from the literature.

Color coupler for producing the purple partial color image are usually couplers of the type of 5-pyrazolone, the Indazolone or pyrazoloazole; suitable examples this is described in large numbers in the literature.

The color couplers may be 4-equivalent couplers, but also act around 2-equivalent couplers. Latter derive from the 4-equivalent couplers in that they contain a substituent in the coupling site, which is split off at the clutch. To the 2 Equivalent couplers are those that are colorless are, as well as those that have an intense intrinsic color  have, which disappears in the color coupling or replaced by the color of the generated image dye is (mask coupler), as well as white couplers, the reaction with color developer oxidation products substantially give colorless products. To the 2-equivalent couplers Furthermore, such couplers are to be expected, the the coupling point contain a cleavable radical, at Reatkion with color developer oxidation products is in freedom and thereby either directly or, after the primary split-off remainder one or several further groups have been split off (eg DE-A 27 03 145, DE-A 28 55 697, DE-A 31 05 026, DE-A 33 19 428), a particular desired photographic Effectiveness unfolded, z. B. as a development inhibitor or -accelerator. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or FAR coupler.

Since the DIR, DAR and FAR couplers mainly the effectiveness of the released in the coupling Restes is desired and it is less on the color-forming Properties of this coupler arrives are also those DIR, DAR or FAR couplers suitable, the in the coupling substantially colorless products give (DE-A 15 47 640).

The cleavable residue may also be a ballast residue, so that in the reaction with color developer oxidation products Coupling products are obtained which are diffusible are or at least weak or restricted Have mobility (US-A 44 20 556).  

High molecular color couplers are for example in DE-C 12 97 417, DE-A 24 07 569, DE-A 31 48 125, DE-A 32 17 200, DE-A 33 20 079, DE-A 33 24 932, DE-A 33 31 743, DE-A 33 40 376, EP-A 27 284, US-A 40 80 211 described. The high molecular color couplers are in usually by polymerization of ethylenically unsaturated produced monomeric color couplers. You can but also by polyaddition or polycondensation to be obtained.

The incorporation of the couplers or other compounds in silver halide emulsion layers can in the way be done first by the relevant connection prepared a solution, a dispersion or an emulsion and then the casting solution for that particular Layer is added. The selection of the appropriate Solvent or dispersant depends on the particular Solubility of the compound.

Methods for introducing into water substantially insoluble compounds by grinding processes are For example, in DE-A 26 09 741 and DE-A 26 09 742 described.

Hydrophobic compounds can also be made using high-boiling solvents, so-called oil formers, be introduced into the casting solution. Appropriate Methods are for example in US-A 23 22 027, US-A 28 01 170, US-A 28 01 171 and EP-A 00 43 037 described.  

Instead of high-boiling solvents can Oligomers or polymers, so-called polymeric oil formers, Find use.

The compounds may also be in the form of loaded latices be introduced into the casting solution. Is referred For example, DE-A 25 41 230, DE-A 25 41 274, DE-A 28 35 856, EP-A 00 14 921, EP-A 00 69 671, EP-A 01 30 115, US-A 42 91 113.

The diffusion-resistant inclusion of anionic water-soluble Compounds (eg of dyes) can also with the help of cationic polymers, so-called pickling polymers, respectively.

Suitable oil formers for other couplers and other compounds are z. Phthalic acid alkyl ester, phosphoric acid ester, Citric acid ester, benzoic acid ester, Alkylamides, fatty acid esters and trimesic acid esters.

Each of the photosensitive layers may consist of a single layer or even two or more Silver halide emulsion partial layers comprise (DE-C 11 21 470). In this case, the red-sensitive silver halide emulsion layer closer to the substrate as the green-sensitive silver halide emulsion layer and these in turn closer than the blue-sensitive, being between green-sensitive layers and blue-sensitive layers also a non-photosensitive layer yellow filter layer can be located.  

With suitably low intrinsic sensitivity of the green or Red sensitive layers can be waived the yellow filter layer choose other layer arrangements, in which on the carrier z. B. the blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow.

The usually between layers of different Spectral sensitivity arranged non-photosensitive Interlayers may contain agents the unwanted diffusion of developer oxidation products from a photosensitive to a other photosensitive layer with different prevent spectral sensitization.

If several sublayers have the same spectral sensitization before, so they can with regard to their Composition, in particular what the type and amount of silver halide grains concerns, differ. In general becomes the sub-layer with higher sensitivity be located more distant from the carrier than the sub-layer with lower sensitivity. sublayer same spectral sensitization can each other adjacent or through other layers, e.g. B. by Layers of other spectral sensitization, separated his. So z. B. All the most sensitive and all low-sensitive layers in each case to a layer package be summarized (DE-A 19 58 709, DE-A 25 30 645, DE-A 26 22 922).  

The photographic material can still be whitened, Spacers, formalin catchers and other included.

Suitable whiteners are z. In Research Disclosure, December 1978, page 22 ff, Unit 17 643, Kaptel V, described.

Certain binder layers, in particular those of Wearer furthest away, but also occasionally Interlayers, especially if they are during production the furthest from the wearer represent distant layer, can photographically inert Contain particles of inorganic or organic nature, z. B. as a matting agent or as a spacer (DE-A 33 31 542, DE-A 34 24 893, Research Disclosure, December 1978, page 22 et seq, Unit 17 643, chapter XVI).

The mean particle diameter of the spacers is in particular in the range of 0.2 to 10 microns. The spacers are insoluble in water and can be alkali-insoluble or alkali-soluble, the alkali-soluble generally in the alkaline development bath removed from the photographic material. Examples suitable polymers include polymethylmethacrylate, copolymers from acrylic acid and methyl methacrylate as well Hydroxypropylmethyl cellulose.

As a reflective carrier comes in particular on both sides polyethylene-coated paper in question.  

The layers of photographic material can with hardened the usual curing agents. suitable Hardeners are z. As formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis- (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and others Compounds containing reactive halogen (US-A 32 88 775, US-A 27 32 303, GB-A 9 74 723 and GB-A 11 67 207); Divinyl sulfone compounds, 5-acetyl-1,3-diacryloylhexahydro 1,3,5-triazine and other compounds, which contain a reactive olefin bond (US-A 36 35 718, US-A 32 32 763 and GB-A 9 94 869); N-hydroxymethyl phthalimide and other N-methylol compounds (US-A 27 32 316 and US-A 25 86 168); Isocyanates (US-A 31 03 437); Aziridine compounds (US-A 30 17 280 and US-A 29 83 611); Acid derivatives (US-A 27 25 294 and US-A 27 25 295); Carbodiimide type compounds (US-A 31 00 704); Carbamoylpyridiniumsalze (DE-A 22 25 230 and DE-A 24 39 551); Carbamoyl oxypyridinium compounds (DE-A 24 08 814); Compounds with a phosphorus-halogenated Compound (JP-A 1 13 929/83); N-Carbonyloximid compounds (JP-A 43 353/81); N-sulfonyloximido compounds (US-A 41 11 926), dihydroquinoline compounds (US-A 40 13 468), 2-sulfonyloxypyridinium salts (JP-A 1 10 762/81), formamidinium salts (EP-A 01 62 308), compounds with two or more N-acyloximino groups (US Pat 40 52 373), epoxy compounds (US Pat. No. 3,091,537), Isoxazole-type compounds (US-A 33 21 313 and US-A 35 43 292); Halogencarboxyaldehyde, such as mucochloric acid; Dioxane derivatives such as dihydroxydioxane and di-chlorodioxane;  and inorganic hardeners such as chrome alum and zirconium sulfate.

The curing can be effected in a known manner by that the curing agent of the casting solution for the hardening layer is added or in that the to be hardened layer with a layer overcoated which contains a diffusible curing agent.

Among the listed classes, there are slow-acting ones and fast-acting hardeners and so-called Instant hardeners that are particularly beneficial. Under Emergency workers are understood to be compounds which are suitable Crosslink the binder so that immediately after Beguß, at the latest after 24 hours, preferably Hardening completed at the latest after 8 hours is that no further through the crosslinking reaction conditional change of the sensitometry and the Swelling of the layer dressing occurs. Under swelling is the difference between wet film thickness and dry film thickness in the aqueous processing of the film understood [Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci., Eng. (1972), 449].

In these with gelatin very fast reacting hardeners is it z. Carbamoylpyridinium salts, those with free carboxyl groups of gelatin react, so that the latter with free amino groups gelatin to form peptide bonds and crosslinking of the gelatin.  

Suitable examples of instant hardeners are e.g. B. compounds the general formula

wherein
R₁ is alkyl, aryl or aralkyl,
R₂ has the same meaning as R₁ or alkylene, arylene, aralkylene or Alkaralkylen means, wherein the second bond with a group of the formula

linked, or
R₁ and R₂ together are the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, the ring being e.g. B. may be substituted by C₁-C₃-alkyl or halogen,
R₃ is hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxy,

or a bridge member or a direct bond to a polymer chain, wherein
R₄, R₆, R₇, R₉, R₁₄, R₁₅, R₁₇, R₁₈ and R₁₉ are hydrogen or C₁-C₄-alkyl,
R₅ is hydrogen, C₁-C₄-alkyl or NR₆R₇,
R₈ -COR₁₀,
R₁₀ NR₁₁R₁₂,
R₁₁ C₁-C₄-alkyl or aryl, in particular phenyl,
R₁₂ is hydrogen, C₁-C₄-alkyl or aryl, in particular phenyl,
R₁₃ is hydrogen, C₁-C₄-alkyl or aryl, in particular phenyl,
R₁₆ is hydrogen, C₁-C₄alkyl, COR₁₈ or CONHR₁₉,
m is a number 1 to 3,
n is a number 0 to 3,
p is a number 2 to 3 and
Mean YO or NR₁₇ or
R₁₃ and R₁₄ together represent the necessary to complete an optionally substituted heterocyclic ring, such as a piperidine, piperazine or morpholine ring atoms, wherein the ring z. B. may be substituted by C₁-C₃-alkyl or halogen,
Z for the completion of a 5- or 6-membered aromatic heterocyclic ring, optionally with fused brenzo ring, C atoms required and
X⊖ represents an anion which may be omitted if an anionic group is already linked to the remainder of the molecule;

wherein
R₁, R₂, R₃ and X⊖ have the meaning given for formula (a).

There are diffusible curing agents that work on everyone Layers within a layer structure in the same Way hardening act. But there are also stratum-limited acting, non-diffusing, low molecular weight and  high molecular weight hardener. With them you can single Layers, z. As the protective layer, especially strong network. This is important when considering the silver halide layer because of the Silberdeckkrafterhöhung little hardens and with the protective layer the mechanical properties must improve (EP-A 01 14 699).

For the production of color photographic images, the inventive color photographic recording material developed with a color developer compound. As a color developer compound All developer compounds can be used use that have the ability in Form of their oxidation product with color couplers to Azomethinfarbstoffen to react. Suitable color developer compounds are aromatic, at least one primary Amino-containing compounds of the p-phenylenediamine type, for example N, N-dialkyl-p-phenylenediamines, such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methyl- sulfonamidoethyl) -3-methyl-p-phenylenediamine, 1- (N-ethyl- N-hydroxyethyl-3-methyl-p-phenylenediamine and 1- (N-ethyl) N-methoxyethyl) -3-methyl-p-phenylenediamine.

Other useful color developers are, for example described in J. Amer. Chem. Soc. 73, 3100 (1951), and in G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, pp. 545 ff.

The recording material according to the invention with high Chloride content is excellent for processing in an abbreviated processing process, e.g. In a processing process, its development step at temperatures between 25 and 45 ° C less than  3 minutes, preferably less than 1 minute. Especially when developed with benzyl alcohol-free Developer baths are beneficial results receive.

Preferably, the color developer solution contains 0.01 Mol / l bromide and 5 ml / l benzyl alcohol.

After color development, the material is usually bleached and fixed. Bleaching and fixation may be carried out separately or together. As bleaching agent, the usual compounds can be used, for. B. Fe ³⁺ salts and Fe ³⁺ - complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes, etc. Particularly preferred are iron-III complexes of aminopolycarboxylic acids, in particular z. Ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids. Suitable bleaching agents are persulfates.

Followed by watering and drying.

Example 1

A color photographic recording material which was suitable for a fast processing process has been made by placing on a substrate of both sides polyethylene coated paper the following Layers applied in the order given were. The quantities refer to each 1 m². For the silver halide order, the corresponding Amounts indicated AgNO₃.

Layer structure 1

1st layer (substrate layer):
0.2 g of gelatin

2nd layer (blue-sensitive layer):
Blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.8 microns) from 0.63 g of AgNO₃ with
1.38 g of gelatin
0.95 g yellow coupler
0.29 g Trikeresyl phosphate (TKP)

3rd layer (protective layer):
1.1 g of gelatin
0.06 g of 2,5-dioctylhydroquinone
0.06 g dibutyl phthalate (DBP)

4th layer (green-sensitive layer):
Green-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.6 microns) from 0.45 g AgNO₃ with
1.08 g of gelatin
0.45 g magenta coupler
0.16 g of α - (3-t-butyl-4-hydroxyphenoxy) -myristinsäureethylester
0.04 g of 2,5-dioctylhydroquinone
0.24 g of diisononyl phthalate
0.24 g TKP

5th layer (UV protection layer):
1.15 g of gelatin
0.6 g UV absorber UV 12
0.045 g of 2,5-dioctylhydroquinone
0.3 g TKP

6th layer (red-sensitive layer):
Rotsensibilisierte silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.5 microns) from 0.3 g AgNO₃ with
0.75 g of gelatin
0.36 g cyan coupler
0.36 g TKP

7th layer (UV protection layer):
0.35 g of gelatin
0.15 g of UV 12
0.075 g TKP

8th layer (protective layer):
0.9 g of gelatin
0.3 g of curing agent of the formula

The color couplers used were the following compounds:

Yellow coupler:

Magenta coupler:

Cyan coupler:

Layer structure 2

In the 5th layer, 0.5 g UV absorber UV 12 and 0.1 g of UV 20 with 0.3 g of OL 12 used as an oil former. In the 7th layer, 0.125 g of UV 12 and 0.025 g of UV 20 are added used with 0.075 g OL 12.

Layer structure 3

In the 5th layer, 0.6 g of UV 12 with 0.25 g of OL 5 and 0.05 g of dibutyl phthalate (DBP) as an oil former and in Layer 7 0.15 g of UV 12 with 0.072 g of OL 5 and 0.013 g of dibutyl phthalate (DBP) used.

Layer structure 4

In the 5th layer, 0.5 g UV absorber UV 12 and 0.1 g of UV 20 with 0.3 g of OL 1 and 0.17 g in the 7th layer UV 12 and 0.03 g UV 20 with 0.1 g OL 1 used.

Layer structure 5

In the 5th layer, 0.5 g UV absorber UV 12 and 0.1 g UV 20 with 0.2 g OL 4 and 0.1 g DBP and in the 7. Layer 0.17 g UV 12 and 0.03 g UV 20 with 0.067 g OL 4 and 0.033 g DBP.  

Layer structure 6

In the 5th layer, 0.5 g UV absorber UV 12 and 0.1 g UV 20 with 0.15 g OL 9 and 0.15 g DBP and in the 7. Layer 0.17 g UV 12 and 0.03 g UV 20 with 0.05 g OL 9 and 0.05 g of DBP.

Layer structure 7

In the 5th and 7th layer, a gelatin layer becomes more appropriate Thickness used without UV absorber and oil former.

The 7 superstructures are after the pouring behind a blue color separation filter exposed with a ³√-wedge and developed according to the following information. In the same way, a neutral wedge by exposure made behind blue, red and green color separation filters.

The yellow color separation wedges (FAZ) and Neutral wedges (NK) are behind with a densitometer measured by a blue filter and thus sensitivity, Shoulder gradation and maximum color density in yellow certainly.  

The results show the following overview:

In the neutral wedges was in the constructions 2 to 7 also the maximum density of purple is 0.1 to 0.2 higher.

It can be seen clearly that the composite according to the invention UV layers in the color structures a significant give better color density and gradation in yellow and approach a structure without UV emulsifier.

a) Color developer - 45 s - 35 ° C

Triethanolamine | 9.0 g / l N, N-diethyl 4.0 g / l diethylene glycol 0.05 g / l 3-methyl-4-amino-N-ethyl-N-methane-sulfonamidoethyl-aniline sulfate 5.0 g / l potassium sulphate 0.2 g / l triethylene 0.05 g / l potassium carbonate 22.0 g / l potassium hydroxide 0.4 g / l ethylenediaminetetraacetic @ (Di-sodium salt) 2.2 g / l potassium chloride 2.5 g / l 1,2-dihydroxybenzene-3,4,6-trisulfonic acid trisodium salt 0.3 g / l Make up to 1000 ml with water; pH 10.0

b) Bleach-fix bath - 45 s - 35 ° C

Ammonium thiosulphate | 75 g / l sodium bisulfite 13.5 g / l ammonium acetate 2.0 g / l ethylenediaminetetraacetic @ (Ferric ammonium salt) 57 g / l Ammonia 25% 9.5 g / l acetic acid 9.0 g / l Make up to 1000 ml with water; pH 5.5

c) watering - 2 min - 33 ° C

d) drying  

example 2

A color photographic recording material suitable for the previous standard development process (eg AP 92 Agfa-Gevaert AG or EP 2 of the Eastman Kodak Comp.) was prepared by placing on a Support made of polyethylene coated on both sides Paper the following layers in the specified Order were applied:

Layer structure 1

1st layer (substrate layer):
0.2 g of gelatin

2nd layer (blue-sensitive layer):
Blue-sensitive silver halide emulsion (97 mol% bromide, 3 mol% chloride, average grain diameter 0.8 microns) from 0.5 g AgNO₃ with
1.5 g of gelatin
0.75 g yellow coupler
0.75 g tricresyl phosphate (TKP)

3rd layer (protective layer):
as in Example 1

4th layer (green-sensitive layer):
Green sensitized silver halide emulsion (20 mole% chloride, 80 mole% bromide, average grain diameter 0.5 μm) from 0.5 g AgNO₃ with
1.4 g of gelatin
0.45 g magenta coupler
0.18 g of α - (3-t-butyl-4-hydroxyphenoxy) -myristinsäureethylester
0.04 g of 2,5-dioctylhydroquinone
0.22 g of diisononyl phthalate
0.2 g TKP

5th layer (UV protection layer):
as in Example 1

6th layer (red-sensitive layer):
Rotsensibilisierte silver halide emulsion (20 mol% chloride, 80 mol% bromide, average grain diameter 0.5 microns) from 0.35 g of AgNO₃ with
0.9 g of gelatin
0.4 g of cyan coupler
0.4 g TKP

7th layer (UV protection layer):
as in Example 1

8th layer (protective layer):
as in Example 1

Purple couplers and cyan couplers are the same as in Example 1. As a yellow coupler, the following compound used:

Layer structure 2

Layers 5 and 7
as in layer structure 2 in Example 1

Layer structure 3

Layers 5 and 7
as in layer structure 5 in Example 1

Layer structure 4

Layers 5 and 7
as in layer structure 7 in Example 1

Again, in the same manner as in Example 1 a yellow color separation portion and a neutral wedge exposed, but then, as described above, in the standard process Developed AP 92 (3.5 min, 33 ° C).  

The sensitometric results show the following Overview:

Again, in the composite according to the invention UV layers in the color structures in yellow a better Color density and gradation to recognize the structure comes close without UV emulsifier.

Claims (7)

A color photographic silver halide material comprising a support, at least one light-sensitive silver halide emulsion layer and at least one room-temperature UV absorber-containing layer, the UV absorber of which is dissolved in an oil former and the solution is emulsified in the layer, characterized in that at least one oil-former is used at room temperature liquid organic compound is used, which meets the following conditions:

• a) she is saturated,
  b) it contains at least one ester or amide group,
  c) it is electrically neutral,
  d) their carbon number is 14 to 40.

2. Color photographic material according to claim 1, characterized characterized in that the oil former except where appropriate Halogen atoms, ether groups and others Ester groups contains no functional groups. 3. Color photographic material according to claim 1, characterized characterized in that the oil former as saturated Radicals aliphatic and cycloaliphatic Contains radicals and has a carbon number of 18 to 28 has.   4. Color photographic material according to claim 1, characterized characterized in that the oil former is a monocarboxylic acid ester, a dicarboxylic acid ester or a with monocarboxylic acids is di-esterified diol, optionally by up to 10 halogen atoms and up to 4 ether groups are substituted. 5. A silver halide color photographic material according to claim 1, characterized in that the Gesamtölbildnermengen of the UV absorber emulsifier up to 70 wt .-% of oil forming agents, according to the oil formers Claim 1 are different, may contain. 6. Color photographic material according to claim 1, characterized in that the solid at room temperature UV absorber of the formula corresponds to, in which
R₁ and R₂ are alkyl, aryl, alkoxy or aryloxy and
R₃ is hydrogen, halogen, alkyl, aryl, alkoxy, aryloxy, alkenyl, nitro or hydroxy
mean. 7. Color photographic material according to claim 1, characterized characterized in that the total amount of UV absorber up to 25% by weight at room temperature liquid UV absorber can exist.