DE2532926A1 - DEVELOPMENT INHIBITORS PURPLE COUPLERS, COLOR PHOTOGRAPHIC RECORDING MATERIALS AND COLOR PHOTOGRAPHIC PROCESSES CONTAINING THESE COUPLERS - Google Patents

Description

splitting purple couplers that do so Color photographic recording materials containing Kupplec and color photograpliisclies process

The invention relates to development inhibitors Magenta couplers, color photographs containing these couplers On drawing materials and a color photo graphic process where these magenta couplers are used.

It is known that color images are formed when color couplers react with the oxidation product of an aromatic primary atom developer. US Pat Color reproduction that improve the grain and sharpness of color photographs. US Pat. No. 3,227,554 describes couplers which release a mercaptan as a development inhibitor. The specified Purpv.rkuppler are ^ -ΈγνζίΖοΙοΏο , which have a Konothio group in the 4 - position to which an alkyl, aryl or

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heterocyclic radical is bonded. These purple couplers have however, the disadvantage that they have low coupling activity, only extremely little activity as a development inhibitor Couplers which split off develop and are so unstable that they can only be used with difficulty in color photographic recording material ien can be incorporated and cannot be used in treatment baths.

U.S. Patent 3,615,506 discloses 3-cycloamino-4-organomonothio-5 ~ pyrazolone couplers are described as having some of these deficiencies are fixed. However, these couplers still have unsatisfactory coupling activity and stability.

The object of the invention is therefore to find new development inhibitors to create cleaving magenta couplers which have high coupling activity and good stability and which are suitable for subtractive color photographic recording methods are suitable «. Another object of the invention is to provide a color photographic recording method in which the silver halide emulsion is developed in the presence of the novel magenta coupler so that color images with excellent color reproduction, Grain and sharpness arise. Finally, it is the object of the invention to provide color photographic recording materials which have a silver halide emulsion layer containing the novel magenta coupler.

The invention relates to new development inhibitors Purple coupler of the general formula (I)

H - C - .CH - S - H ₁₁ (D

Il

Ή V.

i.

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in which R _x and Rp are alkyl radicals, R ^ is a hydrogen atom or an alkyl, aryl or heterocyclic radical and. R. represents an alkyl, aryl or heterocyclic radical.

The invention also relates to a color photograph Silver halide recording material on a support has at least one silver halide emulsion layer containing one or more couplers, at least of which one is a magenta coupler of the general formula (I) which in the oxidative coupling with an aromatic primary ?! Amine-developing releases a development inhibitor.

The invention also relates to a color photographic A recording process which is characterized in that an image-wise exposed silver halide emulsion layer is used with an aromatic primary amine builder in the presence of a purple coupler of the general formula (I) developed «

In a special embodiment of the method according to the invention the image-wise exposed silver halide emulsion layer is developed in an alkaline color developer which an aromatic primary amine developer and a color coupler represented by the general formula (I).

The layer structure of the recording materials from Examples 1 and 2 is shown schematically in FIGS.

Suitable alkyl radicals R ^, R ^, R * and R ^, in general Formula (I) contain, for example, 1 to 25 carbon atoms. Specific Examples are unsubstituted alkyl radicals, such as the ethyl, butyl, 2-ethylhexyl or octadecyl groups, and substituted ones Alkyl radicals. Examples of suitable substituents are aryl radicals, such as the phenyl, tolyl or uaphthyl group, alkoxy radicals, such as

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the ethoxy or hexyloxy group, aryloxy radicals, such as the phenoxy, Tolyloxy or faphthoxy group, alkoxycarbonyl radicals such as the Methoxycarbonyl or butoxycarbonyl group, acylamino radicals, such as the acetylamino or butyrylamino group, carboxyl radicals, Carbamoyl radicals, such as the methylcarbamoyl or butylcarbamoyl group, Sulfamoyl radicals, such as the methylsulfamoyl or butylsulfamoyl group, Cyano groups or halogen atoms, such as the chlorine or bromine atom.

Suitable aryl radicals E, and B ^ are, for example, unsubstituted aryl radicals, like the phenyl or naphthyl group, and one or more times substituted aryl radicals. Examples of suitable substituents are alkyl radicals, such as the methyl or butyl group, Aryl radicals, such as the phenyl, tolyl or naphthyl group, alkoxy radicals, like the Ä * tho: xy or hexyloxy group, aryloxy radicals, like the phenoxy, tolyoxy or haphthoxy group, alkoxycarbonyl radicals, such as the methoxycarbonyl or butoxycarbonyl group, acylamino radicals such as the acetylamino or butyrylamino group, Sulfonamido radicals, such as the methylsulfonamido or butylsulfonamido group, Carboxyl radicals, carbamoyl radicals, such as the methylcarbamoyl or butylcarbamoyl group, sulfamoyl groups such as the Methylsulf amoyl or butyl sulf amoyl group, cyano or nitro groups or halogen atoms such as the chlorine or bromine atom.

The heterocyclic Eest E, is about a single carbon atom to the nitrogen atom in the 1-position of the pyrazolone ring bound. Suitable heterocyclic bests include, for example, heterocycles with one or more nitrogen, sulfur and / or Oxygen atoms, which are optionally condensed with a further input, such as the pyrimidinyl, acridinyl, thiazolyl, Benzothiazolyl, piperidinyl, quinolinyl, thiazolyl or tri azoIyIgroup e.

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The heterocyclic radical H. is bonded to the sulfur atom in the 4-position of the pyrazolone ring via a ring carbon atom. Examples of suitable heterocyclic groups are heterocycles with one or more nitrogen, sulfur and / or oxygen atoms, which may have a fused-on input, for example tetrazolyl radicals, v / ie the 1-phenyltetrazol-5-yl group, thiazolyl radicals, such as the 3-Ga Nitrophenyl) -4-phenyl-1,2,4-triazol-5-yl or 3-methyl-4-phenyl-1,2,4-triazol-5-yl group, thiadiazolyl radicals such as 5-methylthio-1 , 3j4-thiadiazol-2-yl group, pyrimidinyl radicals,% -iie the 3-amino-3,6-dihydro-4,6, e-trimethylpyrimidin ^ -yl- or 3 »6-dihydro-4,6,6- trimethylpyrimidin-2-yl group, thiadiazinyl radicals such as the 6-garboxy-5-pb.enyl-1,3,4-thiadiazin-2-yl group, oxadiazolyl radicals such as the 2-phenyl-1,3j4-oxadiaz; ol-5- yl, Oxazolinylreste, v, ie the 4,5-Hihydro-5-iaethyl-oxazolin-2-ylgx''uppe, imidazolyl, such as the 4 _s 5-dihydroimidazolin-2-yl or 2-4-0xoimidazolin-yl group, Thiazolinyl residues such as the 4,5-dihydrothiazolin-2-yl group, pyridazinyl residues such as the 6-chloropyridazin-3-yl group, triazinylres te, such as the 5-hydroxy-6-methyl-'1,2,4-triazin-3-yl group, oxazolyl groups such as the benzoxazol-2-yl group, and thiazolyl groups such as the benzothiazol-2-yl group.

The purple couplers of the general formula (I) include couplers of the general formulas (II) and (III) particularly preferred:

N-Ii

Ή - Ή

N-C-CH-S-C

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N-E

ρ - gh -SC C- SCH ₃ (in)

Ή C = O

where E., Ep and E, have the preceding meanings. Specific examples of purple couplers according to the invention are:

Coupler (1) 1- {4 - ^ - (2, AI> i-tert-amylphenoxy) -butyramido7-phenylj - 3- (din ~ butylamino) - ^z 1- (1 ~ phenyl-5-tetrazolylthio) ~ 5-pyrazolone

Coupler (2) 1 ~ Benzyl-5- (di-n-hexylamino) -4- (i-phenyl-5-tetrazolylthio) -5-pyrazolone

Coupler (3) Λ - \} \ - / 5ί- (2,4-di-tert-amylphenoxy) -butyramide ^ / ~ phenyl3 -5 ~ (din-benzylamino) -4- ( ^/ l-phenyl-5 -tetrazolylthio) -5 ~ pyrazolone

Kupp ler (4) 1-phenyl-5-bis- (2-ethylhexyl) amino-4- (1-phenyl-5-hl tetrazolyrt ο) - 5-py3 "a ζ ο 3 on.

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Coupler (5) 1- (4-chlorophenyl) -3- (di-n-hexylamino) ~ 4- (1-phenyl-5 ™ tetrazolylthio) -5-pyrazolone

Coupler (6) 1- ( 2,4,6-Tricloroplienyl) -3- (di-n-octylamino) -4- (2-carl3OxyphenyltMo) -5-pyrazolone

Coupler (7) 1- (2,4-Dimethyl-6 ~ c3alorplienyl) ~ 3 «(di-n-TDutylamino) n-hexadecylcarbamoyl) -phenyltliio / -5-pyrazole

Coupler (8) 1 - (2,4,6-trichlorophenyl) - 3- (di -n -liexyl amino) -4- (1-phenyl-5-tetrazolylthio) -5-pyrazolone

Coupler (9) Λ - (2,6-Diclilor-4-tet radecyloxycarbonylphenyl) ~ 3- (K-ethyl-N-benzylamino) -4- (2-ethoxycarbonylphenyltliio) -5-pyrazolone

Coupler (10) 1- ^ A-If- (2 _} 4-Di-tert-amylplienoxy) -butyraiiiido7-plienylj ätb.yl-li-n-butylaniino) -4- (1 ~ plienyl-5-tetrazolyltMo) - 5-pyrazo

Coupler (ΛΛ) 1-Benzyl-3- (H-metliyl-li-ii-octadecylaiiiino) -4- (2-carbo25rpb.enyl t3aio) -5-pyrazolone

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_ ₈ _ 253292b

Coupler (12) 1- (2,4,6-Tri octadecylcarbamoyl) -phenylthijg7-5-pyrazolone

Coupler (15) 1- (4-n-tetradecyloxycarbonylphenyl) -3- (di-benzylamino (i-phenyl-5-tetrazolylthio) -5-pyrazolone

Coupler

1- ί4- / 6: - (2,4-Di-tert-amylphenoxy) -butyramido7-phenylj- -3- (di-n-butylamino) -4- (4-nitrophenylthio) -5-pyrazolone

Coupler (15) 1- ί4 - ^: - (2,4-Di-tert-amylpb.enoxy) -butyramido-7-phenylj - 3- (di-n-butylamino) -4- / 5-methyltliio-2 - (i, 3,4) -thiadi 5-pyrazolone

Coupler (16) 1-i4 - / ^ - (3-n-Pentadecylpb.enoxy) -butyramido7-phenyl? -3- (diii-butylamiiio) -4- (1-plienyl-5-th "trazolyltliio) -5-pyrazolone.

The couplers of the invention can generally be worked out manufacture in the following way:

3,3-diethoxyacrylic acid ethyl ester becomes approximately equimolar Amount added in the absence of a solvent to a secondary amine and mixed, e.g. an amine of the formula: E ^, - ^

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in which R, - and Rp have the above meaning. The resulting mixture is then stirred for about 15 hours at about ⁰ C to 140 1JO. The resulting 3- (disubstituted) -Aßiino-3-ethoxyacrylic acid ethyl ester is added to an approximately equimolar amount of a monosubstituted hydrazine in ethanol and refluxed. An alcoholate is then added and the mixture is refluxed further. A pyrazolone derivative is obtained by acidifying the reaction solution. If the pyrazolone derivative has a nitro group, a pyrazolone derivative with an amino group is obtained by reduction with hydrogen in the presence of a Pd-C catalyst. The pyrazolone derivative having an amino group is then condensed with an acid chloride having a ballast group in acetonitrile with heating, a pyrazolone having a ballast group being formed. This is reacted with Räumtemperatur (about 20 to 30 ⁰ C) in chloroform with a sulfenyl chloride, wherein a coupler is formed with a thio group at the 4-position of pyrazolone.

Suitable methods for making typical inventive Couplers are illustrated in the following examples. All parts, percentages and ratios relate to the weight> unless otherwise stated.

MANUFACTURING EXAMPLE 1

Preparation of 1- £ 4- / R- (2,4-di-tert-amylphenoxy) -butyramiäo7-pheiiylV-3- (di-n-butylarßino) -4- (1- phenyl-5-tetrazolylthio) -5 - pyrazolone (coupler (1))

(1) Preparation of 1-H - / ^ (2,4-Di-tert-amylphenoxy) -butyraraido7-phenyl ^ -3- (di-n-butylamino ) -. 5-pyrazolone:

70 g of 3-dibutylamino-3-ethoxyacrylic acid ethyl ester, which is obtained by reacting 3 ₅ 3- ^ iethoxyacrylic acid ethyl ester with di-n-butylarin

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according to the process of GB-PS 1 129 333 and 41 g of p-nitrophenylhydrazine are dissolved in 100 ml of acetic acid and then ^{stirred for 1 hour at room temperature (about 20 to 30 °} C.). The deposited crystals are filtered off and washed with methanol to obtain 36 g of 1- (4-nitrophenyl) -3-OE.I-nbutylamino) -5-pyrazolone, S ¹ · 146-147 ° C, was obtained.

10.2 of this nitro compound and 10 g of reduced iron are added to 200 ml of acetic acid and ^{stirred at 90 °} C. under a stream of nitrogen. After the reaction has ended, the reaction solution is cooled to room temperature, 2.7 g of sodium acetate and 11 g of dL- (2,4-di-tert-amylphenoxy) butyryl chloride are added and the mixture is finally stirred for 30 minutes at room temperature under a stream of nitrogen. The reaction solution is then poured into water and the oil obtained is extracted with ethyl acetate. After the material has been washed with water, the solvent is distilled off. The residue is recrystallized from methanol, 11 g of 1 ~ 4 ~ / ^ (2,4-di-tert.-amylpheno: ^) - butyramidi> / - phenyl ^ 3- (di-n-butylamino) -5 ~ pyrazolone, 1. 110 to 111 C, can be obtained in the form of white needle-shaped crystals.

(2) Production of 1 - ^ - ^ oG- (2,4-Di ~ tert.-amylpheno3cy) -butyramid67-phenyls ~ 3- (di-n-butylamino) -4 ~ (1-phenyl-5-tetrazolylthio) -5-pyrazolone:

A sulfenyl chloride solution prepared by the method of U.S. Pat 3,615,506 by introducing chlorine gas into 50 nil of a carbon tetrachloride A solution of 1.78 g of 1-phenyl-2-tetrazoline-5-thione is obtained in 50 ml of a chloroform solution of 6.04 g of 1-J4- / X- (2,4-di-tert-araylphenoxy) -butyrami.do7-ph.enylj ■ 3- (di-n ~ butylamino) -5-pyrazolone, which has been prepared by the method of step (1) ^ poured and added for 30 minutes Room temperature stirred. After distilling off the solution

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by means of the residue is recrystallized from methanol, 3.5 g of 1 ™ _? '4- ^ L- (2,4-M-tert-amylphenoxy) -butyramido7-phenyl ^ -3- (di-n-butylamino) -4- (1-phenyl ~ 5-tetrazolylthio) -5-pyrazolone, M.p. 197 to 198 ° C.

Hep s tellimgo example 2

Preparation of 1-benzyl-3- (di-n-hexylamino) -4- (1-phenyl) -5-tetrazolylthio) -5-pyrazolone (Coupler 2)

(1) Preparation of 1-Benzyl-3- (di-n-hexylamino) ~ 5-pyrazolone:

A mixture of 17 g of 3-I ⁾ yn-hexylamino-3-ethoxyacrylic acid ether, which has been obtained by the process of Preparation Example 1, and 5 g of benzylhydrazine is stirred for 3 hours with heating at 120.degree. A solution which has been prepared by dissolving 7 g of sodium ethylate in 50 ml of ethanol is then added, and the mixture is boiled for 30 minutes under kick flow. After cooling, the solution is acidified with acetic acid and poured into water, an oil separating out. The oil is extracted with ethyl acetate, the extract is washed with water and the solvent is distilled off. The residue is recrystallized from η-hexane, F. be obtained from 59 to 60 ⁰ C, in the form of white crystals nadelföriniger 10 g of 1-benzyl-3- (di-nhexylamino) -5-pyrazolone.

(2) Preparation of 1-Benzyl-3- (di-n-hexylamino) -4- (1-phenyl-5-tetrazolylthio) -5-pyrazolone:

The 1-benzyl-3- (di-n-hexylamino) -5-pyrazolone obtained above is converted to 1-benzyl- 3- (di-n-hexylamino) -4- (1-phenyl-5-tetrazlolylthio) -5-pyrazolone, Έ. 68 to 73 ° E.

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The couplers of the present invention can be used in various ways be incorporated into photographic emulsions. Typical suitable procedures are summarized below:

(a) The coupler is dissolved in a water-slightly miscible organic solvent having a high boiling point (above about 200 ⁰ C), followed by emulsifying the coupler solution in an aqueous medium or dispersed and the dispersion of the emulsion is added "Suitable organic solvents for this Processes are, for example, dibutyl phthalate, tricresyl phosphate, H, H-diethylcaproic acid amide, pn-nonylphenol and 2-methyl-4-noctylphenol.

(b) The coupler is dissolved in a low-boiling solvent which is relatively difficult to mix with water the coupler solution is emulsified or dispersed in an aqueous medium and the dispersion then the photographic emulsion clogs. The organic solvent is separated off during the manufacturing steps of the recording material. as Solvents for this process are e.g. ethyl acetate, cyclohexanone and ß-butylethoxyethyl acetate.

(c) The coupler is dissolved in an organic solvent which is readily miscible with water, and the resulting solution is then added to the photographic emulsion, so that the coupler is dispersed in the form of fine colloidal particles. The solvent can either be removed during the production of the recording material or it can remain in the emulsion layer. Examples of suitable solvents for this process are dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, glycerol and tetrahydrofuran. _:

The degree of dispersion of the coupler can thereby be improved

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that one used those in methods (a), (b) and (c) Solvent depending on the solubility of the coupler mixed together.

Conventional anionic surface-active surfactants, for example, can be used as dispersants Agents, such as sodium alkylbenzenesulfonates, Sodium dioctyl sulfosuccinate, sodium dodecyl sulfonate, sodium alkylnaphthalene sulfonate and Fischer couplers, amphoteric surfactants such as IT ~ tetradodecyl-N, E ~ dipoly ~ ethylene, ε-betaine, and nonionic surface-active gowns, such as sorbitan monolaurate can be used.

The couplers according to the invention can either be used in the emulsion layer be incorporated individually or in combination with other couplers customary in color photography. If the fiction according to the coupler are used in combination with a known coupler, the addition is made separately or mixed dispersions or in the form of a single dispersion. The coupler of the present invention is used in an amount from about 0.01 to 100 mole percent, preferably 0.5 to 20 Mole percent based on the total amount of couplers in the layer. Applied.

The couplers of the present invention may of course be green-sensitive Silver halide emulsion layer is added; however, they are also useful as color correction couplers in red-sensitive or green-sensitive silver halide emulsion layers, improving color reproduction; see JA-OS 50 O5I / 73.

In multilayer color photographic materials that are in a light-sensitive unit have two or more emulsion layers (JA-OS 50 051/73) can be according to the invention

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Coupler of a single or also two or more silver halide emulsion layers added to the photosensitive unit.

The color photographic recording materials of the invention In addition to the magenta couplers according to the invention, they may contain other couplers customary in color photography. For this Couplers of the general formulas (A), (B), (C) and (D) are particularly suitable:

- C - CH

in the H ₁ - an alkyl radical, for example a primary, secondary or tertiary alkyl radical, such as methyl, propyl, n-butyl, tert-butyl, hexyl, 2-hydroxyethyl, 2-phenylethyl or Pentadecyl group, an aryl radical such as the phenyl or 2,4-di-tert-amylphenyl group, an alkoxy radical such as the methoxy, itoxy or benzyloxy group, an aryloxy radical such as the phenoxy group, a heterocyclic radical, v / ie the quinolinyl -, pyridyl, benzofuranyl or oxa ζ ο IyI group, an amino radical, such as the methylandno, diethylamino, phenylamino, tolylamino, 4- (3 ~ sulfobenzamino) -anilino-, 2-chloro-5-acylaminoanilino -, 2-chloro-5-alkoxycarbonylanilino or 2-trifluoromethylphenylamino group, an amido group, for example an alkylcarbainido group, such as the ethylcarbamido group, an arylcarbamido group, vn.e the phenylcarbaiaido group, a heterocyclic carbonamido group,

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like the benzothiazolylcarbuciido group, a sulfainido radical, like the phenylsulfamido group, a heterocyclic sulfamido group, such as the pyridinylsulfamido group, an ureido group, e.g., an alkylureido group such as the a'tbylureido group, a Arylui ^ eido radical, such as the phenylureido group, or a heterocyclic Ureido radical, like the pyridinylureido group, means

Eg an aryl radical, for example ITaphthyl, phenyl, 2,4,6-trichlorophenyl, 2-chloro-4,6-dimethylphenyl, 2,6-dichloro-4- methoxyphenyl, 4-methylphenyl, 4-acylaminophenyl, 4-alkylaminophenyl, 4-trifluorinethylphenyl or 3 »5-dibroirvphenyl group, a heterocyclic group, for example a benzofuranyl, benzothiazolyl or quinolinyl group, or an alkyl radical, 2.B. a methyl, ethyl, tert-butyl or benzyl group, and Z * denotes a hydrogen atom or a group which can be split off during color development, for example a thiocyanate group, an acyloxy group such as the benzoyloxy group, an aryloxy group, v / ie the Phenoxy group, an alkoxy group such as the benzyloxy group, an alkoxycarbonyloyry group such as the benzyloxycarbonyloxy group, an aryloxycarbonyloxy group such as the phenoxycarbonyloxy group, a disubstituted amino group such as the piperidinyl group, an arylazidyl group such as the pyrlazozo group, or a heteroazo group such as the naphthyloxy group; See e.g. US-P3en 3 ^ 19 39 ^ i 3 252 924 ·, 3 311 4-76 and 3 227 550 and JA-OSen 4-1 869/73 and 56 050/73.

- CO - CH - CO - HH - E ₈ (B)

^Z 2

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in which E _{7 is} an alkyl radical, for example a primary, secondary or tertiary alkyl radical, such as the tert-butyl, 1,1-dimethylpropyl or 1,1-Mmethyl ~ 1-methoxyphenoxymethyl group> or an aryl radical, for example a phenyl or Alkylphenyl radical, such as the 2-methylphenyl or 3-octadecylphenyl group, an alkoxyphenyl radical such as the 2-methoxyphenyl or 4-methoxyphenyl group, a halophenyl, 2-chloro-5-alkylcarbamidophenyl, 2-chloro ~ 5 - ^ - ( 2, ^z t ~ di-tert-amylphenoxy) -butyramido / -phenyl, 2-metho3iy-5-alkylamidophenyl or 2-chloro-5-sulfamidophenyl group, Bg denotes a phenyl radical, for example a 2-chloro-phenyl -, 2-IIalogen-5-alkylamidophenyl-, 2-chloro-5- / £ \ - (2,4 ~ di-tert-amylphenoxy) -acetamido7-plienyl-, 2-chloro-5- ( ^/ t ~ methylphenylsulfamido) - phenyl or 2 ~ methoxy-5- (2,4 ~ di-tert, -amylphenoxy) -acetamidophenyl group, and Zp denotes a hydrogen atom or a group that can be split off during color development, in particular a fluorine atom, an acyloxy radical, such as the benzoyloxy group Arylo xy radical, such as the phenoxy group, a heteroaromatic carbonyloxy radical, such as the furancarbonyloxy group, a sulfimido radical such as the saccharine group, an alkylsulfoxy radical such as the methylsulfoxy group, an arylsulfoxy radical such as the phenylsulfoxy group, a phthalimido or dioxazoimidinyl, dioxazolide or dioxazoimidinyl Dioxomorpholine residue; See e.g. US-PS 3,227,550, 3,253,924, 3,277,155, 3,265,506, 3,4-08,194 and 3,415,652, FE-PS 1,411,384, GB-PS 944 49Ο, 1,040,710 and 1 118 028, DT-OSen 2 057 941, 2 163 812, 2 213 461, 2 219 917 and the JA-OS 54 456 / 73-

OH

(C)

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(D)

in which Rq represents a substituent customary in cyan couplers, for example a carbamyl radical, for example an alkylcarbamyl radical such as the methylcarbamyl group, an arylcarbamyl radical such as the phenyl carbamyl group, a heterocyclic carbamyl radical such as the benzothiazolylcarbainyl radical, for example an alkylsulfamyl radical such as the sulfamyl radical Methylsulfaniyl group, an arylsulfamyl group, such as the phenylsulfamyl group, or a heterocyclic sulfamyl group, such as the pyridinylsulfamyl group, an alkyloxycarbonyl group, such as the tetradecyloxycarbonyl group, or an aryloxycarbonyl group, such as the phenoxycarbonyl group, R ^ q an alkyl group, such as the phenoxycarbonyl group , a heterocyclic radical, such as the furanyl group, an amino radical, a carbamido radical, for example an alkylcarbamido radical, such as the dodecylcarbamido group, an arylcarbamido radical, such as the phenylcarbamido group, a sulfonamido, sulfamyl or carbamyl radical, R / j ^{<j R ^ j2} i R ^ i -ζ the f have the meaning given for Ro and can also represent a halogen atom, e.g. a chlorine atom, or an alkoxy radical, e.g. a methoxy group, and Z, a hydrogen atom or a group which can be split off during the development of the color, e.g. a halogen atom, e.g. a chlorine or iodine atom, a Thi ο cyano group, a cycloimido radical, e.g. a malcinimido. Succinimido or 1,2-dicarboxyimido group, one

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Amylazo radical, e.g. a Phenylaz o group, or a heterocyclic one Azo radical, e.g., a pyridinylazo group.

To make the couplers diffusion-resistant, a hydrophobic residue with 8 "to 52 carbon atoms is incorporated into the coupler molecule introduced. This remainder, known as the ballast group, is either directly or e.g. via an imino, ether, carbonamido, sulfonamido, ureido, ester, imido, carbamoyl or sulfamoyl linkage attached to the coupler molecular structure.

Special examples for suitable ballast groups are listed below:

(1) alkyl and alkenyl groups:

e.g. -CH ₂ -CH- (C ₂ H ₅ ) ₂ , -C ₁₂ H ₂₅ , -C ₁₆ H ₃₃ , -C ₁₇ H ₃₃ ,

(2) alkoxyalkyl groups

e.g. -

(JA-AS 27 563/74)

(5) alkylaryl groups:

e.g.

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(IV) alkylaryloxyalkyl groups:

e.g.

^CH 2 °

-co

CH

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E ₁₁ Ct)

E ₁₁

C " π η"

- ⁵ I.

-CHO

Cl

(V) acylamidoalkyl groups:

e.g.

COC

COC

(U.S. Patents 3,337,344 and 3,418,129)

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(VI) alkoxyaryl and aryloxyaryl groups:

e.g.

(VII) residues with long-chain aliphatic groups (e.g. alkyl or alkenyl groups) and hydrophilic residues (e.g. carboxyl or sulfo groups):

e.g.

-CH-CH = CH-C ₁₆ H ₃₃ CH ₂ COOH

-CH-C ₁₆ H ₃₃ SO ₃ H _

(VIII) alkyl radicals substituted with ester groups:

e.g.

_c (η)

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(IX) alkyl groups substituted with aryl or heterocyclic best:

e.g. r -y

COOCH ₅ 0

Il

-CFCH / T \ ^C

H;

(X) Ar-yl groups substituted by aryloxyallcoxycarbonyl radicals: e.g.

CH-,

C H (t)

; / \ Vcoocii co - (/ \\ - c.h (t)

Examples of those in the multilayer color photographic recording materials The materials that can be used in the invention are summarized below:

The following compounds, for example, are suitable as yellow couplers:

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.-amylphenoxy) - "butyraniido 7-benzoyl -2 methoxyacetanilide

-J-Z ^ (2,4-di-tert-aaylphenoxy) -butyramido 7-benzoyl-2-methoxyacetanilide

N- (4-Anisoylacetamidobenzenesulfonyl) -N -benzyl-p -toluidine

<? C ~ Z3 ~ (2,4-Dioxo-5,5-dimethyloxazolidinylI7- <£ -pivaloyl-2-chloro ~ 5-cC- (2,4-di-t ert. -amylphenoxy) -butyramido-acetanilide

dG- (4-carboxyphenoxy) -cGrpivaloyl-2-clilor-5 - /! iC- (2,4-di-tert-amylphenoxy) -butyramiaO7 ~ acetanilide

cG- / 3- (1-Benzyl-2,4-dioxo) -hydantoinyi7-cGrpivaloyl-2-clilor-5 - ^^ (2,4-di-tert-amylphenoxy) -butyramido / -acetanilide

t ert.-amylphenoxy) -butyr ami d_ö7-2-c3al ο r ac e t ani lid

The following compounds, for example, are suitable as purple couplers:

1- (2 _ί 4 _l 6 * · ίEricb.lorphenyl) -3 - /> - (2, ² l - di-tert-amylpheno2ς5Γ-acetamido) -benzamidö7-5-pyrazolone

1- (2 _} 4,6-Trichiorphenyl) -3- (2,4-di-tert-amylphenoxy) -acetamido-4-acetoxy-5-pyrazolone

1- (2,4,6-Trichlorophenyl) -3-tetradecanamido-4- (4-hydroxy ~ phenyl) azo-5-pyi "azolone

1- (2,4,6-Trichlorophenyl) -3-ZT2-chloro-5-tetradecanamido) -aniline p7-3-pyra ζ olon

509886/1167

1- (2,4,6-TrictLloroplie] iyl) ~ 3- (2-chloro-5-tetradecyloxycarbonyl ) ~ anilj no ~ 4- (i-naphthylazo) ~ 5-pyrazolone

1- (2,4 ~ Di-clilor-6 ~ metlioxyphenyl) -4- / 3 [2-chloro-5-tetradecane amido) -anilinö7-4-'beiizyloxycarbonyloxy-5-pyi'azolone

1- (2,4,6-Trichlorophenyl) -3- £ 3-ΖΓ'2,4-di-tert. -amylphenoxy) acetamidJ ^ -benzamidoV - ^ - piperidino-lp-pyrazolone

amylphenoxy) butyramido7-anilino ^ "^ - N-pIitlialimido · -5-pyrazolone

1- (2,4,6-TrictLLoxphenyl) -3- (2-chloro-5-tetradecanamidoanilino-4- (3-methyl-4-hydroxyphenylazo) -5-pyrazolone The following compounds, for example, are suitable as blue-green couplers: 1- Hydroxy-li- _i / ^ - (2,4-di-tert-amylplienoxy) -propyI7-2-naphthamide

1-Hydro2 ^ -4-y / 2- (2-hexyldecyloxycarbonyl) -phenylaz_ö7-2-N - (1-naphthyl) -naphthamide

1-Hydroxy-4-chloro-N- _<! ^ - (2,4-di-tert-amylpheno3qy) -butyl-2-naphthamide

5-methyl-4,6-dic3alor-2 - / ^ £! .- (3-n-pentadecyl phenoxy) butyramido / phenol

i-Hydroxy-4- (2-ethyloxycarbonylphenylazo) -N- (2-ethylamyl) -2-naphthamide

Loved the couplers can use the interlayer color correction Hydroquinones of the general formula (E) can also be used,

509886/1 167

A. ^^ S-Z I. - O I. O A.

(E)

in which A and A ^{1 represent} hydrogen atoms or groups which can be split off with alkalis, e.g. alkoxycarbonyl or acyl radicals, and A ¹ together with E or Q can form an input, e.g. an oxathiol ring, P, Q and E hydrogen atoms, alkyl radicals, e.g. methyl, Ithyl, 1,1,3 · 3-ietramethylbutyl or n-penta ~ decyl groups, aryl radicals, e.g. phenyl or p-tolyl groups, best of the formula: - -SY, in which Y is an alkyl radical, e.g. a 2- Ethylhexyl, n-dodecyl, n-hexadecyl, n-octadecyl, hydroxycarbonylmethyl, ethosycarbonylmethyl or 2-hydroxyethyl group, or an aryl radical, e.g. a phenyl group, hydroxyl groups, halogen atoms, e.g. chlorine atoms, best of the formula: -SZ, alkoxy radicals, aryloxy radicals, for example ethoxy or ethoxy groups or best of the formula: -0-Y, or heterocyclic best, for example benzotriazolyl groups, and Z is a heterocyclic best in the bound state, in particular a tetrazolyl radical, such as a 1-Phenyltetrazolylgruppe, an I'riazolylrest, e.g. a 4-phenyl-1,2,4-triazol-5-yl- ~ or 3-n-pentyl ~ 4-phenyl-

a thiadiazolyl radical, e.g. a 2-

609886/1167

- 26 - 253292t?

Methylthio-1,3,4 ~ thiadiazol-5-yl or 2-amino-1,3> 4-thiadiazol-5-yl group, an oxadiazolyl radical, e.g. a 2-phenyl-1, 3j4-oxadiazol-5-yl group, a tetrazaindenyl radical, e.g. a 6-methyl-1,3, 3a, 7-tetrazainden-4-yl- or G-n-nonyl-1, 3,3a, 7- tetrazainden-4-yl group, an oxazolyl group, e.g. a benzoxazol-2-yl group or a tliiazolyl radical, e.g. a benzothiazol-2-yl group. Of the radicals P, Q and E, R is preferably a radical of the formula: -S-Z. A Ballant group is preferred introduced into the molecular structure in the form of the radicals P, Q or R. Me ballast group used in accordance with the invention ICC hydroquinone derivatives is an aliphatic radical with 8 to etvra 32 carbon atoms, which makes the molecule diffusion-proof «

Specific examples of suitable ICC hydroquinones are: 2-n-Dodecylthio-5- (1'-phenyltetrazole-, 5 '-yl t hi ο) -hydroquinone 2-n ~ octadecylthio-'l - (1 ^l -phenyltetrazole ~ 5-3 ^{r (} l "tliio) -hydroquinone 2-n-hexadecylthio-5- (1'-phenyltetrazol-5-ylthio) -hydroquinone

2- (i ^f -Phenyltetrazol ~ 5 ^! -Ylthio) -3- ~ phonylthio-6- (1 ', 1 ", 3", 3 "-tetramethylbutyl) -hydroquinone

2 ~ n-Hexadecylthio-5- (1 ^l -phenyltetrazole ~ 5 ^l -yl'fc ⁿ i ^o ) ~ 6-phenylthiohydroquinone

2-n-octadecylthio-5- (i ^l -phenyltetrazol-5 -'-ylthio) -6-phenylthiohydroquinone

2-n-Pentadecyl-5- (i 'phenyltetrazol-5'-ylthio) hydroquinone

5098 8 6/1167

2-Z2 ^{T "5-dihydroxy-l} 6 ^l - (1 ^l '-phenyltetrazol-5 ^1' -ylthio) -3 'octadecyTZ-phenylthiobenzoesaureiaethylester

2-ß? ^ '- Dihydroxy-G'-d' · -phenyltetrazol-5'-ylthio) -3 'amyl hexadecylthio7-phenylthiobenzoate

2 ~ (2'-methylthio-1 ^!, 3 ', 4 -'-thiadiazol-5'-ylthio) -6-n-pentadecylhydroquinone

2- (3'-n-Pentyl-4'-phenyl-1 ', 2', 4 -'-triazol ~ 5'-ylthio) -5-hexadecylthiohydroquinone

2- (6'-methyl-1 ', 3', 4a ¹ , 7 ^! -Tetrazainden-4 -'- ylthio) -6- (1 '', 1 · ', 3'',3''- tetramethylbutyl) -hydroquinone

Silver halide emulsions are usually prepared by mixing a solution of a water soluble silver salt such as silver nitrate with a water soluble halide such as potassium bromide in the presence of a water soluble polymer such as gelatin. In addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide, silver iodobromide and silver chloroiodobromide can also be used in accordance with the invention. The silver halide preferably contains about 0.1 to 15 mol percent iodide and preferably has a grain size of about 0.03 to 3 Ά . However, any grain sizes and grain size distributions can be used. The silver halide grains are produced in the usual way, for example by the so-called single-jet, double-jet or controlled double-jet process. Mixtures of two or more separately prepared silver halide emulsions can also be used. The silver halide grains can have a homogeneous crystal structure, a layer structure with different

509886/1167

" ²⁸ " 253292b

interior and exterior areas or a so-called conversion structure (GB-PS 635 841 and US-PS 3,622,318). Silver halide grains containing the latent Form image mainly on the grain surface or mainly inside the grain. These photographic emulsions can be produced in different ways, e.g. by the ammonia, neutral or acid process.

The above-mentioned silver halide emulsions can be based on conventional ones Way to be chemically sensitized. Specific examples of suitable chemical sensitizers are gold compounds, such as chloroaurates and gold trichloride, (US Pat. No. 2,399,083, 2,540,085, 2,597,856 and 2,597,915), precious metal salts, e.g. of platinum, palladium, iridium, rhodium and ruthenium (U.S. Patents 2,448,060, 2,540,086, 2,566,245, 2,566,263, and 2,598,079), Sulfur compounds capable of forming silver sulfide when reacted with a silver salt (US Pat

1 574 944, 2 410 689, 3 189 458 and 3 501 313), tin (II) salts, Amines and other reducing agents such as those described in U.S. Patents

2,487,850, 2,518,698, 2,521,925, 2,521,926, 2,694,637, 2,983,610, and 3,201,254.

Suitable binders for the silver halide grains are, for example, hydrophilic colloids such as gelatin, colloidal albumin, Casein, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, agar, sodium alginate, starch derivatives, synthetic hydrophilic colloids, such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymers and Polyacrylamide and its derivatives and partially hydrolyzed Products. If necessary, a compatible mixture can also be used from these colloids can be applied. Gelatin is the most widely used of the colloids mentioned. The gelatin can be completely or partially replaced by synthetic polymers, so-called gelatin derivatives, which e.g.

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253292b

by reacting or modifying the imino, imino, hydroxyl or imino groups present as functional groups in the gelatin molecule Carboxyl groups have been produced with a compound capable of reacting with these groups, or by grafting Gelatin obtained by grafting another polymer chain onto the gelatin molecule int.

The photographic emulsion can optionally be spectrally sensitized or become hypersensitive. A cyanine dye is used for this, e.g. a cyanine, merocyanine, Carbocyanine or styryl dye individually or in combination. These spectral sensitization methods are known and e.g. U.S. Patents 2,688,545, 2,912,329, 3,397,060, 3,615,635 and 3 628 964, GB-PS 1 195 302, 1 242 588 and 1 293 862, DT-OSen 2 030 326 and 2 121 780 and JA-Aßen 4935/68 and 14 030/69 described. The sensitizers are e.g. sensitizing spectral range and the intended use of the recording materials selected.

Various conventional stabilizers and antifoggants can also be added to the photographic emulsions in order to avoid a reduction in sensitivity or fog formation during manufacture, storage and processing. J ¹ A large number of compounds are known for this purpose, e.g. heterocyclic compounds, mercury compounds, mercapto compounds or metal salts, but in particular 4-hydroxy-6-methyl-1, 3, 3a »7-tetrazaindene, 3-methylbenzothiazole and i-phenyl- 5-mercaptotetrazole.

The photographic emulsions can be hardened in a conventional manner. Examples of suitable hardening agents are Aldehydes such as formaldehyde and glutaraldehyde, ketones such as diacetyl and cyclopentadione, reactive halogen compounds such as

509886/1167

Bis (2-chloroethyl urea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and those in U.S. Patents 3,288,775 and 2,732,313 and GB-PS 974 723 and 1 167 207, divinyl sulfone, 5-acetyl-1,3-diacryloyl-hexahydro-1,3,5-triazine and those in GB-PS 994 869 and US-PS 3,635,718, 3,232,763, 2,732,316, 2,586,168, 3,103,437, 3,017,280,

2 983 611, 2 725 294, 2 725 295, 3 100 704-, 3 091 537,

3,321,313 and 3,543,292.

The photographic emulsions can also contain one or more wetting agents. The wetting agents serve as coating aids, Dispersants, sensitizers, agents for improving photographic properties, antistatic agents or anti-stick agents. Let the wetting agent are divided into natural surface-active substances, such as Saponin, nonionic surfactants such as alkylene oxides, glycerols and glycidols, cationic surfactants Means j such as higher alkyl amines, quaternary ammonium salts, heterocyclic Compounds such as pyridine, or phosphonium or sulfonium compounds, anionic surface-active agents with an acid group, e.g. a carboxylic acid, sulfonic acid, phosphoric acid, sulfuric acid ester or phosphoric acid ester group, and amphoteric surfactants such as amino acids, aminosulfonic acids, sulfuric acid esters or phosphoric acid esters of amino alcohols. Suitable surfactants Agents are, for example, in U.S. Patents 2,271,623, 2,240,472,

2 288 226, 2 739 89I, 3 068 101, 3 158 484, 3 201 253,

3,210,191, 3,294,540, 3,415,649, 3,441,413, 3,442,654. 3,475,174 and 3,545,974, DT-OS 1 942 665 and GB ~ PSen 1,077,317 and 1,198,450.

The color image fading preventing agents are e.g. those in BE-PS 777 487, DT-PS 1 547 684 and DT-OS 2 146 668

509886/1 167

compounds described in U.S. Patents 2,336,327, 2 728 659 and 2 835 579, JA-OS 2128/71 and JA-PA 75 126/73 described phenol and hydroquinone derivatives and their Pre-stages.

The color photographic recording materials of the invention A TJV absorbent can be used in a protective layer, an intermediate layer, an emulsion layer, or a backing layer contained, for example, in U.S. Patents 2,685,512, 2,739,888, 2,784-087, 3,253,921, 3,533,793-, 3,738,837 and 3,754-919 is.

The photographic emulsion can be substantially planar Materials are applied that do not undergo any significant change in dimension during processing. Suitable for this e.g. rigid supports such as glass, metals or ceramics, or flexible supports. The are suitable as flexible carriers materials commonly used in photography, e.g. foils made of cellulose nitrate, cellulose acetate, cellulose acetate butyrate, Cellulose acetate propionate, polystyrene, polyethylene terephthalate or polycarbonate and laminates of these polymers, thin glass films and papers. Also baryta paper and papers that come with a. ^ - Olefin polymers, especially polymers of monomers with 2 to 10 carbon atoms, such as polyethylene, polypropylene or ethylene-butene copolymers, coated or have been laminated, and synthetic resin films, which are used to improve the adhesiveness to other polymers and the printability have been roughened on the surface (JA-AS 19 068/72), can be used with advantage as a carrier v; ground. The silver halide is usually applied in an amount of about 5 ^ 10 to 10 mol / m.

The supports can be used depending on the purpose of the recording materials be transparent or opaque. Colored

509886/1 167

transparent support containing a dye or pigment can also be used. Examples of opaque supports are foils that can be worked into of a dye or a pigment such as titanium dioxide have been made into a transparent film, and surface-treated Synthetic resin films, as described in JA-AS 19 O68 / 72, as well as inherently opaque Materials such as papers. Completely opaque papers and synthetic resin foils that contain, for example, uss or dyes, can also be used. If the adhesion between the support and the photographic layer is unsatisfactory is, an adhesive layer can be applied to the support which is opposite both to the support and to the photographic Layer has good adhesion. The carrier surface can also be e.g. by spray discharge, UY irradiation or flame treatment to improve adhesion.

The color photographic recording materials of the invention are subjected to color processing after exposure. This essentially consists of a color development, a Bleaching stage and a fixing stage. Each stage can be carried out on its own or two or more can be combined Steps to a step, using treatment baths that perform two or more functions accordingly. A An example of such a bath is the bleach-fix bath. Each stage can be carried out in two or more individual steps will. For example, you can carry out a dye development, an initial fixation and a bleach fixation. The color processing can further include, for example, a pre-hardening, a neutralization, a black and white development, a stabilizing treatment and.comprising a washing stage. The processing temperature depends on the particular recording material and the development process used in each case. In general

509886/1167

- 33 - 253292b

if the temperature is above about 18 ^° C., temperatures below about 18 ^° C. can also be used. The temperature is usually in the range from about 20 to 60 ° C., in particular from about 30 to 60 ^° C. The individual stages do not necessarily have to be carried out at the same temperature.

The color developing bath is an alkaline solution with a pH above about 8, preferably 9 to 12, which contains as a developer a compound whose oxidation product in the Reaction with the color coupler gives a colored compound.

Examples of suitable developers are compounds which are capable of developing exposed silver halide and have a primary amino group on an aromatic ring, as well as precursors of such compounds. Preferred examples of developers are 4-amino-N, N-diethylaniline, 3-methyl-4-amino-ΙΤ, ΪΤ-diethylaniline, 4-amino-N-ethyl-N - ^ - hydro27ethylaniline, 3-methyl-4-amino -N-ethyl ~ IT-ß-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-Ji-ß-methanesulfonamidoethylaniline, 4-amino-N, IT-dimethylaniline, 4-amino-3-methoxy-IT, IT diethylaniline, 4-amino-3-methyl-N-ethyl-N-ß-methoxyethylaniline, 4-amino ~ 3-methoxy-M-ethyl-IT-ß-methoxyethylaniline, - 4-amino-3-ß-methanesulfonamidoethyl -N, li-diethylaniline and their salts, for example sulfates, hydrochlorides, sulfites and p-toluenesulfonates. Other developers are described, for example, in US Pat. Nos. 2,193,015 and 2,592,364, JA-OS 64 933/73 and in LPA Mason, Photographic Processing Chemistry, pp. 226 to 229, Focal Press, London (1966). 3-I ^> yi ^> azolidonne can also be used together with these developers.

The color developer bath can optionally contain customary additives. Examples of such additives are alkaline agents

509886/1167

(e.g. hydroxides, carbonates or phosphates of alkali metals or ammonia) pH regulator or buffer (e.g. weak acids such as acetic acid or boric acid, weak bases or their salts), development accelerators (e.g. various pyridinium compounds or cationic compounds as described in U.S. Patents 2,648,604 and 3,671,247, potassium nitrate, sodium nitrate, condensation products of polyethylene glycol and their derivatives, such as those described in U.S. Patents 2,533,990,

2,577,127 and 2,950,970, non-ionic compounds, e.g. those in GB-PS 1 020 033 and 1 020 032 described polythioethers, polymeric compounds with sulfite ester groups, as described, for example, in U.S. Patent 3,068,097, organic amines such as pyridine and ethanolamine, benzyl alcohol or hydrazines), antifoggants (e.g. alkali metal bromides, Alkali metal iodides, nitrobenzimidazoles, such as them are described, for example, in U.S. Patents 2,496,940 and 2,656,271; Mercaptobenzimidazole, 5-methyl-benzotriazole, 1-phenyl-5-mercaptotetrazole, Compounds for rapid developing baths, such as those described in U.S. Patents 3,113,864, 3,342,596, 3,295,976,

3,615,522 and 3,597,119 are described, thiosulfonyl compounds, as described, for example, in GB-PS 972 211, phenazine N-oxides, as described, for example, in JA-AS 41 675/71 and the compounds described in Kagaku Shashin Binran (Manual of Scientific Photography), Vol. II, pp. 29 to 47), Stain and sediment preventing agents, such as those used e.g. in U.S. Patents 3,161,513 and 3,161,514 and British Patents 1,030,422; 1,144,481 and 1,251,558, which are described in U.S. Pat 3,536,487 described interlayer effect accelerator and preservatives (e.g. sulfites, bisulfites, hydroxylamine hydrochloride, Form sulfite and alkanolamine sulfite adducts).

509886/1167

After the color development, the recording materials become of the invention subjected to a conventional bleaching treatment. The bleaching treatment is used either on its own or in combination performed with the fixation. The bleach bath can optionally contain a fixative so that a bleach-fix bath is produced. e.g. ferricyanides, bichromates, water-soluble cobalt (III) salts, water-soluble copper (II) salts, water-soluble quinones, nitrosophenols, Complex salts of polyvalent cations, such as iron (III), Cobalt (III) and copper (II), with organic acids, e.g. aminopolycarboxylic acids, like l'thylenediaminetetraacetic acid, nitrilotriacetic acid, Iminodiacetic acid or N-hydroxyethylethylenediamine triacetic acid, Malonic acid, tartaric acid, malic acid, diglycolic acid or dithioglycolic acid, the copper complex of 2,6-dipicolinic acid, peracids, e.g. alkyl peracids, persulfates, Permanganates and peroxides, hypochlorites, chlorine, bromine or suitable Combinations of these compounds. The bleach bath can optionally also contain bleach accelerators, such as those in the TJS-PSs 3,042,520 and 3,241,966 and JA-PSen 8506/70 and 8836/70 are described, and numerous other additives are included.

The couplers of the invention can be used in color photographic Recording materials with a low silver halide content, as described in DT-OS 2,357,694, are used are. For the same image density, they require recording material! en about 1/2 to 1/100 of that used in conventional color photographic recording materials Amount of silver halide, e.g. about 65 to 375 mg / m silver halide every layer.

The color photographic recording materials with a low silver shark content also enable advantageous results, if this occurs during dye development according to e.g.

509886/1167

2,623,822 and 2,814,565 Silver undergoes halogen bleaching and color development is carried out again in order to increase the amount of dye obtained (e.g. by treatment with peroxides, See e.g. U.S. Patents 3,674,490 and 3,761,265, DT-OS 2,056,360 and JA-OSen 6338/72 and 10 538/72). The same applies to color processing using color-intensifying cobalt complex salts (see e.g. DT-OS 2 226 770, JA-OSen 9728 / 7'3 and 9729/73) and the process carried out using chlorous or bromous acid or their salts (JA-OSen 128 327 / 74- und 139 917 / 74-).

The examples illustrate the invention,

example 1

The multilayer color photographic material shown in FIG A is made by applying layers 1 through 8 to a transparent cellulose triacetate support.

1st layer (Idchthof protection layer)

1 g of the curing agent mentioned below becomes 1 g of one Added 5 percent aqueous gelatin solution containing black colloidal silver. The solution obtained is in applied to a dry layer thickness of 1 η.

2nd layer (intermediate layer)

50 g of 2,5-di-tert-octy-hydroquinone are dissolved in 100 ml of tricresyl phosphate and 200 ml of ethyl acetate and then dissolved in 1 kg of a 10 percent aqueous gelatin solution emulsified, with 5 S Sodium di (2-ethylhexyl) sulfosuccinate ("Aerosol OT" der American Cyanamide Co.) with a high speed stirrer are mixed in. 250 g of the resulting emulsion I are mixed with 1 kg of a 10 percent aqueous gelatin solution

S098 86/1167

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and then 1 g of a curing agent is added. The emulsion obtained is applied in a dry layer thickness of 1 η .

3rd layer (red-sensitive silver halide emulsion layer) 1 kg of a silver bromoiodide emulsion (amount of silver: 0.6 mol; iodine content: 7 mol percent; average grain size: 0.5 u) is mixed with 4 χ 10 * 5 mol of the sensitizer dye I and 1 χ 10 ~ ^ Moles of sensitizer dye II added to spectrally sensitize the emulsion. 450 g of an emulsion II are then added which, similar to emulsion I, has been prepared by dissolving 100 g of coupler I in 100 ml of tricresyl phosphate and 200 ml of ethyl acetate, whereupon 0.7 g of a hardening agent is added and the emulsion obtained applies in a dry layer thickness of 4.5 #.

4th layer (intermediate layer
According to the second layer »

5th layer (green-sensitive silver Î iulsionssch i cht)

1 kg of the silver bromoodide emulsion used for the 3x layer

—4

is made using 2 × 10 moles of the sensitizer dye III and 6 χ 10 "^ moles of sensitizer dye 17 spectrally sensitized. 600 g of an emulsion are then applied III was added, which was similar to emulsion I by dissolving 80 g of coupler II, 15 g of coupler III and 5 g of des Coupler (16) in 100 ml of tricresyl phosphate and 200 ml of ethyl acetate has been prepared, whereupon 0.9 g of hardener is added and the emulsion in a dry layer thickness from 4h applies.

6th layer (yellow filter layer)

200 g of emulsion I with 1 kg of a 5 percent aqueous Gelatin solution containing yellow colloidal silver, and

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253292b

1 g of a hardening agent is added, whereupon the emulsion is applied in a dry layer thickness of 1 u.

7th layer (blue-sensitive silver halide emulsion layer) 1 kg of the silver bromoiodide emulsion used for the 3 x layer is washed with 500 g of an emulsion IY offset similar vr ± e, the emulsion I prepared by dissolving 100 of the coupler IV g in 100 ml of dibutyl phthalate and 200 ml of ethyl acetate has been prepared. Then 1 g of a hardening agent is added and the emulsion is applied in a dry layer thickness of 3.

.8th. Layer (protective layer ).

1 kg of a 10 percent aqueous gelatin solution is mixed with 1 g of a hardening agent and then in a dry layer thickness of 1 u applied.

The following materials are used with sample A:

Hardening agent: 2 percent aqueous solution of the sodium salt of 2,6-dichloro-4-hydroxy-s-triazine

Coupler I:

2-naphthamide

Coupler II:

1- (2,4,6-Trichlorophenyl) -3-Z3 ^ (2,4-di-tert-amylphenoxyac et amido) -benzamidö7-5-pyrazolone

Coupler III: 1- (2,4,6-trichlorophenyl) -3-ZT2-chloro-5-tetradecanamido ) -anilino7 "-4- (3-methyl-5-hydroxyphenylazo) ■ 5-pyrazolone

609886/1167

253292B

Coupler IV: JL- (2,4-Dioxo-5i5-dimethyloxazolidinyl) -irpivaloyi- 2-chloro- b-βjr (2,4-di-tert-amylplienoxy) -butyramido / -acetanilide

Sensitizing Dye I:

Pyridinoum salt of anhydro ~ 5 »5'-dichloro-3 ₎ 3 ^l disulfopropyl-9-ethylthiacarbocyanine hydroxide

Sensitizing dye II:

Triethylammonium salt of anhydro-9-ethyl-3 _i 3'-di- (3-sulfopropyl) -4,5,4 ', ^' - di-benzothiacarbocyanine hydroxide

Sensitizing Dye III:

Sodium salt of anhydro-9'-ethyl-5,5'-dichloro-3,3 'disulfopropyloxacarbocyanine

Sensitizing Dye IV:

Sodium salt of anhydro-5 ₅ 6,5 ', 6'-tetrachlor-1, Ί'-diethyl-3 ₅ 3'-di sulfopropoxyethoxyethylimidazolocarbocyanine hydroxide

For comparison, a sample B similar to \ ύ. & Sample A is prepared, with o'ecl · ⁰⁰ * ¹ 84 g of coupler II and 16 g of coupler III instead of 80 g of coupler II, 15 g of coupler III and 5 g of the coupler (16) can be used.

Samples A and B to be processed color negative materials, exposed in a still camera and subsequently processed in the following Veise at 38 ⁰ C:

609886/1167

4Π -

1. Color development

2. Bleach 3 · Wash

4. Fixate

5. Soak

6. Stabilize

The treatment baths used have the following composition:

3 min 15th lake 6th ti 30th It 3 It 15th dd 6th It 30th Il 3 Il 15th It 3 ti 15th Il

Color developer bath 1.0 g Sodium nitrilotriacetate 4.0 g Sodium sulfate 30.0 g sodium 1.4 S. Potassium bromide 2.4 g Hydroxylamine sulfate 4- (N-ethyl-N-ß-hydroxyethylamino) - 4.5 g 2-methylanilino sulfate 1 liter Water on

Bleach bath

jämmmonium bromide 160.0 g

Aqueous ammonia (28%) 25.0 ml

Iron-sodium-ethylenediaminetetraacetate 130 g

Glacial acetic acid 14 ml

Water to 1 liter

Fixer

Sodium tetrapolyphosphate 2.0 g

Sodium sulfite 4.0 g

Sodium thiosulfate (70% aq. Solution) 175.0 ml

Sodium bisulfite 4.6 g

Water to 1 liter

609886/1167

Stabilizing bath

Formalin (40% aqueous solution) 8.0 ml

Water to 1 liter

It is found that the sample A with the invention Color negative film produced by Coupler has far better sharpness, grain and color purity than that obtained from Sample B. Movie"

Example 2

The multilayer color photographic recording material D shown in FIG. 2 is produced according to Example Λ . The individual layers have the following composition:

1st layer (antihalation layer)
Corresponding to the 1st layer of sample A.

2nd layer (intermediate layer)
Corresponding to the 2nd layer of sample A.

3rd layer (first red-sensitive silver halide emulsion layer; dry layer thickness 2 u)

Silver bromoiodide emulsion.

(Amount of silver: 0.05 mol percent; 1.2 g / m

Iodine content: 7 mole percent; mean grain size: 0.4 u; Gelatin:
6.2%)

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Sensitizing Dye I Sensitizing Dye II Coupler I

Coupler V

Coupler VI

Hydroquinone derivative I hardener

S 2C 10 "'·' moles / moles of syllable dd 1.2 χ ₁₀ -5 It 0.9 ti 0.02 Il 0.01 0.15

mg / m ^£

4th layer (second red-sensitive silver halide emulsion layer; dry layer thickness 1 «5 VÜ

Silver bromoiodide emulsion (Amount of silver: 0.048 mol percent; mean grain size: 0.7, #; iodine content: 8 mole percent; Gelatin: 6.4

Silver application rate: 1.0 g / m ²

Sensitizing dye I. 5 x 10 ^ Mc ) l / r! Sensitizing dye II 1.2 χ 10 " ⁵ It Coupler I 0.05 dd Coupler V 0.04 dd Coupler VI 0.01 ti Hardening agents 15 mg / m ²

5th layer (intermediate layer)

Corresponding to the second layer of sample A.

6 "layer (first green-sensitive silver halide emulsion layer; dry layer thickness 2.4 u)

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Silver bromoiodide emulsion (as with the 3-layer)

Sensitizing Dye III Sensitizing Dye IV Coupler II Coupler III Coupler (16) Coupler VII Hydroquinone derivative II curing agent

Silver application amount: Mole / mole silver 1.4 g / m ² Il 3 x 10 ~ ⁵ Il 1 χ 10 ~ ⁵ It 0.05 Il 0.01 ! I 0.003 Il 0.005 0.004

25 mg / m ^£

_f 7th layer , (second p; green sensitive silver halide emulsion

layer; Dry film thickness 1.6 yes) Il 2 μ) Silver bromoiodide emulsion It (as with the 4th shift) Silver application amount: It Sensitizing Dye III 2.0 g / m ² ) Il Sensitizing Dye IV Coupler II 2.4 10 ~ ⁵ mol / mol of silver Coupler III 0.8 χ 10 "~ 5 Coupler (16) 0.005 5). Layer (first blue-sensitive silver halide emulsion Coupler VII 0.05 layer; Dry film thickness Hardening agents 0.0002 8th layer (yellow filter layer) 0.001 Corresponding to the 6th layer of sample A. 20 mg / m ²

£ 09886/1167

Silver bromoiodide emulsion silver application:

(Amount of silver: 0.047 mol; 1.3 g / m

Iodine content: 7-5 mole percent;
mean grain size: 0.5 ^;
Gelatine: 6.2%)

Coupler IT 0.23 mole / mole silver

Hardener 20 mg / m

10 »layer (second blue sensitive silver halide emulsion layer; dry layer thickness 1., 2Ju)

Silver bromoiodide emulsion Silver application amount:

(Amount of silver: 0.052 mol percent; 1.2 g / m iodine content: 6 mol percent; mean grain size: 0.7 JQj Gelatine:
6%)

Coupler IV 0.06 mole / mole silver

Hardener 8 mg / m

11th layer (intermediate layer)
Corresponding to the 8th layer of sample A.

The materials used for preparing sample B are couplers I to IV, sensitizer dyes I to IV and the hardening agent from sample A, as well as the following materials:

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Coupler V: 1-Hydroxy-4 - (2-ethyloxycarbonylphenylazo) ~

N- (2-ethylamine 1) -2-naphthamide

Coupler VI: <£ j- (4 ~ Octadecyloxybenzoyl) -.- £ r (5- or 6-bromo-

1-benzota ± azo] yl) -2-methoxyacetanilide

Coupler VII: 1- (4-ButylaMnophenyl) -3- (2-methoxy-5-tetra-

decylox3roarbonylanilino) -4- (5- or 6-bromo-1-benzotriazolyl) -5-pyrazolone

Hydroquinone derivative I:

2- (2'-MeWIyItMo-I ¹ , 3 ', 4'-thiadiazole ¹ -yltMo) ~ 6-n -pentadecylhydroquinone

BydrocMnonderivat II:

2-n-hexadecylthio- 5- (1'-phenyltetrazole-5 ' -ylthio) -6-ph.enyltliiohydrocliinon

Sample B is processed into a 35 nm color negative film, exposed in a film camera and then developed into a color negative for film purposes in the following manner:

processing

Color development Stop bath watering bleaching watering fixation watering stabilizing bath

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(Temperature Time min 38 ⁰ C 3 ti It 1 It ti Λ ti Il 2 ti U 1 ti If 2 It It 1 Il Il 1

The treatment baths have the following composition:

Color developer bath

Sodium hydroxide 2 g

Sodium sulfite 2 g

Potassium bromide 0.4 g

Sodium chloride 1 g

Borax 4 g

Hydroxylamine sulfate 2 g

Disodium ethylenediamine tetraacetate

dihydrate 2 g

4-Ämino-3-methyl-N-ethyl-N- (ß-hydroxy-

ethyl) aniline monosulfate 4 g

Water to 1 liter

Stop bath

Sodium thiosulphate 10 g ammonium thiosulphate (70 % aqueous solution) JO ml

Acetic acid 30 ml

Sodium acetate 5 g

Potash I5 g

Water to '1 liter

Bleach bath

I'e (III) ethylenediaminetetraacetic acid (Na) complex salt potassium bromide

Ammonium nitrate boric acid

aqueous ammonia on water

100 g 50 g

50 g 5 g

up to pH 5.0 1 liter

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Fixing bath

Sodium Thiosulfate 150 S

Sodium sulfite 15 g

Borax 12 g

Glacial acetic acid 15 ml

Potash alum 20 g

Water to 1 liter

Stabilizing bath

Boric acid 5 g

Sodium citrate 5 g

Sodium metaborate tetrahydrate 3 g

Potash alum 15 g

Water to 1 liter

It is found that the sample C, the inventive Coupler (16), the two-layer color correction couplers described in JA-OS 33 238/73 VI and VII and the hydroquinone derivatives I and II described in JA-OS 41 870/73 in combination contains a color negative film with excellent color purity, grain and sharpness.

Similar results are obtained when the coupler (16) in the 6th and 7th layers in Example 2 is replaced by one of the couplers (D, (2), (3), (5), (7), (9), (12) or (15) are substituted for, or when two or more of these couplers are used in combination.

At game 3

A "silver bromoiodide emulsion (amount of silver: 0.6 mol; iodine content: 7 mole percent; mean grain size: 0.4 · u) is 2 χ 10 "" ^ mol of the sensitizer dye III and 6 χ 10 "^ mol

509886/1167

of the sensitizer dye IV added. In addition, 75 g of coupler II, 20 g of coupler III and 5 g of coupler (1) according to the invention are dissolved in 100 ml of tricresyl phosphate and 200 ml of ethyl acetate and processed into an emulsion V similar to emulsion I. 600 g of this emulsion V are added to the silver bromoiodide emulsion, whereupon 1 g of a hardening agent is added. The obtained coating solution is applied within 30 minutes (Sample E) .Außerdem a sample F is prepared that the same coating solution stored for 18 hours at 40 ⁰ C and then brushing.

In a manner similar to Samples E and F, Samples G and H, but using 5 g of the comparative coupler VIII instead of 5g of the coupler according to the invention (1).

Samples E, P, G and H are exposed to green light in stages and then processed according to Example 1. The sensitivity is determined on the basis of the resulting purple images. The sensitivity of the sample H is lower by a factor of 0.1 than that of the sample G if the sensitivity is expressed as a logarithm the amount of exposure required to produce a fog density of +0.1 is determined (sensitivity A). When determining the sensitivity as the logarithm of that required to produce a fog density of + 0.3 Exposure amount (sensitivity B), sample H has a sensitivity lower than that of sample G by a factor of 0.25 on. It can be seen from this that the comparative coupler VIII undergoes a change during the storage of the coating solution. On the other hand, samples E and · F with the inventive Coupler no different sensitivities A and B observed, since no desensitization occurs. Of the Thus, the coupler of the present invention has excellent stability.

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Comparative coupler VIII:

1 - \ ^ - / k - (2., 4-I> i-tert -amylphenoxy) -butyramidq7 ~ phenyly -3-pyrrolidino-4- (1-phenyl-5-tetrazolylthio) -5-pyrazolone.

The examples show that the couplers according to the invention excellent image sharpness, grain and parreproduction enable and extraordinary in coating solutions are stable.

509886/1167

Claims (9)

Claims 1. Eat development inhibitor-releasing purple couplers of the general formula (I) N-C-CH-S-R. Il I N C = O (I) in which R ^ and Rg are alkyl radicals, R ^ is a hydrogen atom or represents an alkyl, aryl or heterocyclic radical and R ^ represents an alkyl, aryl or heterocyclic radical. 2. magenta coupler according to claim 1 of the general formulas (II) and (III) c - CH - s - c ILf If I ^ NN ■ (II) NC = O .... " Y " 509886/1167 OWQINAi. Ji -C-CH-S- N-N Il Il C C-SCH- \ / (III) N "C = O- in the E ^ ,, Ep and E, the meaning given in claim 1 to have. 3. magenta coupler according to claim 1 of general formula (I), in which the alkyl radicals B ^, R ^ B-, and B ^ are unsubstituted alkyl radicals having 1 to 25 carbon atoms or substituted alkyl radicals having 1 to 25 carbon atoms, which are one or more aryl , Alkoxy, aryloxy, alkoxycarbonyl, acylamino, carboxyl, carbamoyl, sulfamoyl or cyano radicals or halogen atoms as substituents, the aryl radicals E, and E ^ are unsubstituted aryl radicals or substituted aryl radicals which are one or more alkyl, Have aryl, alkoxy, aralkoxy, alkoxycarbonyl, acylamino, sulfonamido, carboxyl, carbamoyl, sulfamoyl, cyano or nitro groups or halogen atoms as substituents, the heterocyclic Eest E, a pyrimidinyl, acridinyl, thiazolyl -, Benzοthiazolyl, piperidinyl, quinolinyl, thiazolyl or triazolyl group and the heterocyclic Eest E ^ a tetrazolyl, thiazolyl, thiadiazolyl, pyrimidinyl, thiadiazinyl, oxadiazolyl, oxazolinyl, imidazolyl, , Pyridazinyl, triazinyl, oxalolyl or thiazolyl group. 509886/1 167 4. silver halide color photographic recording materials; characterized by a support and at least one silver halide emulsion layer applied thereon, which contains at least one coupler, at least one of which is a magenta coupler of the general type Formula (I) according to claim 1 is. 5. Recording materials according to claim 4, characterized g e indicates that it is a magenta coupler of the general formula (II) ^K 3 ¹ N - C - CH - S - Il I ¹ J? = ° J ^ (ID included in the E ^, Ep and E ^ mentioned in claim 1 Have meaning. 6. Recording materials according to claim 4, characterized in that they have a magenta coupler general formula (III) 609886/1167 -C-CK-S NN
" H K ι ι ■ - C C N C = O V V (III) contained in the Iti> Eo ^{un <} ^ · ^R 3 ^ - ^Θ ^ ⁿ - ^ claim 1 have the meaning mentioned. 7. Recording materials according to at least one of the claims 4 to 6, characterized in that the magenta coupler represented by the general formula (I) and a cyan coupler in the same silver halide emulsion layer are included. 8. Farbphotographisch.es recording method, thereby characterized in that one exposed imagewise Silver halide emulsion layer containing an aromatic primary amine converter in the presence of a magenta coupler of the general formula (I) according to claim 1 developed. 9. The method according to claim 8, characterized g e k e η η ζ e i c h ne t that the image-wise exposed silver halide emulsion layer with an alkaline color developer bath developed that contains an aromatic primary amine and 509886/1167 a magenta coupler of the general formula (I) according to claim 1. 609886/1167