DE1925359A1 - Photographic recording material - Google Patents

Description

1915359

PATENTANWÄLTE 25/81/77. May 19, 1969

DR.-ING. WOLFF, H. BARTELS, ⁸ t !! i? R? Chs "rasse ² 8

DR. BRANDES, DR.-ING. HELD phone = pn) 293297

Reg. No. 121 863

Eastman Kodak Company, 3 ^ 3 State Street ,. Rochester, New York State * United States of America

Photographic recording material

The invention relates to a photographic recording material, consisting of a layer support and at least two silver halide emulsion layers applied thereon and containing color couplers en (A) and (B) with different sensitivity.

It is known, for example from British Patents 774 655 and 1021 56k , to produce photographic recording materials with a wide latitude for coating by applying a very sensitive and a less sensitive silver halide emulsion layer to a support. Although such recording materials are suitable for many purposes *, they cannot be used in many cases, in particular not because they do not show sufficient contrast in low-light images and a wide exposure latitude of low contrast in high-light images.

However, many uses require that Photographic recording materials have a high contrast

in the case of faint images and a wide scope of low contrast in bright images, so that Record images of very different light intensities, without the bright picture due to its "radiation effect" or its spread on the film surface makes the fainter image invisible.

There is a particular need for such recording materials for the recording of incidents that occur when, for example, a satellite re-enters the earth's atmosphere from its orbit (which has a very faint image) and burns out, producing a more luminous image. If the satellite first enters the atmosphere, the image is very faint, which is why a recording material is graded ₃ which has a high contrast and a high sensitivity. Such a recording material is necessary in order to be able to record the low contrast images which represent the satellite with the sky in the background as it enters the earth's atmosphere. As soon as the satellite begins to burn or glow in the earth's atmosphere, the image of the satellite becomes bright and the black sky and the satellite form a strong contrast. This vivid image is to be recorded by a recording material which has a low contrast and a wide latitude for viewing.

To date there are no photographic recording materials have become known that are high-contrast and have a high sensitivity for faint images and the also have a low contrast with extensive exposure latitude for bright images.

A particular disadvantage of the known recording materials Is it that the faint images do not appear with them.

009837/1834

let draw showing the initial stages of the entry of a satellite from its orbit into the earth's atmosphere. The satellite image taken when re-entering the earth's atmosphere was found to be so faint that it could not be photographically evaluated, namely therefore not because the image is made by the emanation of the more luminous Image of the burning satellite in the lower atmosphere was made to disappear. Until today has been The degree of radiation used by the stronger image of the burning satellite is used to indirectly determine the orbit of the satellite to measure in the initial stages of re-entry into the earth's atmosphere.

The object of the invention is to provide a photographic recording material which has a wide exposure latitude and which furthermore produces images with sharp contours in the entire, practically possible exposure range. A further aim was to provide a recording material which would produce high contrast images when exposed to weak images and which would also produce low contrast images and wide exposure latitude when exposed to strong, bright objects with a dark background .

It was found that the task at hand was thereby can be solved by having at least two silver halide emulsion layers different from one another on the support Sensitivity applies and thereby in the one silver halide emulsion layer a non-diffusing, one Image & dye forming color coupler and a development inhibitor incorporated in liberation setting coupler and in the second silver halide emulsion layer a non-diffusing, introduces an image dye forming color coupler.

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_ Z ₁ _

The invention thus relates to a photographic recording material IaI ₃ consisting of a layer support and at least two silver halide emulsion layers (A) and (B) applied thereon containing color couplers and having different sensitivity, which is characterized in that the silver halide emulsion layer (A) -I. a non-diffusing image dye-forming color coupler and (2) a development inhibitor releasing coupler and that the silver halide emulsion layer (B) contains a non-diffusing image dye-forming color coupler and is more effective in sensitivity than the silver halide emulsion layer (A).

The coupler releasing a development inhibitor in the less sensitive silver halide emulsion layer causes a widening of the clearance scope and decreases the contrast.

The photographic recording materials of the invention are characterized by a wide exposure latitude and are particularly suitable for recording images of very different intensities, which are very close to one another on the recording material with excellent contour sharpness sign off.

With the photographic materials of the invention, images excellent in sharpness can be obtained. the Images have a high contrast in the case of faint image objects and a low contrast in the case of bright image objects.

An advantageous recording material of the invention is characterized in that it is between the layer support and the No image recording silver halide emulsion layers

0 9 8 3 7/1834

I vl 4 ^ y /

or a non-image-forming light diffusing halide emulsion layer having. Photographic recording materials of this type lead to a particularly strong reduction in image distortion (image spread).

Another advantageous recording material of the invention is characterized in that it is between layer supports and the imaging silver halide emulsion layers have an antihalation layer.

The stronger and less sensitive silver halide emulsions Layers used for recording images can be used as silver halides, those conventionally known in photographic Recording materials contain conventional silver halides, for example silver bromide, silver iodide, silver chloride as well as llischhalogenide, z. B, silver bromoiodide and Silver chlorobromide.

The silver halide grains of the silver halide image-recording emulsion layers can be spectrally sensitized, for example when the recording materials with Light of such wavelengths are exposed, which are longer than blue light.

Preferably, the silver halide grains of the two image-recording layers are panchromatically sensitized. For the spectral sensitization of the silver halides, the usual known dyes can be used, which as spectral sensitizers for silver halide are known. Preferably used to generate the image-recording Layers use negative developable silver halide grains t.

009837/1834

The optimal sensitivities of the imaging layers depend on the particular purpose for which the Recording materials are intended. The sensitivity of the two layers preferably overlaps.

Particularly advantageous results are obtained when the effective sensitivity of the less sensitive image-recording layer is about 0.6 log E to about 1.2 log E less than the sensitivity of the more sensitive image-recording layer. It can prove to be advantageous if the more sensitive silver halide emulsion layer has a detection capacity in the range of about 5 quanta per square micron. Preferably, the Aufzelehnungsmat e possess rials of the invention, an exposure latitude of about ICR above the practically applicable exposure width.

The effective sensitivities of the emulsion layers can be set differently in a known manner, for example by using silver halides of different grain sizes, by using chemical sensitizers Use of various concentrations of photographic couplers and the like.

The more sensitive and the less sensitive recording layer can be adjacent to each other. Each of the layers can be closest to the substrate, ie both the more sensitive layer and the less sensitive layer can be the lower or the upper layer.

The less sensitive emulsion layer is preferably located closest to the support and the more sensitive emulsion layer is applied to the less sensitive emulsion layer.

00 9 83 7/183 A

As used herein, the term "photographic image-recording or image-forming couplers" includes organic compounds understand that with the oxidation products of developing compounds consisting of primary aromatic amines Formation of image dyes react.

For the preparation of the photographic recording material of the invention, known image-forming color couplers can be used as well as known development inhibitor releasing couplers can be used.

Typical advantageous ones for the production of the recording material Couplers suitable according to the invention are, for example, those having a 5-pyrazolone coupler radical, a phenolic or α-naphtholic coupler radicals and open-chain ketomethylene coupler radicals.

The known 5-pyrazolone couplers are usually used Generation of the magenta image dyes is used, while the phenolic or naphtholic couplers are used for generation the blue-green egg dyes are used and the open-chain ones Ketomethylene couplers for the production of the yellow image dyes can be used.

The coupling positions of the couplers are known. The 5-pyrazolone couplers couple on their carbon atom in the 4-position, while the phenolic and α-naphtholic couplers couple on the carbon atom in the 4-position with respect to the hydroxyl group and the open-chain ketomethylene couplers couple on the carbon atom which forms the methylene group, ie, for example the position indicated in the following structural formula with the ^{ll + fr:}

H ₊

C LiI ₂

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Heterocyclooxy, e.g. B. a pyridinyloxy radical, a tetrahydropyranyloxy radical, a tetrahydroquinolyloxy group and the like, or an alkoxy group.

For the production of the photographic recording material according to the invention particularly suitable image-forming and Are development inhibitors liberating couplers 5-pyrazolone couplers of the following general formula II:

Il

wherein R, R ₆ and Y _{2 represent} substituents typical of known 5-pyrazolone couplers.

In detail it can be, for example;

Rr is a radical as defined for R ₁ ;

Rf- an optionally substituted alkyl or carbamyl radical or an optionally substituted amino radical, which may be substituted, for example, by 1 or 2 alkyl or aryl radicals, an optionally substituted amido radical, for example an optionally substituted benzamido radical or an optionally substituted alkylamido radical and

Y2 is a residue of the meaning given for Y-.

The images used for the production of the photographic recording material according to the invention ζ eugenJen and Ent-

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1325359

For the production of the recording material according to the invention are particularly suitable open-chain ketomethylene couplers those of the formula I given below:

0 H
I.

C-C

Herein, R _1, X ₁ and Y ₁ represent conventional substituents as ψ in conventional, known open chain Ketomethylenkupplern occur.

In detail, for example:

R _{1 is} an optionally substituted alkyl radical with preferably 6 to 22 carbon atoms, an aryl radical, preferably of the phenyl or maphthyl series or a heterocyclic radical, preferably a heterocyclic radical containing at least 1 carbon atom with 5 to 6 ring atoms, which consists of at least 1 from an oxygen, Has a heteroatom consisting of a sulfur or nitrogen atom;

' X _{1 is} a cyano radical or an optionally substituted carbamyl radical and

Y _{1 is} a radical which is typical of colorless image-forming couplers, ie for example a hydrogen atom or a coupling-off radical, e.g. B. a halogen atom, for example a chlorine or a fluorine atom, or a thiocyano group, an acyloxy group, for example an optionally substituted Alko ^ yloxy group or an optionally substituted aryloxy group or an optionally substituted heterocycloyloxy group or a cyclooxy group, including an aryloxy group, e.g. . a phenoxy or naphthoxy radical or a

00 98 37 / 183A:

Resolving inhibitors can also advantageously consist of plienolic and a naphtholic couplers of the following general formula III:

OH

^Y 3

where R-iq ^"r i ι" ^R i? * ^R 13 ^{un (* Y} 3 J ^ewe i ^ls a Sübstituenten represent, as is typical for phenolic and o-naphtholic known couplers.

In detail, for example:

R ₁ Q and R ₁₁ radicals of the _{meaning given for R 1} and also in each case a hydrogen or halogen atom or an amino, carbonamide, sulfonamide, sulfamyl, carbamyl or alkoxy radical;

R-2 and R ₁ , together the atoms required to complete a benzo radical, it being possible for this benzo radical to be substituted by one or more radicals as defined for R ₁₀ and R ₁₁ ;

R ₁₂ and R ₁ - each individually radicals as defined for R ₁₀ and R ₁₁ and

the Y, a radical of the meaning given for Y- with / exception that Y, is not an aryloxy radical, but is also a cycloimido radical can be, for example a maleimido, a

Ö09837 / 183A

Succinimido, a 1,2-dicarboximido or a phthalimido radical when R- ₂ ^ ¹ ^ - ^ ₁ ? together form a benzo residue.

The couplers used according to the invention are preferably non-diffusing couplers.

Particularly advantageous leftovers for the Y .., Y _? and Y, can be represented, for example, by the following structural formulas:

0 X ₀ 0 OX,

2 π ι ·. 3

R ₂ C— CHOC— ■ and R ^ C — CH-0 -

in which R ₉ and R have the meanings given _{for R 1 and X 2} and X- have the meanings given for X-.

Particularly advantageous results are obtained when the imaging agents used in the silver halide emulsion layers Couplers are colorless. However, colored couplers can also be used. With "image-generating couplers" are meant that do not have a development inhibitor in Ηεί-unit set.

For the preparation of the photographic recording material Image-forming couplers useful in accordance with the invention may be used both so-called 4-equivalent couplers and so-called 2-equivalent couplers, and indeed not tdif founding matchmakers sän. Typical suitable 4-equivalent couplers that are used to generate yellow Let dye images be used, for example:

1. N-Amyi-p-benzoylacetaminobenzenesulfonate;

2. N- (4-anisolyacetaminobenzenesulfonyl) -N-benzyl-; Tn- .., ^ν

toluidine;

3. N- (4-Benzoylacetaminobenzenesulfonyl) -N-benzylaniline;

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BATH ORIGINAL

4. (D- (p-Benzoylbenzoyl) acetaniline;

5. ω-benzoyl-p-sec.-amylacetaniline;

6th N, N'-di (ω-benzoylacetyl) -p-phenylenediamine;

7. a- {3- / ct- (2,4-di-tert-amylphenoxy) butyramido7-benzoyl} -2-methoxyacetaniline;

8. 4,4 · -di (acetoacetamino.) -3, 3'-dimethyldiphenyl;

9. ρ, ρ ¹ -di (acetoacetamino) diphenyl methane;

10. Nonyl p-benzoylacetaminobenzenesulfonate;

11. N-phenyl-N ^l - (p-acetoacetaminophenyl) urea;

12. n-propyl-p-benzoylacetaminobenzenesulfonate acetoacetpiperidide;

13. N- (üj-Benzoylacetyl) -1, 2,3,5-tetrahydroquinoline and

14. N- (oj-Benzoylacetyl) morpholine.

2-equivalent couplers suitable for the production of the photographic recording material according to the invention, which are for generating yellow dye images are derived from the corresponding 4-equivalent couplers in that one of the two water to ff atoms on the a-I carbon atom, d. H. of Ilethylene residue, through a non-chromophore decoupling The radical is replaced, for example by a fluorine atom, a chlorine atom, an i'xyloxy radical, a cyclooxy radical or a Thiocyano radical.

Typical, for the production of the recording material according to 2-equivalent couplers suitable for the invention are, for example the ot fluorocouplers known from US Pat. No. 3,277,155, also the α-chlorocouplers known from US Pat. No. 2,778,658 and also those from the US Pat 3,253,924 known ct-thiocyanocoupler, which from the British Patent 1 118 028 - - '· - ·

BAD ORfGiNAL

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known α-acyloxy couplers and also those from

U.S. Patent No. 2,933,033

α-cyclooxy couplers and those from U.S. Patent 3,227 known α-alkoxy couplers.

Typical ones used in the manufacture of the photographic recording material 2-equivalent couplers which form yellow image dyes and which are suitable according to the invention and have open-chain ketomethylene radicals are for example:

1. 4- (α-2 '-fiethoxybenzoyl-α-chloroacetamido) -3 "- (4 ^MI -tert.-amylphenoxy) benzanilide;

2. α-0-methoxybenzoyl-α-chloro-4- ^ ö- (2,4-di-tert-amylphenoxy) -n-butyramido7acetanilide;

3. a- {3- ^ ö- (2,4-Di-tert-amylphenoxy) butyramido7benzoyl} -a-fluoro-2-methoxyacetanilide;

4. α-Fluoro-α-pivalyl-5- ^ γ- (2,4-di-tert-amy! Phenoxy) -butyramido7-2-chloroacetanilide;

5. a-Acetoxy-a- {3- ^ Y- (2j4-di-tert-amylphenoxy) -butyramido-7-benzoyl} -2-methoxyacetaniiide;

6. a-Benzoyl-a- / a- (2,4-di-n-amylphenoxy) acetox ^ 7-2-methoxyacetanilide;

7. α-pivalyl-α-stearoyloxy-4-sulfamylacetanilide;

. a-pivalyl-ct-ZS- (3-pentadecy! phenoxy) acetox ^ 7 " 3,5-diamyloxyacetanilide;

α-acetoxy-a- {3- / ci- (2 _> 4 ^ di-tert-amylphamido7benzoyl} -2-methoxyacetanilide;

enoxy) butyr-

10. a- (3-Dodecanamidobenzoyl) -a-octanoyloxy-2-methoxyacetanilide;

11. a- {3- ^ Y- (2,4-Di-tert, -amylphenoxy) butyramido7benzoyl · ο (4-nitrophenoxy) -2-methoxyace tanilide;

2. a- ^ ~ 4- (N-Methyl-N-octadecylsul £ amyl) phenox £ 7 ~ a · " pivalyl-4-octylacetanilide, potassium salt;

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1 3. a-Pivalyl-a- (4-sulfophenoxy-4- (N-methyl-N-octadecylsulfamyl) acetanilide Potassium salt;

14. a- / ~ 4- _(4-Hy> droxyphenylsul £ onyl) phenoxy7-a-pivalyl-2-chloro-5 / Y (2,4-di-tert-amylphenoxyjbutyraBiido7-acetanilide;

15. 4,4 ^l -Bis ^ ä-pivalyl-ai2-cliloro-5- / Y- (2,4-di-tert.-amylphenoxy) butyramido7phenylcarDamyl methox ^ 7-diphenylsulfone and "

16. α-Benzoyl-α-thiocyanoacetanilide.

For the production of the pliotographic recording material typical 4-equivalent couplers suitable according to the invention, that produce purple dye images are, for example:

1. i-p-sec-amylphenyl-S-n-amyl-S-pyrazolone;

2. 2-cyanoacetyl-5- (p-sec-amylbenzoylamino) coumarone;

3. 2-cyanoacetylcuraaron-5- (N-n-amyl-p-tert-aniylsulfanilide;

4. 2-cyanoacetylcoumarone-5-sulfone-N-n-butylanilide;

5. 2-cyanoacetyl-5-benzoylaminocoumarone;

6. ^ -Cyanoacetylcoumarone-S-sulfondimetliylamide;

7. 2-cyanoacetylcoumarone-5-sulfone-N-ynethylanilide;

8. 2-cyanoacetylcoumarone-5- (N-Y-phenylpropyl) -p-tert-amylsulfonanilide;

9. i-p-Laurylphenyl-S-methyl-S-pyrazolone;

10. i-e-naphthyl-S-amyl-S-pyrazolone;

11. i-p-nitrophenyl-S-n-amyl-S-pyrazolone;

12. i-p-Phenoxyphenyl-S-n-aniyl-S-pyrazolone;

13. i-phenyl-3-n-amyl-S-pyrazolone;

14. 1,4-phenylene-bis-3- (1-phenyl-5-pyrazolone);

15. 1-Phenyl-3-acetylamino-5.-p) naz.Qlon; ■

009837/1834

16. i-Phenyi-S-n-valerylamino-S-pyrazolone;

17. i-Paenyl-S-cliloroacetylamino-B-pyrazolone;

18. l-phenyl-S-benzoylamino-S-pyrazolone;

19. 1-phenyl-3- (m-aminobenzoyl) amino-5-pyrazolone;

20. i-phenyl-S-fp-sec-amylbenzoylamino) -5-pyrazolone;

21. i-phenyl-S-diamylbenzoylamino-S-pyrazolone;

22. 1-phenyl-S-β-naphthoylamino-S-pyrazolone;

23. i-Phenyl-S-phenylcarbamylamino-S-pyrazolebn; 24 * i-phenyl-S-palmitylamino-S-pyrazolone;

25. 1-Phenyi-3-betizolsil £ bnylamiiio-5-i) yrazoion;

26. 1-j [p-phenoxyphenyl) -3- (p-tert-amyloxybenzoyl) amino-S-pyrazolone;

27. 1- (2 ^t , 4 ^l , 6'-trichloi'ophenyl) -3-benzamiclo-5-pyrazolone;

28. 1- (2 ^l , 4 ', ^6l "T ^{rit>l> OITl0} Ph ^en yl3" ³ -p ^ ^en yl ^{acetami <} i ^o ~ ⁵ -pyrazolone;

29. 1- (2 ⁱ , 4 ^t -dichlorophenyl) -3 - ^ '3 "- (2 ^l ", 4 ^tII -di-tert-aaiylphehoxyacetami do) benzaniido / -5-pyrazolone;

30. 1- (2 ', 4 ⁱ , 6'-Trichlorophenyi) -3- ^ 3 ^M - (2 ^{H |} , 4 ⁱ "-di-tert-aiiiylphenoxyacetamido) benzamido7-5-pyrazolori;

31. 1- (2V, 4x, 6x -trichlorophenyl) -3- ^ 3-2 "', 4" -di-tert-aiaylphenoxy) -propionamido / -5-pyrazolone;

32. i- (2 ', 5 ⁱ -dichloro) -3 - / "3 ^tl -C4 ^IM -tert.-anyiphenoxy) -benzaisido7-5-pyrazoion;

33. 1- (2 ^t _s 4 ^I _i 6 ^t -Tribtomophenyl) -3 - ^ "3" - (4 ^IM -tert.-ainylphehoxy) -benzamido7-5-pyrazolone and

34. 1- (2 ", 5'-dichlorophenyl) -3- ^ ~ 3" - ( ^2π * "4""- di-tert-asylp]! Ienoxyacetainido) benzainido7-5-pyrazoion.

The 2-equivalent 5-pyrazolone couplers are derived from the corresponding ones 4-Kequivalent-5-Pyrazoioriküpplern from the fact that a hydrogen atom of the carbon atom in the 4-position

of the pyrazolone ring is replaced by a non-chromophoric coupling-off radical. Examples of coupling-off radicals which are present in 2-equivalent couplers of the 5-pyrazolone type are, for example, the thiocyano radical (cf. the couplers known from US Pat. No. 3,252,924) and the acyloxy radical (cf. those from US Pat. No. 3,311 476 known magenta image dye-forming couplers). Further decoupling radicals are, for example, acyloxy, aryloxy and alkoxy radicals, as are known, for example, from US Pat. No. 3,227,550, ₉ the chlorine atom, the fluorine atom and the sulfate radical.

fc Typical 2-equivalent couplers for producing magenta dye images, which can be used for the production of the x ^ hotographic recording material according to the invention are for example:

1. 1 - (2,4,6-Trichlorophenyl) -3- (4-nitroanilino) -4-stearoyloxy-5-pyrazolone;

2. 1- (2,4,6-Trichlorophenyl) -3- {3- / a- (2,4-di-tert-amylphenoxy) acetamido7benzamido} -4-acetoxy-5-pyrazolone;

3. 1 - (2,4,6-trichlorophenyl) -S-pentadecyl ^ -thiocyano-5-pyrazolone;

4. 1- (2,4,6-Trichlorophenyl) -3- / ~ 3- (2,4-di-tert-amylphenoxyacetamido) benzamido7 "4-thioecyano-5-pyrazolone;

W 5. 1-Cp-tert-butylphenoxyphenyl) -3-a- (p-tert-butyl-

phenoxy) propionamido-4-thiocyano-5-pyrazolone;

6. 1- (2,4,6-trichlorophenyl) -3-pentadecyl-4-sulfo-5-pyrazolone;

7. 1 - (2,4,6-Trichlorophenyl) -S-pentadecyl ^ -chloro-S-pyrazolone and

8. 1- ^ 5- (3,5-Dimethoxylbenzamido) phenyl7-3-ethoxy-4- (3-octadecylcarbamylphenylthio) -5-pyrazolone.

For the production of the photographic recording material according to the invention suitable 4-equivalent couplers, which for Production of blue-green dye images are suitable and

009837/1834

consist of phenolic or naphtholic couplers for example:

1. 5- (p-Amylphenoxybenzenesulfonamino) -1-naphthol;

2. 5- (n-Benzyl-N-n-valerylamino) -1-naphthol;

3. 5-caproylamino-i-naphthol;

4. 2-chloro-5- (N- n -valeryl-N- p -isopropylbenzylamino) -1-naphthol;

5. 2-chloro-5-palmitylamino-1-naphthol;

6. 5-diphenyl ether sulfonamido-i-naphthol;

7. 1-Hydroxy-2- (H-isoamyl-N-phenyl) naphthamide;

8. 8-Hydroxy-1-ot-naphthoyl-1,2,3,4-tetrahydroquinoline;

9. i-Naphthol-S-octyl-cyclohexylamide;

10. 5-phenoxyacetamino-i-naphthol;

11. Monochloro-S-CN-Y-phenylpropyl-N-p-sec.-amylbenzoylamino) -1-naphthol;

12. 2-benzoylamino-3,5-dimethylphenol;

13. 2-a- (p-tert-amylphenoxy) -n-butyrylamino-5-methylphenol;

14. 1-i-hydroxy-N- / δ (- (2,4-di-tert-amylphenoxy) butyl7-2-naphthamide;

15. 2- (4-tert-amyl-3-phenoxybenzoylamino) -3,5-dimethylphenol;

16. 2- (4-tert-amyl-3-phenoxybenzoylamino) phenol;

17. 2- ^ ä- (4'-tert-butylphenoxy) propionylamino7phenol;

18. 2 » ₍ /~N-Methyl-N°(4-tert.-amyl-3-phenoxybenzoylamino ^ 7 ^> phenol;

19 »2-a- (4-part Amy! Phenoxy) butyrylamino-1» phenol;

20. 2- (4-tert-amyl-3-phenoxybenzoylamino) -3 _f 5 phenol;

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92535

21. 2- / ä- (4-tert-Ai3ylphenoxy) -n-butyrylamino7 "5 ° methylphenol;

22. 3- (4-tert-amyl-3 ^l -ph.enoxybenzoylamino) piienol;

23. 2- / ~ <x- (4-tert-amylphenoxy) -n-butyrylamino7-6-chloro "= · phenol;

24. 3- / ~ a- (4-tert-amylphenoxy) -n-butyrylamino7-5-chlorophenol;

25. 5-benzenesulfonamido-1-naphthol;

26. 2-chloro-5-benzenesulfonamido-1-naphthol;

27. 5- (1,2,3,4-Tetrahydronaphthalene-6-sulfonamido) -1-naphthol and

28. 2-chloro-5- (4-broinodiphenyl-4-sulfonamido) -1-naphthol,

For the production of the photographic recording material according to the invention it is also possible to use the known phenolic and a naphtholic 2-equivalent couplers which are suitable for producing blue-green dye images. Such 2-equivalent couplers are derived from the corresponding phenolic and α-naphthol! see 4-equivalent couplers by the fact that the carbon atom in the 4-position of the phenolic or naphtholic ring is uncoupled by a non-chromophore, the remainder is substituted, typical such decoupling residues

can for example consist of acyloxy residues (cf., for example, from the
the / USÄ patent 3 311 476 known 4-acyloxyphenols and 4-acyloxynaphthols) _f furthermore cyclooxy radicals (see for example the! 4-cyclooxynaphthols known from British patent 1,084,480), furthermore a TMocyano radical (see ο for example the 4-thiophenols and 4-thionaphthols known from US Pat. No. 3,255,294), cyclic imido radicals (cf., for example, the 4-cyclic imido derivatives of 1-hydrogen-2-haphth = amide known from the Öeutsehen patent) “the chlorine atom (cf. for example the chlorophenols known from US Pat. No. 2,423,730), Alkoxyrest® (cf. for example those from US Pat. No. S 227

009837/1834

Γ - IS -. '

known 4-AlkoxymaplntliojLe) as well as SuI for es te like them occur in 4-sulfophenols and 4-sulfophenols.

Typical recording material used for the production of the photograph blue-green image dyes suitable after exposure Generating 2-equivalents are for example:

1 . 1 -hydro: xy-4-decyloxy-2-naplithamide;

2. 1-Hydroxy-4-acetoxy-M- "£ K- (2,4-di-te rt.-amy! Phenoxy) b utyIj-2-iiapktkaaid;

3. 1-hydroxy-4-ethoxy-fI-octadecyl-3 ', 5' -dicarboxy-2-naphth.anilide;

4th 1-Hydroxy-4-tliIocya3io-] M- £ ä-2,4-di-tert-amylphenoxy) b uty l7 - Z-mapktäiami d;

5. 1-Hydroxy-4- (pentafluorophenoxy) -N- {B- {4- ^ a- (2,4-di - ter t. -anylplienoxy) ace tamido / phenyl} a thy 1} - 2 naphthamide;

6. 1-Hydroxy-4- (4-n.i troplienoxy) -N- / O-2,4-di-tert. amylphenoxy) butyl7-2-iiaplithamid '"and

7th 1-hydroxy-4- (4-caloropliejioxy) -2 '-tetradecyloxy-2-naphthanilide.

The image-forming color complexes are used in such concentrations applied that image dyes obtained a zv / square density v / earth. The optimal concentration to be used in each individual case depends on the properties or characteristics of the dyes produced by the couplers, as well as the nature of the photographic emulsion into which the couplers are incorporated have been.

It is preferred to use non-diffusing colorless imaging couplers. The couplers can form diffusing dyes which can be transferred to an image-receiving sheet, or the couplers can provide non-diffusing dyes.

009837/1834

In general, all customary known ones can be used for the production of the photographic recording material according to the invention Use color couplers, which by image-wise reaction with the oxidation products of primary aromatic Color developing agents consisting of amines produce dye images.

It has proven particularly advantageous to use color couplers for the production of the recording materials according to the invention which produce cyan dye images. It however, other conventional couplers which form magenta or yellow dye images can also be used with excellent Err results can be used.

Those in the image-recording layers of the recording material Couplers used may produce dyes of the same or substantially the same color, or those in both Couplers placed in silver halide emulsion layers can form various dye images.

"Development ^{inhibitors r} liberating couplers" are understood here as those which, when reacted with the oxidation products of developer compounds consisting of primary aromatic amines, generate dyes and release compounds which inhibit development. Couplers which release development inhibitors of this type are often referred to in the literature as so-called "DIR" couplers.

Such development inhibitor-releasing couplers can be represented by the following general formula:

^zc p

where mean:

00 98 3 7/18 34

C is a customary photographic coupler radical, preferably a radical of an open-chain ketomethylene coupler, a 5-pyrazolone coupler or a phenoli see or a-naphtholic coupler produced by the Radical Z are substituted in the coupling position and

Z is an organic residue that is not chromophore, not with the oxidation products of developer compounds consisting of primary aromatic amines couples to form a dye, does not inhibit development as long as it is attached to residue C ,, however, the radical C is split off in the reaction with the oxidation products of primary aromatic amines, where Z is either a development inhibitor or forms a compound which inhibits development.

Particularly advantageous couplers which release development inhibitors are those of the formulas I ₈ II and III, in which Yp, Yg and Y- can each have one of the following meanings;

e A® »Monothiones Z _s for example a ο ° η-.ίΐχΌ» or an o ° siffiisi © Sbstitui®rten Arylmonothiofsstc % ₀ B ₀ pli © njl ° or 2 = ÄsiiaophemyIi? © st ₀ © iaea. Hiind @ st @ RS 1 Sealer gt © ££ st © Ffl containing ligt®irocyclisefe © B. 'UQnotkioTes.t with w @ TZiiQSi-i®ls® 5 to β Ringstomsa lamd siEd.habengt@as οίη & Μ mis- ιθο St £ ekstoff = _ß San® έμ toff «© ds? Sciixfofslatom hüszekm m uad iasbssoiidoi? ® 1 to 4 SticksZu £ fk ^ Z®T <s ^ Tet

in

_{chain alkyl radicals, short-chain alkyl amides, 8} short-chain alkoxy radicals, short-chain alkylsulfonamido radicals, α-chloroacetylthio radicals, short-chain alkyl carbamylaminores, and the like

typical monothio radicals are as well as, for example, 2-aminophenyl, 2-nitrophenyl-, 2-benzothiazolylthio-, 1-phenyl-5-tetrazolylthio-, 1- (4-carbomethoxyphenyl) -5-tetrazolylthio-g 5-phenyl-1,3,4-oxadiazolyl-2-thio-, 2-phenyl-5- (1,3,4) -oxadiazolylthio- or 2-benzoxazolylthio radicals;

W 2. a 2-aminoarylazoxy radical, e.g. B. a 2-amino-4-iaethylplienyl = ·

azoxy-, 2-aminophenylazoxy- or a 2-amino ~ 4-chlorophenyl ~ azoxyrest;

3. a 2-amidoarylazoxy radical, e.g. B. a 2-Acetamldophenylazoxy-j, 2-AcetaInido-4-metllylpllenylazoxy'- _# Z-Acetamido ^ -chlorophenyl'azoxy-, 2-Palmitamidophenylazoxy ° _{l (} 4-Methoxy ~ 2-palinitamido = phenylazoxy-, or a 4- Chloro- "2" palmitaraidoplienylazoxy ~ remainder;

4 * a 2-aryltriazolyl radical, e.g. B ₀ a 2 "Benzotriazolyl-5-chloro 2-b © n2otriazolyl-, 5-hydroxy-2" benzotriazQlyl- _s 4,7 "Dinitro = 2-benzotria2olyl- _s S

j, 2-Naphthotriasolyl- ₈ 4 => Metliyl ~ 2 »naphtho ⁱ = ^> f, G3ol * / I-" 5-Chloro-2-naplithothiazolyl ■ = · ₀ 5-Hydroxy-2 ° naplitIiQ '

or benzo <

^{r 1} ^ - T ₁ nr & ä ΊΛ forms iai if c, T * - <- ":;'* r © iKl3 Ms ^ eaptsa. © saiiä in case © v 3) IMi (4) fiiS £ maÄs £ © i? @ s! €! © "Äry

(3

Typical development inhibitors suitable for the preparation of the photographic recording material according to the invention Liberating couplers (DIR couplers) are for example:

1. α-Benzoyl-α- (2-nitrophenylthio) -4- / N- (Y-phenylpropyl) -N- (p-tolyl) -sulfamyl / acetanilide;

2. a- enzoyl-a- (2-benzothiazolylthio) -4- / M- (y-phenylpropyl) N- (p-tolyl) sulfamyl7acetanilide;

3. a- {3- / a- (2,4-di-tert-amylphenoxy) butyramido7-benzoyl} -α-2-nxtropnenylthio-2-πιethoxyacetanilide;

4. a- {3- / Y- (2,4-di-tert-amylphenoxy) butyramido7benzoyl} -a- (2-Denzoxazolylt! Iio) -2-methoxyacetanilide; "

5 · α-Benzoyl-α- / ~ 1- (3-phenyl) -5-tetr.azolylthio7stearamidoacetanilide;

6v a- {3- / ä- (2 _> 4-di-tert-amylphenoxy) butyramido7benzoyl} -a- (2-aminophenylazoxy) -2-methoxyacetanilide; "*

7. o- {3- ^ Y-C2,4-di-tert-amylphenoxy) butyramido7 "benzoyla- (2-amino-4-methylphenylazoxy) -2-methoxyacetanilide;

8. a- (5-Chloro-2-benzotriazolyl) -a-pivalyl-5- ^ ä- (2 _i 4-di-tert-amylphenoxy) propylamido7-2-chloroacetanilide;

9. a- (4,7-Dinitro-2-benzotriazolyl) -a-pivalyl-Sjo-dichloro-4- (N-methyl-K-octadecylsulfyl) acetoacetanilide;

10. a- (6-Chlpro-5-methoxy-2-benzotriazolyl) -a-pivalyl-2-chloro-57ü- (3-pentadecyl-4-sulfophenoxy) -butyramido7-acetanilide, Sodium salt;

11. 1-Pb.enyl-3-octadecylaInino-4- / 5-pheήyl-5-C1,3,4) -oxadiazolylthio7-5-pyrazolone;

12. 1-14- / Y- (2,4-di-tert-amylphenoxy) butyramido7phenyl} -3-ethoxy-4- (1-phenyl-5-tetrazolylthio) -5-pyrazolone;

13. 1- {4- £ a- (3-pentadecylphenoxy) butyramido7phenyl} -3-ätlioxy-4- (1-plienyl-5-tetrazolylthio) -5-pyrazolone;

14. 1- (2,4,6-Trichlorophenyl) -3- {4- / ä- (2,4-di-tert-amylplienoxy) butyramido / anilino } -4- (T-phenyl-5-tetrazolyltliio) -5-pyrazolone J.

009837/1834

15. 1-phenyl-3-octadecylamino-4- (1-phenyl-5-tetrazolylthio) -5-pyrazolone;

16. 1- / 4- (4-tert-butylp3ienoxy) phenyl7-3-phenyl-4- (1-phenyl- S- tetrazolylthio) -5-pyrazolone;

17. 1- ^ 4- (4-tert.-butylphenoxy) phenyl7-3- / ä- (4-tert.- _ butylphenoxy) propionamido / -4- (5-phenyl-1,3,4-oxadiazolyl-2-tliio) -5-pyrazolone;

18. 1- β- (4-tert-butylphenoxy) pb.enyl.7-3- / a- (4-tert-butylph.enoxy) propionamido / -4- (2-nitropilienylthio) 5-pyrazolone;

19. 1- / 3- (4-tert.-butylphenoxy) phenyl7-3- / α- (4-tert.-butylphenoxy) propionamido / -4- ^ T-t4-methoxyphenyl) -S-tetrazolyltiiio / '- S -pyrazolone;

20. 1- ^ 4-C4-tert-butylpienoxy) phenyl7-3- ^ α-C4-tert-butylphenoxy) propionamido / -4- (2-eenzothiazolylthio) -5-pyrazolone;

. 1- ^ 4 * - (4-tert-butylphenoxy) phenyl7-3- ^ ä- (4-tert-butylphenoxy) propionamide / -4- (2-nitrophenylthio) -5-pyrazolone;

22. 1 - /? - (4-tert-butylphenoxy) plienyl7-3- ^ ö- (tert-butylphenoxy) propionamido / -4- (2-eenzoxazolylthio) -5-pyrazolone;

23. 1- (2,4-Dicliloro-6-methoxyphenyl) -3- ^ ä- (3-pentadecylphenoxy) acetainido7-4- (1-phenyl-5-tetrazolylth.io) -5-pyrazolone; "

24. 1-Phenyl-3-octadecyl-4-C1-pjienyl-5-tetrazolylthio) -5-pyrazolone;

25. 1-phenyl-3 ~ ^ ä- (2,4-di-tert-amylphenoxy) acetamido7-4- (1-phenyl-5-tetrazolylthio) -5-pyrazolone;

26. 1-phenyl-3- ^ Y- (2 _l 4-di-tert-amylphenoxy) butyrainido7-4- (1-phenyl-5-tetrazolylthio) -5-pyrazolone;

27. 1-phenyl-3- (3,5-didodecyloxybenzamido) -4-C2-nitrophenylthio) -5-pyrazolone;

28. 1-Phenyl-3- / α-C2,4-di-tert-amylphenoxy) acetamido7 ~ 4- (2-aminophenylazoxy) -5-pyrazolone;

29. 4-Benzotriazolyl-3-pelltadecyl-1-phenyl-5-pyrazolone;

30. 4-Benzotriazolyl-1- (2,4,6-trichlorophenyl) -3- ^ 3- {a-

(2,4-di-t-amylphenoxy) acetamido} benzamido / -5-pyrazolone;

009837/1834

ORSQfNALlNSPSCTED

31. 4- (5-Methoxy-2-benzotriazolyl) -3-pentadecyl-1-phenyl-5-pyrazolonj

32. 4- (4-carboxy-2-benzotriazolyl) -1- (2,4,6-trichlorophenyl) -3-pentaaecyl-5-pyrazolone;

33. 1-Hydroxy-4- (2-nitrophenylthio) -N- / 6- (2,4-di-tert, -amylphenoxy) butyl7-2-naphthamide;

34. 1-Hydroxy-4- (2-benzothiazolylthio) -N- ^ 6- (2,4-di-tert-araylphenoxy) butyl7-2-naphthamide;

35. 1-Hydroxy-4- (1-plienyl-5-tetrazolylthio) -N- / δ- (2,4-di-tert-amylphenoxy) butyl7-2-naphthamide;

36. 1-Hydroxy-4- (2-benzothiazolylthio) -N-octadecyl-3 ·, 5 · - dicarboxy-2-naphthanilide;

37. 1-Hydroxy-4- (1-phenyl-5-tetrazolylthio) -2'-tetradecyloxy-2-naphthanilide;

38. 1-H ^ droxy-4 - ^ "i- (4-methoxyphenyl) -S-tetrazolylthio? - N- ^ 6- (2,4-di-tert-amylphenoxy) butyl-2-naphthamide 7

39. 1-Hydroxy-4- (5-phenyl-1,3 _> 4 »oxadiazolyl-2» thio) -N- ^ 6- (2 _> 4-di-tert-amylphenoxy) butyl7-2-naphthamide;

40. 5-methoxy-2- / α- (3-n-pentadecylphenoxy) butyramido7-4- (1-phenyl-5-tetrazolylthio) phenol; . 1-Hydroxy-4- (2-amino-4- »methylphenylazoxy-N- ^ δ-C2,4-di-tert-amylphenoxy) butyl7-2» naphthamid5

42. 4- (2-Benzotriazolyl) -2- / 6 - (2 _s 4 »diamylphenoxybutyl] [7-1-hydroxynaphthamide;

43. 1 -Hyd.roxy-4- (6 = "nitro ° 2 =" bensotriazolyl) "° N '° £ 6- ⁱ (2 _i 4" di "t" -amy! Phenoxy) butyl.? " 2 * ¹ ^ ¹ '^

ο 5 »methoxy = 2- / a- (3" pentad © cyl

(5 »chloro-2-denzotriazolyl) pIienol and

45 _β 5y ^ pypyy (6 = chloro-5-methoxy-2 ° bensotriagolyl) phenol

Dia couplers 1 to S ₃ 11 to 27 and 33 to 40 are, for example, from the USA "Paten.tsclirift" 3 227 SS4 known Dia couplers 6, 7 _S 28 and 41 can be produced in each process, such as si® from the USA Patent specification 3,148,062 known siado Di © Coupler

1925353

- 2β -

8 to 10, 29 to 32 and 42 to 45 are known from German patent specification 1,800,420.

Couplers which liberate development inhibitors and which have a monothio radical in the coupling position have proven to be particularly advantageous, ie for example couplers of the formulas I, II and IH ₃ in which Y-, Yp and Y ^ represent monothio radicals. Very particularly advantageous couplers which liberate development inhibitors are those of the formulas I ₃ II and III, in which Y ,, Y “and Y ^. each represent a heterocyclic monothio radical, the heterocyclic radical having 5 to 6 ring atoms, at least one heteroatom consisting of an oxygen, sulfur or nitrogen atom and wherein the heterocyclic ring can have 1 to 4 nitrogen heteroatoms. Such a heterocyclic radical can be, for example, a 5-tetrazolylthio radical.

For the production of the photographic recording materials according to the invention it is preferred to use those couplers _{which release development inhibitors 3} which produce dyes which have practically the same hue as the dyes which are formed from each image-forming coupler.

The development inhibitors or retarders in Freedom-setting couplers are used in such consentrations that the desired widening of the H and D curves in the Area of low contrast, i.e. a curve that is characteristic of a wide, practically applicable exposure range.

The optimum in individual cases concentration of inhibitor development in freedom releasing couplers depends either depend on whether _s adjacent to the less sensitive Silberhalogeniäemulelöxisschicht a no BIM erseugende Silberlialogenidemulsions-

009837/1834

layer is arranged, as well as the characteristics of the Silver halide emulsion layer, the development inhibitor releasing coupler itself, and other variables. It has proven to be useful to achieve favorable results in about 1 to 50 mg of a development inhibitor in Freedom to use coupler office 0.09 m (1 sq.ft.).

If necessary, between the support and the image-recording Silver halide emulsions deposited a non-imaging hydrophilic colloidal silver halide layer will. Advantageously, this non-image-recording silver halide emulsion layer contains silver halide grains, which have an average diameter - from about 0.1 to 1 micron exhibit. Such a relatively fine-grain silver halide emulsion in a layer thickness of about 10 to 40 microns applied to reduce image distortion (image spread).

The use of such layers to reduce image distortion is, for example, from the German patent 1 772 531 and Belgian patent 716 915 known.

Such layers have the puncture of light diffusing Layers. The silver halide of these layers can be removed during the development of such recording materials e.g. with a silver halide solvent, z. B. sodium thiosulfate.

Advantageously, such non-image-forming silicon / overhalide emulsion layers are used free of light diffusing substances, e.g. B. Starch that cannot be easily removed. If necessary, such layers can also be used

009837/1834

Contain bonds that turn the layers into filter layers make, for example dyes that can absorb green and red light, for example. In this way, the Image distortion can be further reduced when using the recording materials become spectrally sensitized and when exposed to light of wavelengths longer than blue light will. Such methods are known from German Patent 1,772,531, for example.

It may be advantageous to use an antihalation layer to be used, preferably on the side of the layer

"carrier on which the imaging silver halide emulsion layers are applied. The antihalation layer is therefore preferably applied on the same side as the emulsion layers, because this is advantageous in this way an additional reduction in image distortion is achieved. Customary starting materials can be used to produce the antihalation layer be used. For example, dyes can be used to produce the antihalation layer, in particular those which absorb light of longer wavelengths or the longest wavelengths compared to those of the emulsion is sensitive. The one used to create the Licnthof protective layers The dyes used should be able to be decolorized during the development process, for example in sulfite solutions. To produce the antihalation layers, for example the dyes known from US Pat. No. 3,282,699 can be used. Colloidal silver can also be used to produce the antihalation layers; H. a dispersion can be used to produce the antihalation layers of neutral (gray) colloidal silver in a suitable colloid, e.g. B. gelatin, use. Particularly suitable are dyes that can be bleached to produce the antihalation layers.

009837/1834

NSPECTED

The emulsion can also azaindenes, ζ. B. as in the United States patent 2,933,388 described, benzothiazolium compounds, such as. B. in U.S. Patent 2,694,716, or thioethers such as described in U.S. Patent 3,046,132.

As a binder for producing the silver halide emulsion layers of the photographic material according to the invention can be conventionally known ones for preparation binders used for photographic recording materials. Gelatin is preferably used. Other suitable binders are known, for example, from column of US Pat. No. 3,039,873. Finally, for For the production of the photographic recording materials according to the invention, such binders can also be used which from US Patents 3,142,568, 3,193,386, 3,062,674 and 3,220,844, including those insoluble in water Polymers of alkyl acrylates and alkyl methacrylates, acrylic acid, sulfoalkyl acrylates, and sulfoalkyl methacrylates.

In the drawing is a photographic recording material shown according to the invention

An unsensitized gelatin-silver bromoiodide emulsion layer 2 is arranged on the layer support 1. On this layer there is a silver halide emulsion layer Z ₆ , namely a panchromatically sensitized gelatin-silver bromoiodide emulsion layer with a color coupler forming an image dye and a coupler which releases a development inhibitor. On the emulsion layer 3 a golatine separating layer 4 is applied on which the panchromatically sensitized Gelatin silver bromoiodide emulsion layer 5 is located, which contains a color coupler forming an image dye. On the enusion layer 5 is

009837/1834

a gelatin coating layer 6.

The following example is intended to illustrate the invention in more detail.

example

A photographic recording material of the structure shown in the drawing was prepared, based on the Layer support 1 was applied:

An unsensitized gelatin-silver brosioiodide emulsion such that on a support area of 0.09 ei (1 sq.ft.) 1000 mg gelatine and 500 mg silver were used; a panchroma = table sensitized gelatine-silfoerbromojodideBUilsion in such a way, that accounted for a support area of 0.09 m (1 sq.ft.); 263 mg gelatin, 60 mg of a blue-green color pen, 12 mg a coupler releasing a development inhibitor and 200 mg of silver; a gelatin separating layer with S 2 mg gelatin

2
per 0.09 ni support area; a panchromatically sensitized gelatin-silver bromoiodide emulsion, in such a way that 300 mg of gelatin _s 22 mg of a blue-green dye-forming coupler and 200 mg of silver were applied to a carrier area of 0.09 m, and also a gelatin solution such that a carrier area of 0.09 m 8 2 mg gelatine were omitted »

As a cyan image dye forming color coupler, the coupler 1-hydroxy-2- ^ ~ 8 (2 ' ₈ 4 * -di-tert _e- amy! Phenoxy) -N-butylJ * naphthamide was used.

As a development inhibitor releasing coupler became 1-hydroxy-4 - (1-phenyl-5-tetrazolylthio) "2 £" A "(2,4-di-tert-amylphenoxy) -N-butyl / naphthamide used.

009837/1834

ORIGINAL INSPECTED

ia25359

- 51 -

The layer 5, dl ·. H. the panchromatically sensitized gelatine Silver bromoiodide emulsion cliff with a blue-green color The dye-forming coupler consisted of a highly sensitive one negative silver bromoiodide emulsion (silver bromojadide in the ratio 94: 6). The one used in the layer, a cyan image dye supplying coupler is from the United States patent 2,474,293 known.

Layer 4, i.e. h «the gelatine intermediate layer had the task of prevent dye staining or contamination by migration of oxidized developer.

Layer 3 consisted of a panchromatically sensitized one negative silver broiaiodide emulsion (silver bromoiodide in the ratio 97: 3) the one sensitivity about 0.6 log E units lower possessed as the silver halide emulsion layer 5. Layer 3 contained the same cyan image dye forming couplers such as layer 5 and, in addition, a coupler which, as a development inhibitor, is a mercaptan in freedom sat. This coupler corresponds to compound no. 11 of US Pat. U.S. Patent 3,227,554.

Layer 2, i.e. H. the non-sensitized, non-image-forming Silver bromoiodide emulsion-proof (silver bromoiodide in ratio 94: 6) had silver calogenide grains whose I grain diameter below 1 micron. An emulsion which can be used to prepare such a layer is, for example, from German Patent 1,772,531 known.

The recording material was used for 1/5 second in a conventional Sensitometer exposed and for 15 minutes in usual Developed with a primary aromatic amine color developing agent. The color development was carried out as in Example 1 of the Canadian patent 7 26 137.

009837/1834

The developed recording material had a 5 log E exposure latitude and resulted in very little image distortion.

The recording material could be used to record strong, bright images with low contrast and weak images as well high contrast.

The recording material is suitable, for example, for direct Record and identify the incidents that occur when a satellite enters the earth's atmosphere from its orbit * and burns out.

Another recording material was used for comparison purposes of the type described, except that none release a development inhibitor Coupler was used. It turned out to be an undesirable one Increase in the contrast of the strong, light image areas and that the exposure latitude of the more sensitive emulsion layer was too low. Furthermore, it was found that the recording produced by the bright picture object obscured the recording, which was generated by a sharp picture object, namely in close geometric proximity to the bright image.

009837/1834

Claims (1)

Patent claims 1. Photographis this recording material consisting of a Layer support and at least two color coupler-containing silver halide emulsion layers applied thereon (A) and (B) with different sensitivity, characterized in that that the silver halide emulsion layer (A) 1. A non-diffusing, image dye-forming dye Color coupler and 2. a development inhibitor liberating coupler and that the silver halide emulsion layer (B) contains a non-diffusing image dye forming color coupler and to the silver halide emulsion layer (A) the has greater effective sensitivity » 2. Photographic recording material according to claim 1, characterized in that the in the silver halide emulsion layers containing couplers correspond to the following structural formulas: 0 ii i. I I RJ - C - C - YJ ₈ ^X 1 C- I »^ y ₇ 0 · and / or 009837/1834 III. wherein ^R 1 for known open chain ketomethylene couplers, 5-pyrazolone couplers or phenolic couplers are the usual radicals and Y ₁ , Y ₉ and Y- to complete a coupler providing an image dye each (a) a hydrogen atom or (b) a customary colorless radical which decouples in the coupling reaction or ( c) to complete a development inhibitor-releasing coupler, a colorless residue completing a development inhibitor-releasing coupler Photographic recording material according to claims 1 to 2, characterized in that the couplers in the silver halide emulsion layers have the following structural formulas correspond: H I ί ' Xi R ₅ -N N »C R, C-C 0 and or Ί3 009837/1834 where mean: R- and R ₁ . . in each case an alkyl or aryl radical or a heterocyclic radical with at least one of an oxygen, sulfur or Hetero atom consisting of nitrogen atom; R, an optionally substituted alkyl, Carbamyl, amino, amido, benzamido or Alkamido radical; R-Q and R-- each a hydrogen or halogen atom, an alkyl or aryl radical or a heterocyclic radical with at least one of an oxygen, sulfur or nitrogen atom consisting of a heteroatom or an amino, Carbonamido, sulfonamido, sulfamyl, Carbamyl or alkoxy radical; Pv ₁₂ and R ₁₃ individually each one of the for R- _Q and R-- specified radicals or atoms or together to complete an optionally sub-situated benzo radicals required Atoms; X- is a cyano- or optionally substituted ter carbamyl radical and Y-, Y ₂ and Y- each to complete an image dye-forming coupler (a) hydrogen or (b) halogen or thiocyano, acyloxy, aryloxy or cyclooxy, with the proviso that if R- ₂ and R -, the 0 9837V183A to complete a benzo residue represent required atoms, Y_ cannot be an aryloxy radical, but additionally can have the meaning of a cycloimido radical or (c) to complete a a development inhibitor • liberating coupler one o-amino-substituted each Arylmonothio, an o-nitro-substituted arylmonothio or a heterocyclic radical with at least one of an oxygen, Existing sulfur or nitrogen tomes Heteroatom. 4. Photographic recording material according to Claims 1 to 3, characterized in that the couplers which are contained in the silver halide emulsion layers and which liberate a development inhibitor correspond to the stated formulas I, II and / or III, heterocyclic _{ones in Y, Y 2 and Y} Are monothio radicals with 1 to 4 nitrogen atoms. 5. Photographic recording material according to claim 4, characterized in that the couplers which are contained in the silver halide emulsion layers and which release a development inhibitor correspond to the stated formulas I, II and / or III, in which Y-, Y ₂ and Y are each a 2-nitrophenylthio -, 2-aminophenylthio, 5-tetrazolylthio, 2-benzothiazolylthio or 5-phenyl-1,3,4-oxadiazolylthio radical. .6. Photographic recording material according to Claims 1 to 5, characterized in that the effective sensitivity of the silver halide emulsion layer (B) is about 0.6 to 1.2 log E greater than the sensitivity of Silver halide emulsion layer (A). 009837/1834 7. Photographic recording material according to Claims 1 to 6, characterized in that between the layer support and a non-image recording emulsion layer (C) is arranged on the silver halide emulsion layers, which contains silver halide grains an average diameter of less than 1 micron. 8. Photographic recording material according to claim 7, characterized in that the strength of the between the Support and layer (C) disposed on the silver halide emulsion layers is about 10 to 40 microns. 9. Photographic recording material according to claims 7 and 8, characterized in that the layer (C) consists of a non-sensitized gelatin-silver halide emulsion layer, preferably gelatin-silver bromoiodide emulsion layer, whose silver halide grains have an average grain diameter of about 0.1 to 1 micron. 10. Photographic recording material according to Claims 1 to 9, characterized in that the silver halide emulsion layers (A) and (B) of panchromatically sensitized gelatin-silver bromoiodide emulsion layers exist. 11. Photographic recording material according to claims 1 to 10, characterized in that the layer support and Silver halide emulsion layers (A) and (B) through a Antihalation layers are separated from each other. 009837/1834 12. Photographic recording material according to claims 1 to 11, characterized in that the silver halide ^{emulsion layer (A) as a blue-green dye image-forming coupler 1-hydroxy-2- ^ δ (2 ', 4 l} -di-tert-amylphenoxy) -N- butyl7-naphthamide and, as a development inhibitor, contains 1-hydroxy-4- (1 »phenyl-5-tetrazolylthio) -2- ^ Ä- (2,4-di-tert-amylphenoxy) <N-butyl7naphthamide, 13. Photographic recording material according to claims 1 to 12, characterized in that the silver halide emulsion layer (B) as a bluish-preared dye image-forming coupler 1-hydroxy-2- ^ ~ 5 (2 ¹ , 4'-di-tert-amylphenoxy) -N -butyl7naphthamide contains. 009837/1834