DE3113009A1 - PHOTOGRAPHIC RECORDING MATERIAL - Google Patents

Description

AGFA-GEVAERT * * ' D 5090 Leverkusen 1

AKTIENGESELLSCHAFT Federal Republic of Germany

Patent department Zb / bc / c

Photographic recording material

The invention relates to a photographic recording material with several silver halide emulsion layers, which contains stored color couplers. At least one silver halide emulsion layer lies between them color coupler-containing layers which are not photosensitive Contain silver halide or contain silver halide, which is comparatively insensitive to light is. The invention also relates to a method for producing photographic images by imagewise exposure and development of the material of the invention.

It is known to use recording materials for the production of colored photographic images, one red-sensitive, one green-sensitive and one blue-sensitive silver-halide emulsion layer on a substrate each of said silver halide emulsion layers being non-diffusing Contains color coupler for generating the cyan, purple and yellow partial color image and wherein in each case the color of the partial color image produced is related to the spectral sensitivity of the silver halide emulsion layer is complementary. Customary

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borrowed color photographic materials also contain further layers such as a yellow filter layer between the blue-sensitive layer on top Silver halide emulsion layer and the underlying green-sensitive silver halide emulsion layer and an antihalation layer between the Support and the lowest silver halide emulsion layer. Furthermore, additional gelatin intermediate layers can be used and cover layers may be provided.

It is also known to use such recording materials for the production of color photographic images, in which at least one or more of the three different partial color images are generated two silver halide emulsion layers are provided each. According to GB-PS 818 687, for example, there is the lowest light-sensitive color-forming layer unit of a color photographic multilayer material composed of two sensitized for light of the same spectral range, containing silver halide and color couplers Partial layers, of which the upper one has the greater sensitivity.

DT-PS 1 121 470 discloses the use of such double layers of different sensitivity known, of which the more sensitive results in the lower color density in color development.

This makes it possible to increase the sensitivity without reducing the graininess adversely affect. Reference is also made to US Pat. No. 4,173,479 and that stated therein Literature.

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The increased demands on photographic recording materials require a material which has good sharpness and graininess at high sensitivity. From US-PS 4,040,829 (German Offenlegungsschrift 2 524 835J is known / for improving the sharpness of color photographic images, color couplers and silver halide to be introduced into different layers of the recording material. Here the thickness of the Reduced silver halide emulsion layer and a color coupler with limited diffusivity used. The use of color couplers with limited diffusivity is also from the US patent 2,546,400 known.

From the German Auslegeschrift 1 002 626 (GB-PS 818 233) it is known that color photographic Materials an improved color separation is obtained by interposing adjacent color couplers Emulsion layers arranges a gelatin layer which contains a color coupler. Such color coupler-containing Gelatin layers can be above and below the associated silver halide emulsion layer be arranged. From the German Offenlegungsschrift 2,650,715 (U.S. Patent 4,186 01IJ is a color photographic Recording material having a silver halide emulsion layer known, which is divided into 2 or more sub-layers of different sensitivity. Direct Over the more sensitive silver halide emulsion layer is a color coupler-containing binder layer arranged that does not contain silver halide. The last specified color coupler layer

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has a high concentration of color couplers and can be kept very thin. From U.S. Patent 2,350 are color photographic recording materials with a Silver halide emulsion layer known, to which at least one further layer is adjacent, the one Contains coloring compound. This layer is preferably 1.5μ to 5.0μ thick. The silver halide emulsion layer generally has a thickness between 2.0 and 6.0μ.

It is also known in photographic recording materials To use layers in which there is a relatively small gelatin / silver ratio. For example, a color photographic recording material is known from US Pat. No. 3,372,030 in which the individual layers are generally not thicker than 4μ and in which the ratio gelatine / silver is around 1. In this material, the color couplers are in the silver halide emulsion layer stored in order to be as close as possible between the silver halide grains and the color couplers to ensure. From GB-PS 531 243 are also materials with a relatively small Gelatine / silver halide ratio known, but which do not contain any color couplers.

It was an object of the invention to provide an improved photographic material which has improved sharpness and color graininess, especially at higher sensitivity.

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It has now become photographic recording material with at least one photosensitive silver halide emulsion layer E found, which is surrounded by layers K containing color couplers. Is according to the invention At least one color coupler-containing layer K is arranged above and below the layer E, these layers containing color couplers Layers are in a water-permeable relationship to layer E and no silver halide contain or wherein in these color coupler-containing layers th only comparatively insensitive silver halide is included. Layer E is relatively thin and has a relatively high silver halide packing density. Under The silver halide packing density is the ratio of silver contained in a layer (calculated as Grams of silver nitrate) to the dry layer volume of this layer (calculated in cm).

In a preferred embodiment, the layer E is at most 1.5μ thick and has a packing density of at least 1.0. The binder / silver ratio in this embodiment is a maximum of 0.4. The binder / silver ratio is defined calculated as the quotient of the binding agent, e.g. gelatine, in grams and the silver contained as grams of silver nitrate.

The color coupler-containing layers K generally contain, in addition to the color coupler, a binder, preferably Gelatin. Different color couplers can optionally be contained in a layer K. In a layer K which is above the silver halide emulsion layer E can use the same color couplers

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exist as in the layer K, which is below the layer E. But it is also possible in the above and assigned color coupler-containing layers K lying beneath the silver halide emulsion layer E are different Color couplers should be used under the conditions of development in the reaction with the oxidized color developers give the same color, a similar color or a completely different color. The latter is appropriate, for example, when only black and white Dye images are to be generated.

As already indicated, the layers K containing color couplers contain no silver halide or only silver halide comparatively low sensitivity. If silver halide is used, a comparatively low sensitivity is used this can contain AgCl, AgBr and AgI as well as mixtures thereof. Preferably an unsensitized one Silver halide emulsion containing at least 20 mol% silver chloride is used. In particular, such silver halide emulsions are used preferred whose silver halide grains have an average grain diameter of less have than 0.5μΐη. Included therein are silver halide emulsions known under the name Micrate emulsion or Lippman emulsion are known and an average grain diameter of less than 0.1 μm to have. Such emulsions are relatively very insensitive to light. Preferably the sensitivity is these silver halide emulsions for blue light are at least 50 times lower than that the image-recording blue-sensitive layer.

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Comparative to such a silver halide emulsion low sensitivity, no image should be recorded. Such an emulsion can but a beneficial effect on the neighboring image-recording Exercise shifts. Such comparatively insensitive silver halide emulsions can also contained in the silver halide emulsion layers E in addition to the light-sensitive silver halide be.

In a preferred embodiment, the silver halide emulsion layer E has no color coupler, has a thickness of preferably not more than 2. Oil, in particular not more than 1.2μ and a binder / silver ratio as defined above of preferably not more than 0.4 / in particular not more than 0.2. The packing density is preferably at least 1.5 and in particular at least 2.0.

In another preferred embodiment, at least E is also present in the silver halide emulsion layer a color coupler. However, this is generally not as reactive as the most reactive color coupler in the associated color coupler Layers K. A measure of the reactivity is the reaction rate constant of the coupling of the color coupler with the oxidation product of the

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Color developer. Such rate constants can be measured in a known manner, noted see, for example, the publication by J. Eggers in the "Mitteilungen aus den Forschungslaboratorien" der Agfa ", Leverkusen-München, Volume III, 1961, page 81 ff. The rate constant is preferred the coupling reaction of the color couplers contained in the color coupler-containing layers K at least by a factor of 2, in particular by a factor of 5, larger than the corresponding size in the SiI overhalide emulsion layer E included color coupler. In this embodiment too, there is the silver halide emulsion layer E has a high packing density. Generally in this embodiment on 1 gram of silver halide in emulsion layer E, 0.5 gram of coupler in layer E before. If conventional color couplers and conventional hydrophilic binders are used, the silver halide packing densities are in the layer in this embodiment E preferably at least 0.7, in particular at least 0.9. In this embodiment, the Silver halide emulsion layer has a maximum thickness of at most 3.5μ, preferably at most 2.8μ and has a binder / silver ratio of a maximum of 0.4, in particular a maximum of 0.2. The color coupler-containing Layers K in this embodiment have a Maximum thickness of preferably at most 3.0μ, preferably of a maximum of 2.5μ. The information regarding the thickness of the layers relate to the

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Dry state. To achieve the lowest possible dry film thicknesses, the weight ratio exceeds from dietary fiber to color couplers in the color coupler-containing layers K has the value 1 in the dry state generally not. The sum of binders / oil formers and plasticizers is used here as dietary fiber and other additions.

The thickness of the coupler layers is appropriate so dimensioned that the color developer oxidation product emerging from the emulsion layer E during color development even at the maximum color density in these coupler layers completely intercepted is without, on the one hand, appreciable amounts of the developer oxidation product in different colored coupling Adjacent layer elements cross over, and without, on the other hand, too large amounts of at the maximum color density unreacted couplers remain.

Both in the emulsion layers E and in the Coupler layers K can also be mixtures of different Color couplers as well as mask couplers, DIR couplers and the like may be present.

The layers K containing color couplers are the silver halide layer E assigned in such a way that, under the conditions of photographic development, those from the From layer E, oxidation products of the color developer in layers K are almost completely eliminated react with the color couplers present there. the end

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this is the reason for the color coupler-containing layers K with the silver halide emulsion layer E in "water permeable relationship". In a preferred Embodiment are the layers K of the silver halide emulsion layer E is therefore directly adjacent, although it is also possible between the layer E and to arrange intermediate layers, for example of gelatin, in the layers K.

usually the color photographic recording materials contain one silver halide emulsion layer unit for recording light each of the three. Spectral ranges red, green and blue. For this purpose, the photosensitive layers are well known Way spectrally sensitized by suitable sensitizing dyes. The blue sensitive silver halide emulsion layer unit does not necessarily have to contain a spectral sensitizer since it is used for recording blue light in many cases the inherent sensitivity of the silver halide is sufficient.

Each of the foregoing silver halide emulsion layer units may have a single silver halide emulsion layer or in a known manner, e.g. with the so-called double-layer arrangement, also 2 or more Include silver halide emulsion layers. Color

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double layer photographic recording materials for the different spectral ranges are for example from the US patents 3 663 228 and 3 849 138 are known. Here, the top of the two indicate the same for light Spectral range sensitive sub-layers the higher sensitivity.

Another suitable layer structure with double layers is from German Offenlegungsschrift 2 530 (US 4 184 876) known. Here they are always the same sensitive red and green sensitive layers combined. Usually the red-sensitive silver halide emulsion layer unit is the support closer than the green-sensitive SiI overhalide emulsion layer unit and this in turn closer than the blue-sensitive, being in general a non-photosensitive layer between the green-sensitive and blue-sensitive layers yellow filter layer is located. However, other arrangements are also conceivable. Different between layers Spectral sensitivity is usually a non-photosensitive intermediate layer arranged the means for preventing the misdiffusion of developer oxidation products may contain.

Preferred arrangements of layers E and K with respect to one another are explained in FIGS.

In FIG. 1, the silver halide emulsion layer E 1 is enclosed by two layers containing color couplers

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K 1 and K 2. As shown in Fig. 2, the silver halide emulsion layer becomes E in 2 sub-layers E 21 and E 22 of different levels of light sensitivity but the same Spectral sensitivity split. The silver halide emulsion layers become the color coupler layers K 21 and K 22 or K 22 and K 23 included. According to Fig. 3, it is also possible that To split the silver halide emulsion layer E into the sublayers E 31 to E 33 lying directly next to one another, where, for example, in layers E and E 31, relatively small silver halide grains and in the layer E 32 may contain relatively coarse silver halide grains. The layers containing color couplers K 31 and K 32 comprise the emulsion layer package.

According to FIG. 4, it is also possible to have several on both sides of the silver halide emulsion layer E 40 to arrange layers containing color couplers (K 41 to K 44) FIG. 5 shows an asymmetrical structure in which the silver halide emulsion layer E 50 on one side through the color coupler-containing layer K 53 and on the other hand is enclosed by the color coupler-containing layers K 52 and K 51.

At. that of the photosensitive silver halide emulsions layer units associated with non-diffusing Color couplers can in principle be any type of non-diffusing connections which, with suitable treatment (development), image dyes with the desired spectral and sensi-

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tometric properties can be generated. The color couplers assigned to a silver halide emulsion layer are understood to be those / those under the conditions of photographic development with that in the respective silver halide emulsion layer resulting developer oxidation product react. In the structure according to the invention are So this is the color coupler contained in the emulsion layer E and in the assigned layers K.

Preferably, each of the above photosensitive silver halide emulsion layers is a non-diffusing one Color coupler assigned to that with color developer oxidation products with the formation of a non-diffusing Able to react dye.

The one or, if appropriate, several sub-layers Color couplers associated with the same spectral sensitivity do not necessarily need to be identical be. They are generally only intended to give the same color upon color development, usually a color that is complementary to the color of the light against which the associated photosensitive Silver halide emulsion layers are sensitive. The red sensitive silver halide emulsion layers is consequently at least one non-diffusing color coupler for generating the blue-green partial color image assigned, usually a phenol or ^ -naphthol type coupler. The green-sensitive

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chen silver halide emulsion layers is at least one non-diffusing color coupler each assigned to generate the purple partial color image, color couplers of the 5-pyrazolone or indazolone type usually being used. There is at least one non-diffusing color coupler in each of the blue-sensitive silver halide emulsion layers assigned to generate the yellow partial color image, usually a color coupler with an open chain Ketomethylene grouping. However, other assignments can also be made for special purposes. Color couplers of this type are known in large numbers and are described in a large number of patents. An example is the publications "Farbkuppler" by W. Pelz in "Mitteilungen aus den Forschungslaboratorien der Agfa, Leverkusen / Munich", Volume III, Page 111 (1961) and K. Venkataraman in "The Chemistry of Synthetic Dyes ", Vol. 4, 341-387, Academic Press (1971), referenced.

The color couplers can be conventional 4-equivalent couplers act as well as 2-equivalent couplers, in which a lesser color generation is used Amount of silver halide is required. It is known that 2-equivalent couplers are derived from 4-equivalent couplers from the fact that they contain a substituent in the coupling point which occurs during the coupling is split off. The 2-equivalent couplers which can be used according to the present invention include both count those that are practically colorless as well

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those that have an intense intrinsic color that disappears when the color is coupled or because of the color of the generated image dye is replaced. The latter couplers can also be added according to the invention in the photosensitive silver halide emulsion layers be present and there as a mask coupler to compensate for the undesired secondary layers the image dyes serve. The well-known white couplers are also part of the 2-equivalent couplers which, however, do not result in any dye when reacting with color developer oxidation products. to the 2-equivalent couplers are also known DIR couplers, which are couplers acts that a detachable in the coupling point Contain remainder, which is set free when reacting with color developer oxidation products as a diffusing development inhibitor.

If necessary, color coupler mixes can be used to create a desired hue or tone Adjust reactivity. For example, water-soluble couplers can be used in combination with hydrophobic water-insoluble ones Couplers are used.

The silver halide emulsions can be by simple Inlet as well as by double inlet. Suitable methods of this type are for example in British Patent 1,027,146 and in the publication by E. Moisar and S. Wagner in "Reports of the Bunsen Society for Physical

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./19.

Chemie ", 67 (1963), pages 356 to 359. It is also possible to dissolve fine-grained starting emulsions in the presence of silver complexing agents and in the presence of the peptizing agents according to the invention produce coarse-grained emulsions. Such methods are known, for example, from U.S. Patents 2,146,938, 3,206,313, 3,317,322 and German Auslegeschrift 1,207,791.

According to the invention, both emulsions with narrower than can also be precipitated with a relatively broad grain size distribution. In particular, according to the invention, both homodisperse as well as heterodisperse silver halide emulsions are produced.

Homodisperse emulsions are understood to mean such with narrow grain size distribution; preferably have at least 95% of the silver halide grains a diameter which is not more than 40%, or preferably not more than 20%, of the mean grain diameter deviates. The silver halide grains can be any of the known shapes, e.g., cubic, octahedral or a tetradecahedral mixed form exhibit.

Heterodisperse emulsions are to be understood in particular as those in which at least 10%, preferably but at least 20% of the silver halide

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grains have a diameter that is at least 40% deviates from the mean grain diameter. The silver halide grains of such emulsions generally have an irregular shape.

The silver halide grains in the layer E preferably have a size of at most 1.5μ. Her The minimum size is generally around 0.1μ.

The silver halide emulsions can be used to remove the water-soluble salts either after the addition of Gelatine can be solidified, noodled and watered in a known manner or with a coagulant coagulated and then washed, as it is, for example, from the German Offenlegungsschrift 2 614 862 is known.

The photographic materials can be developed with common color developing agents, e.g. N, N-dimethyl-p-phenylenediamine, 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline, 2-amino-5-diethylaminotoluene, N-butyl-N- ^ -sulfobutyl-p-phenylenediamine, 2-amino-5- (n-ethyl-N-ß-methanesulfonamidethyl-amino) -toluene, N-ethyl-N-ß-hydroxyethyl-p-phenylenediamine, N, N-bis- (ß-hydroxyethyl) -p-phenylenediamine, 2-amino-5- (N-ethyl-N-ß-hydroxyethylamino) toluene. Further useful color developers are described, for example, in J. Amer. Chem. Spc. 23, 3100 (1951).

Gelatin is preferably used as a binder for the layers. However, this can be wholly or partially

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wisely be replaced by other natural or synthetic binders.

The emulsions can also be chemically sensitized, e.g. by adding sulfur-containing compounds in chemical ripening, for example allyl isothiocyanate, allyl thiourea and sodium thiosulfate. Reducing agents, e.g. those in the Belgian Patent specifications 493 464 or 568 687, described tin compounds, also polyamines such as Diethylenetriamine or aminomethylsulfinic acid derivatives, e.g. according to Belgian patent 547 323, be used. Also suitable as chemical sensitizers are noble metals or noble metal compounds such as Gold, platinum, palladium, iridium, ruthenium or rhodium. It is also possible to use the emulsions with polyalkylene oxide derivatives to sensitize, e.g. with polyethylene oxide with a molecular weight between 1000 and 20,000, also with condensation products of alkylene oxides and alcohols, aliphatic carboxylic acids, aliphatic Amines, aliphatic diamines and amides.

The emulsions can also be optically sensitized, e.g. with the usual polymethine dyes such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, Styry! dyes, oxonols and the like. Such sensitizers are in the work of F.M. Hamer "The Cyanine Dyes an Related Compounds",

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(1964).

The emulsions can also contain the usual stabilizers, such as homeopolar or salt-like stabilizers Compounds of mercury with aromatic 5 or heterocyclic rings such as mercaptotriazoles, simple Mercury salts, sulfonium mercury double salts and other mercury compounds. As stabilizers are especially suitable azaindenes, preferably tetra or pentaazaindenes, especially those with Hydroxyl or amino groups are substituted. Such compounds are e.g. in the article by Birr, Z.Wiss.Phot. £ 7 (1952), 2 to 58. Further suitable stabilizers include heterocyclic mercapto compounds, e.g. phenyl mercaptotetrazole, quaternary benzothiazole derivatives and benzotriazole.

The layers of the photographic material can be hardened in the usual way, for example with Formaldehyde or halogen-substituted aldehydes that contain a carboxyl group, such as mucobromic acid, diketones, Methanesulfenic acid esters, dialdehydes and the like. The photographic layers can furthermore be treated with hardeners of the epoxy type or of the heterocyclic type Ethylenimine or acryloyl type are cured. Furthermore, it is also possible to use the layers according to the procedure of the German Offenlegungsschrift 2 218 009 to harden in order to achieve color photographic materials suitable for high temperature processing

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• 23.

are suitable. It is also possible to use the photographic layers or the multi-layer color photographic materials to harden with hardeners of the diazine, triazine or 1,2-dihydroquinoline series. Examples Such hardeners are diazine derivatives containing alkyl or arylsulfonyl groups, derivatives of hydrogenated Diazines or triazines, such as 1,3,5-hexahydrotriazine, Fluorine-substituted diazine derivatives such as fluoropyrimidine, esters of 2-substituted 1,2-dihydroquinoline or 1,2-dihydroisoquinoline-N-carboxylic acids. Vinyl sulfonic acid hardeners can also be used, Carbodiimide or carbamoyl hardeners, such as in the German OffenlegungsSchriften 2 263 602, 2,225,230 and 1,808,685, French patent 1,491,807, German patent 872 153 and the GDR patent specification 7218. Further usable hardeners are, for example, in the British Patent 1,268,550.

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* ■ tr

3113C09

Examples

The following color couplers are used in the examples described below:

Color coupler no.

OH

Cl CH.

T-rn-rHn- / ⁷

NH-CO-CH-O-

CH-

Cl

CH., - C-CH,

CH.

Color coupler no.

OH

C ₃ F ₇ -CO-NH

-CO-CH-O- \\ Vc-CH ₂ -CH ₃

o-C

CH ₀ ι *

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311 3 * *
3009 ^ Cl
\ - in - ^} - --- CH ₂
NC = O
\ _N / 25- Color coupler no. C ₁₄ H ₂₉ -CO-NH

Cl

Color coupler No. 4

^C 15 ^H 31

O-CH-CO-NH-C-CH

N C = O

Cl. ^^ CH

CH.

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Color coupler No. 5

CH, -C-CO-CH-CO-NH,
^J ι «| l
CH ₃

<Λ J) -COOCH ₃ SO ₂ -NH-CH ₃

Layer structures are described in the following examples. The quantities given relate if

not otherwise indicated, each to 1 ra of the one used Layer carrier. The corresponding amounts of silver nitrate are specified for the silver application. Unless otherwise stated, the layer thicknesses refer to the dried structure.

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example 1

The following layers are applied to a layer substrate in the order shown:

Color coupler-containing layer K 1

The layer contains 800 mg of color coupler no. 1, emulsified with a total of 320 mg of oil formers. In the The layer also contains 160 mg of gelatine as a binder. The one used to make the layer Small amounts of polystyrene sulfonic acid and a wetting agent were added to the casting solution.

Emulsion layer E.

This layer contains 2140 mg of a silver bromide iodide emulsion (6 mol% silver iodide), the mean grain size of the silver halide grains being Ο, δμ. The silver halide emulsion is red sensitized and stabilized with a tetraazaindene. In the Emulsion layer E is still 530 mg of color coupler No. 2, emulsified with a total of 215 mg of oil-forming agent, and 460 mg gelatin as a binder. The layer also contains small amounts of polystyrene sulfonic acid and a wetting agent.

Color coupler-containing layer K 2

This layer corresponds completely to that given above Layer K 1.

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The individual layers were cast at the same time with a so-called cascade arrangement. The layer thicknesses after drying are:

Layer 1

5 shift 2

Layer 3

1.3 µ
1.6 µ
1.3 µ

The material was cured in a conventional manner and according to "The British Journal of Photography", 12, 1974, Pages 597 to 598, subjected to color negative processing.

For comparison, a material was produced which contained the same substances in the same concentrations as contained in the material according to the invention, but with those used for the production of the individual layers Casting solutions were mixed before application to the substrate, so that a total of only one Layer was applied. This material was further processed in the same way as that according to the invention. The values shown in Table 1 below were obtained:

Table 1

material

Graininess D = 1.0 χ 10 ² ) Dei Density D D = 2.5 D = 0.5 6th , 5 D = 1 , 5 D = 2.0 5.0 5.3 8th , 9 6, 0 5 , 6 11.8 5.5 10, 2 11 , 0

sensitivity

Max

Invention comparison

25.8
26.3

2.58 2.87

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An increase in sensitivity of 3 units corresponds to a doubling of the sensitivity. To define and determine the graininess is Reference is made to Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, 1979, pages 412 ff.

From Table 1 it can be seen that with the invention Material a significantly improved graininess is obtained with practically the same sensitivity.

Example 2

The following layers in applied in the order given:

Color coupler-containing layer K 1

This layer contains 600 mg of color coupler no. 3, which is emulsified with a total of 240 oil-forming agents. the The layer also contains 120 mg gelatin and small amounts of polystyrene sulfonic acid and wetting agents.

Color coupler-containing layer K 2

This layer corresponds to the above-mentioned layer K 1 with the exception that instead of the color coupler # 3 450 mg of the slower # 4 purple coupler be used.

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Emulsion layer E.

This layer contains 1500 mg of a silver bromide iodide emulsion (8 mol% iodide), the mean grain size of the silver halide grains being 0.7μ. The silver halide grains are sensitized in green and stabilized with a tetrazaindene. Layer E contains furthermore 500 mg of the slow purple coupler no. 4, 200 mg of oil former for the color coupler and a total of 470 mg gelatin as a binder.

Color coupler-containing layer K

This layer contains 800 mg of color coupler no. 3, emulsified with a total of 320 mg of oil-forming agent. The layer also contains 160 mg gelatin as a binder and small amounts of polystyrene sulfonic acid and Wetting agents.

The layer structure is hardened with a conventional wetting agent. After drying, the layers show the following layer thicknesses:

K 1: 1.0µ

K 2: 0.9 µ

E: 1.1μ

K 3: 1.3µ

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For comparison, a material is made that contains the same substances in the same quantities as Contains the material according to the invention, but the casting solutions for the preparation of the individual Layers were mixed before potting on the substrate, so that a total of only one layer is present.

The materials were imagewise exposed and reverse processed. In reverse processing the material is treated in the following baths:

bath Time
(min) temperature
( ⁰ C) First developer 6th 38 ⁰ C 15 soaking 2 Il Concealment bath 2 Il Color developer 6th Il hair conditioner 10 Il Bleach bath 6th Il 20 fixer 4th Il Watering 2 π

The bath compositions described in the Manual for Processing are essentially used here Kodak Ektachrome Films Using Process E-7, Eastman Kodak Company, 1977.

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The following values are obtained;

Table 2 Graininess
D = 0.5 D = 1.0 , χ 10 ² yrs
D = 1.5 at density D
D = 2.0 D = 2.5 Sensation
opportunity Max 85
2 material 3.8 4
4.0 5 , 2
,8th 3.8
7.0 3.6 3.5
7.5 7.8 23.8
24.0 2,
3, invention
comparison

From the table it appears that the graininess is achieved with the inventive structure, a significant improvement.

Example 3

The following layers are applied to a layer support according to FIG. 6 in the order given:

1. Black noodle layer

This layer contains 1800 mg gelatin and 400 mg Ag

2
(= 618 mg AgNO ₃ J per m.

1.0 2. Color coupler-containing layer K (bg) T

This layer contains 1300 mg of color coupler no. 1 emulsified in a total of 500 mg of an oil former. the Layer also contains 260 mg gelatine as a binding agent

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medium and small amounts of polystyrene sulfonic acid and a wetting agent. The thickness of the dry layer is 2.1 μ.

3. Silver halide emulsion layer E (bg)

This layer contains 2500 mg of a silver bromide iodide emulsion (6 mol% silver iodide, mean grain size 0.8μ), which is sensitized in red and stabilized with an azaind. The layer still contains 640 mg of color coupler no. 2, emulsified in 250 mg of oil former. In total there are 550 mg of gelatin in this layer Contain binders. Furthermore, there are 80 mg of a red mask and 40 mg of a red mask in this layer DIR coupler. The thickness of the layer is 2.1μ.

4. Color coupler-containing layer K (bg) 2

This layer contains 800 mg of color coupler no. 1, emulsified with a total of 300 oil formers. The layer also contains 160 mg gelatine as a binder and small amounts of polystyrene sulfonic acid and wetting agent. The layer thickness is 1.3μ.

5. Color coupler-containing layer K (pp) 1

This layer contains 1000 mg of the fast purple coupler No. 3, emulsified in 500 mg of oil former. In the layer also contains 250 mg of gelatin and small amounts of polystyrene sulfonic acid and a wetting agent contain. The layer thickness is 1.8μ.

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6. Silver halide emulsion layer E (pp)

This layer contains 1700 mg of a silver bromide iodide emulsion with 8 mol% silver iodide and a medium one Grain size of 0.7 μ, which is sensitized in green and stabilized with an azaind. The layer contains further 540 mg of the relatively slow purple coupler no. 4, 270 mg of oil-forming agent and 100 mg of one Yellow mask and 60 mg of a DIR coupler. All in all 520 mg gelatine are contained in the layer as a binder. The layer thickness is 1.6μ.

7. Color coupler-containing layer K (pp) 2

This layer corresponds in composition and thickness to the layer K (pp) 1 given under 5.

8. Filter yellow layer F

This layer contains colloidal silver with a yellow density of D = 0.8 measured behind a blue filter. Dry layer thickness 0.6μ.

9. Color coupler-containing layer K (gb) 1

This layer contains 800 mg of yellow coupler No. 5.

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which emulsifies with 300 mg gelatine without oil former is. The layer also contains small amounts of polystyrene sulfonic acid and wetting agents. The layer thickness is 1.1 μ.

10. Silver halide emulsion layer E (gb)

This layer contains 1800 mg of a silver bromide iodide emulsion with 2 mol% silver iodide and an average grain size of 1.0μ, which sensitizes spectrally blue and is stabilized with an azaind. This layer also contains 800 mg of that specified in layer 9 Yellow coupler, which is emulsified without an oil-forming agent, and a total of 650 mg of gelatin. The layer thickness is 1.8μ.

11. Color coupler-containing layer K (gb) 2

This layer corresponds in thickness and composition to the layer K (gb) 1 specified under 9.

12. Gelatine protective layer of 0.5μ dry layer thickness

The material described is cured in the usual way.

For comparison, as in Examples 1 and 2, a material is produced in which the casting solutions of Partial layers of each color element (bg = blue-green; pp = purple and gb = yellow) in each case in proportion the wet coatings cast in the material according to the invention are mixed. It will that is, the casting solutions mixed with the invented

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proper structure for the production of the following partial layers were used:

a) the casting solutions for the layers specified under 2. to 4.;

b) the casting solutions for the layers specified under 5. to 7. and

c) the casting solutions for the layers specified under 9 to 11.

The mixtures of the casting solutions obtained in this way are cast with wet applications in the case of the comparison material, which is the sum of the partial wet applications of the respective color element in the invention Material. Analogously to the material according to the invention, between the support and the Blue-green element arranged the black noodle layer specified in the material according to the invention and between the purple element and the gel element, the filter yellow layer specified for the material according to the invention. Since the wet applications are the same, are in the comparison material based on the surface unit the same amounts of the substances used in the material according to the invention. The whole The layer thickness in the comparison material has the same value as in the case of the inventive method mentioned above Layer structure. The comparison material is just like the material according to the invention cured.

AG 1764

Both materials are imagewise exposed to white light and the negative processing indicated in Example 1 subject. The following data is received:

5 Table 3

material

Graininess

D = 0.5 pp bg

D = 1.0 pp bg

x 10) at density D

D = 1.5 PP bg

D = 2.0
pp bg

sensitivity

PP bg

Max

pp bg

Invention 10 comparison

2.5 3.2

2.6 3.3

2.8 3.2 3.8 3.4

2.0 2.6 2.8 3.0

1.5 1.9
2.5 2.6

24.1 24.0 24.5 24.3

2.5 2.2 2.8 2.4

The table again shows the clear improvement in the granularity of the material according to the invention emerged. The graininess of the yellow partial color image could not be taken into account, as a yellow color grain visually is of little consequence. As a result, with the structure mentioned in this example conventional yellow layers or yellow layer packages can also be used.

Example 4

In this example the silver halide emulsion layer contains no color coupler. The following layers are applied to a layer support in the specified manner Order applied:

1. Color coupler- containing layer K 1 This layer contains 360 mg of the following purple

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coupler No. 3 and 140 mg of the following purple coupler

CH

-C

CH

CH,

^X 3

.-M

? 2 ^H 5 Γ
-CH-CO-NH

I Cl

CH ₃ CH ₃
The layer contains 1.49 g gelatin and is 1.6μ thick.

2. Silver halide emulsion layer E.

This layer contains a cubic silver bromide emulsion. The silver halide grains have one mean grain size of 0.8μ and are stabilized with an azaind. The silver application is 3.8 g and the gelatin application 0.5 g. The gelatin / silver nitrate ratio so is 0.133. The layer thickness is 1.04μ.

3. Color coupler-containing layer K 2

This layer corresponds in composition and application to layer K 1.

The silver halide packing density P defined in the specification is 3.65, the coupler / silver nitrate ratio 0.265.

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For comparison, a structure is produced in which, as in the comparative structures of Examples 1 to 3 the casting solutions of the individual sub-layers were mixed before casting. The comparison structure contains thus the same substances in the same amount as the material according to the invention and has the same Total thickness, namely 4.24μ.

Both materials are subjected to the negative processing cycle outlined in Example 1. The course of the Granularity in the material according to the invention and in the comparative material shows that in the case of the invention Material, the granularity surprisingly decreases at a higher density, while in the comparison structure the granularity also increases at high densities.

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Claims (10)

■> ■ • * Claims Photographic recording material with at least a photosensitive silver halide emulsion layer E containing those of associated color couplers Layers is included, characterized in that over the layer E at least one color coupler-containing layer and, under layer E, at least one color coupler-containing layer Layer is arranged, these layers assigned to layer E containing no light-sensitive silver halide or only silver halide comparatively low sensitivity and where layer E is relatively is thin and has a high packing density. 2) Material according to claim 1, characterized in that the layer E is at most 1.5μ thick and their packing density at least 1.0 and the binder / silver ratio at most 0.4 amounts to. 3) Material according to claim 1, characterized in that the color couplers in the associated layers result in essentially the same color when coupling. AG 1764 4) Material according to claim 1, characterized in that at least one layer E does not have a color coupler contains, is not more than 2.0μ thick and has a binder / silver ratio of not more than 0.4. 5) Material according to claim 4, characterized in that that the layer E is at most 1.2μ thick and a binder / silver ratio of at most 0.2. 6) Material according to claim 1, characterized in that in at least one silver halide emulsion layer E a color coupler is included. 7) Material according to claim 1, characterized in that in at least one silver halide emulsion layer E a color coupler is included, which couples more slowly than the couplers in the assigned layers containing color couplers. 8) Material according to claim 7, characterized in that the rate constant of the coupling reaction with the oxidation product of a p-phenylenediamine developer compound in the couplers of the assigned color coupler-containing layers is at least twice as large as in the case of the couplers contained in the silver halide emulsion layer E. 9) Material according to claim 1, characterized in that all couplers are embedded in a diffusion-proof manner. AG 1764 10) A method for producing photographic images by imagewise exposure of the in claim 1 indicated material and development with a p-phenylenediamine developing agent. AG 1764