DE2417945A1 - PHOTOGRAPHIC LIGHT SENSITIVE SILVER HALOGENIDE MATERIAL - Google Patents

Description

TELEPHONE: 55547Ä 8000 MD NCH EN 2,

TELEGRAMS: KARPATENT MATHILDENSTRASSE 12

TE LEX: 5 29 068 K AR P D

August 19, 1974-W. 41 977/74 KoAcIi P 24 17 945.1

Fuji Photo Film Co., Ltd. Minami Ashigara-shi, Kanagawa (Japan)

Photographic.es photosensitive Silver halide material

The invention is concerned with color photography and more particularly relates to a new magenta coupler, which is useful for forming a color image of color photography, as well as a color photography containing it Silver halide material.

According to the invention there is provided a photosensitive silver halide emulsion which contains a coupler of the general formulas I or II

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OCO (CO) OR ₃ η

(D

N>

OCO (CO) _n OR ^ OCO (CO) 0-

(II)

contains, wherein R _{1 is} a hydrogen atom or a group with 1 to about 50 carbon atoms from the group of straight-chain or branched-chain alkyl groups, an alkenyl group, a cycloalkyl group, a substituted alkyl or substituted cycloalkyl group, which as substituents a halogen atom or a nitro, Cyano, aryl, alkoxy, aryloxycarboxy, alkoxycarbonyl, aryloxycarbonyl, sulfo, sulemoyl, carbamoyl, acylamino, ureido group, a heterocyclic group, an arylsulfonyloxy group or an oxo group, which can have at least one substituted aryl group -, alkoxy, aryloxy, carboxy, alkoxycarbonyl , acylamino, carbamoyl, alkylcarbamoyl, dialkylcarbamoyl, arylcarbamoyl, alkylsulfonamido, arylsulfonamido, sulfamoyl, alkylsulfamoyl, cyano or nitro group

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has genatome as a substituent, a heterocyclic group, which as a hetero atom is a nitrogen, oxygen * and / or Contains sulfur atom, a substituted heterocyclic group with those given above for the aryl group Substituents, a carbamoyl group or a thioearbamoyl group,

R _{2 is} a group with 1 to about 50 carbon atoms from the group of the same alkyl, substituted alkyl, aryl, substituted aryl groups, heterocyclic or substituted heterocyclic groups as stated above for R., an alkoacycarbamoyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a carboxy group, an amino group, an alkylamino group, a cycloalkylamino group, a Ν, Ν-dialkylamino group, an N-alkyl-N-arylamino group, an N-arylamino group, an amido group, a N-alkylacylamino group, an N-arylacylaraino group, an ureido group, an N-arylureido group, a ΝΑΙ kylureido group, a thioureido group, an N-alkylthioureido group, an N-arylthioureido group, a carbamoyl group, a guidamoylidino group, a pipqridino group, a pyridoylidino group, a pipqridino group N-alkylguanidino group or a K-arylguanidino group, R, a group ppe with 1 to 30 carbon atoms from the group of straight-chain or branched alkyl groups, an alkenyl group, a cycloalkyl group, an alkyl or cycloalkyl group, which with a halogen atom or a nitro ,. Cyano, aryl, alkoxy, carboxy ester, sulfoester, amido, sulfonamido, ureus, carbamoyl or sulfamoyl group, an aryl group which is substituted with one or more halogen atoms or a nitro, cyano, alkyl -, aryl, alkoxy, aryloxy, alkoxycarbonyl, acyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl _T , sulfoester, amido, sulfonamido, ureido,

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2 41 7 9 A 5

Carbamyl or sulfamyl group is substituted, a heterocyclic Group which contains a nitrogen, oxygen and / or sulfur atom as a hetero atom or a substituted one heterocyclic group which contains the substituents given above for the aryl group, Typically a divalent group of 1 to 30 carbon atoms from the group of alkylene groups and arylene groups, in which either R- or Rp is a divalent group of 30 or fewer carbon atoms, the two 5-pyrazolone units of the general formula I and / or II connects, can form, mean and

wherein the coupler forms a dye upon coupling with the oxidation product of an aromatic primary Amine is capable of color developing image

and further according to the invention there is a photosensitive A photographic element containing this light-sensitive silver halide emulsion and a method of formation of color images and application of the photosensitive Silver halide emulsion indicated.

It is known that in the color development of a color photographic Silver halide material, a color developing agent of the aromatic primary amine type and oxidized with a coupler to form a dye, for example Indophenols, indoanilines, indamines, azomethines, phenoxazines, phenazines and the like is converted so that the color image is formed. In this species, the subtractive color method is usually used for color rendering and yellow, purple and blue color images are formed which are the complementary colors of blue, green and red, respectively. For example a coupler of acylacetanilide or dibenzoyl

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methane type used to form a yellow color image, a pyrazolone, cyanoacetophenone or indazolone type coupler is used to form a purple color image, and a phenol type coupler such as phenol or Naphthol, is used to form a blue color image.

In this photographic process, a dye-forming coupler is added to the developer or a photosensitive one incorporated into the photographic emulsion layer. Therefore, an oxidized color developing agent which when the latent image is developed is reacted with the coupler to form the color image.

The color image-forming couplers of the state of the technology are practically all four-equivalent couplers, which theoretically 4 moles of silver halide as an oxidizing agent for the formation of. Require 1 mole of the dye in the coupling reaction. On the other hand, a two-equivalent coupler requires an active methylene group which is formed with one in the coupling of an oxidized product of the developing agent is substituted from an aromatic primary amine, removable group, only the development of 2 moles of silver halide to form one mole of the dye. Because the amount of silver halide required to form a In the case of the two-equivalent coupler, only the dye Half that in the case of an ordinary four-equivalent coupler required amount, have the two-equivalent .coupler numerous advantages in that a thinner photosensitive layer can be used and the layer can be treated quickly. In addition, the photographic properties and economy can be achieved by the Decrease the film thickness can be increased.

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SUBSCRIBED

In particular, a two-equivalent magenta coupler is used is desirable because, in general, a higher coupler to dye conversion ratio than a four-equivalent coupler and less influence on the fading of a color image due to the remaining Coupler is exercised. However, the two-equivalent couplers proposed heretofore have various disadvantages insofar as the reactivity is unsuitable, staining and fogging occur, and numerous difficulties occur in the synthesis of the couplers.

A first object of the invention is therefore in a new two-equivalent pyrazolone magenta coupler in which the 4-position of the 5-pyrazolone nucleus with one at the Coupling reaction with the oxidation product of an aromatic primary amine as a releasable developing agent Group is substituted.

A second object of the invention consists in a new two-equivalent coupler with a suitable reactivity, which for the formation of a colored dye in high yield and without the formation of undesirable stains and Veil is suitable.

A third object of the invention is a color photographic one light-sensitive material with a silver halide emulsion layer, which contains the novel magenta image forming coupler.

A fourth object of the invention is to provide an improved color photographic process, wherein the amount the silver halide in the photographic emulsion layer is reduced and the sharpness of the color image is improved,

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using the new magenta image forming coupler.

The fifth object of the invention is to provide a color photograph with a permanent color image using the novel magenta image forming coupler will.

Further objects will emerge from the following description of the invention and the accompanying drawing.

As part of extensive efforts to achieve the above objectives, it has been found that the trained Color image is quite excellent when a silver halide photographic emulsion containing an aromatic primary amine as a developing agent in the presence of a magenta color image-forming coupler in which the 4-position of the 5-pyrazolone ring with a carbonic acid ester group or it is substituted by an oxalic acid ester group, is treated.

The drawing shows a graph showing that the film A according to the invention is superior to the prior art film B for obtaining a constant color image, with only one small amount of developed silver is required.

In the context of the invention, all 5-pyrazolones in which the 4-position of the pyrazolone ring is substituted with a carbonic acid ester group or an oxalic acid ester group can be used without difficulty. Ie _; all pyrazolones in which the 4-position is used as a four-equivalent magenta coupler can be used. 5-Pyra-Bolons a carboxylic acid ester or an oxalic acid

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has ester bond and all pyrazole-4,5-diesters, which are derived from the enol type of 5-pyrazolones, without Difficulties are used.

These compounds can be expressed, for example, by the following general formulas

-OCO (CO) _n OR ₃

(D

R ₂ "

-oco (co) _n oR "oco (co) _n o-

'R ₂

, N

(II)

where R ₁ and R2 are customary groups as used in the four-equivalent pyrazolone couplers, R, a monovalent group, R, a divalent group and η denote the numbers 0 or 1.

For example, R-, a hydrogen atom, or a group having 1 to about 50 carbon atoms is preferred

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.1 to 35 carbon atoms, ie a straight-chain or branched-chain alkyl group, for example a methyl, ethyl, isopropyl, tert-butyl, hexyl, tert-octyl or dodecyl group, an alkenyl group, for example an allyl group, a Cycloalkyl group, for example a cyclohexyl or norbornyl group, a substituted alkyl or cycloalkyl group which has a halogen atom or a nitro, cyano, aryl, alkoxy, aryloxycarboxy, alkoxycarbonyl, aryloxycarbonyl, sulfamoyl, Carbamoyl, acylamino, ureido, a heterocyclic group, an arylsulfonyloxy or oxo group, for example a / 3-cyanoethyl, β- chloroethyl, benzyl, nitrobenzyl, dichlorobenzyl, y- (2,4-ditert. -Amylphenoxy) -propyl- or / ä-phenoxyethyl group. Furthermore, R ₁ denotes an aryl group which is a phenyl or an α- or ß-naphthyl group, an aryl group with one or more substituents, for example alkyl, alkoxy, aryloxy, carboxy, alkoxycarbonyl, acylamino, carbamoyl, Alkylcarbamoyl, dialkylcarbamoyl, arylcarbamoyl, alkylsulfonamide, arylsulfonamide, sulfamoyl, alkylsulfamoyl, cyano or nitro groups or halogen atoms. A phenyl group in which at least one of the o-positions is substituted with an alkyl group, with an alkoxy group or a halogen atom is particularly suitable as R ₁ . In addition, R ₁ denotes a heterocyclic group, for example a 5-membered or 6-membered heterocyclic group or a condensed heterocyclic group which contains a nitrogen, oxygen or sulfur atom as a hetero atom, for example a pyridyl, quinolyl, furyl, benzothiazolyl , Oxazolyl, imidazolyl or naphthoxa ζ ο lylgru pp ¹ ! or a substituted heterocyclic group having the substituents given above for the aryl group. Furthermore, R ₁ can denote a carbamoyl or thiocarbamoyl group.

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R «means a group with 1 to about 50 carbon atoms, preferably 1 to 35 carbon atoms, i.e. the same alkyl, substituted alkyl, aryl, substituted aryl groups, heterocyclic groups or substituted heterocyclic groups as indicated for R ^. Furthermore, Rp denotes an alkoxycarbonyl group, for example a methoxycarbonyl or ethoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, a substituted oxy group such as an alkoxy group such as methoxy, ethoxy, decyloxy and the like or an aryloxy group, e.g. a phenoxy, Tolyloxy group and the like, a substituted thio group, such as an alkylthio group such as an ethylthio, propylthio group and the like or an arylthio group, e.g. a phenylthio, tolylthio group and the like, a carboxy group, an amino group, e.g. an N-alkylamino, Cycloalkylamino, N, N-rialkylamino, N-Z ^ lkyl-N-arylamino or N-arylamino, an amide group, for example an acetamide, α- (2,4-di-tert-amylphenoxy) acetamide -, α-Butoxyphenoxypropionamido- or a- (3-Pentadecyl-4-sulfonoxyacetamido) benzamido- or Benzamid ο gru ppe, an N-A.lkylacylamino group, an N-arylacylamino group, an ureido group, for example an N-iarylureido or N-alkylureido group, a thioureido group, for example an N-alkylthioureido or N-arylthioureido group, a car bamoy 1 group, for example a carbamoyl, N-octadecylcarbamoyl, Ν, Ν-dihexylcarbamoyl-, N-ifethyl-N-phenylcarbamoyl- or 3-pentadecylphenylcarbamoyl group, a sulfamoyl group, a piperidino group, a pyrrolidino group, a guanidino group, for example a GuanidinoT N-A.lkylguanidino- or N-arylguanidino group.

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R, represents a group having 1 to about 30 carbon atoms, i.e. a straight or branched chain alkyl group, e.g. a methyl, ethyl, isopropyl, isoamyl, 2-ethylhexyl, dodecyl or stearyl group, an alkenyl group, for example an allyl or oleyl group, a cycloallyl group such as a cyclohexy group, an alkyl or cycloalkyl group, the with a halogen atom or a nitro, cyano, aryl, alkoxy, aryloxy, carboxyester, sulfoester, amide, sulfonamido, Ureido, carbamyl or sulfamyl group is substituted, for example a 2-chloroethyl, 2-chloropropyl, 2-chlorocyclohexl, 2-cyanoethyl, benzyl, ß-phenethyl, 3-dodecyloxypropyl, 2- (2,4-di-tert-amylphenoxy) ethyl-, 4- (3-pentadecylphenoxy) -butyl-, α-Dodecyloxy carbonylethyl, 2-N, N-diethylaminoethyl, 2-acetylaminopropyl, 2-benzenesulfonamidoethyl, butyloxycarbonylmethyl, 2-acetyloxyethyl-, 2- (N, N-di-n-butylamino) -sulfonylethyl- or 4-isopropylcyclohexyl group. Farther means R, an aryl group, for example a phenyl or a <£ - or ß-naphthyl group or an aryl group with one or more nitro, cyano, alkyl, aryl, alkoxy, Aryloxy, alkoxycarbonyl, acyl, arylcarbonyl, alkylsulfonyl, Arylsulfonyl, sulfoester, amide, sulfonamide, ureido, carbamyl and sulfamyl groups or halogen atoms. Furthermore, R ^ denotes a 5-membered or 6-membered heterocyclic Group, which 'as a hetero atom, a nitrogen, oxygen and / or contains a sulfur atom, for example a tetrahydrofuryl-, 2-Fury / methyl-, tetrahydrofurfuryl- or 3- or 4-pyridyl group. These rings can be substituted with the substituents given above for the aryl group.

R ^ means a divalent group, for example with 1 to about 30 carbon atoms obtained by removing two hydroxyl groups from a dihydric alcohol or dihydric Phenol was obtained, for example an ethylene group, e.g. ethylene, propylene, hexamethylene, octadecamethylene, 2-butylene, 1 ', 4-r-cyclohexanedimethylene group and the like,

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an aryl group, for example phenylene, methylphenylene, 2,5-di-tert-octylphenylene, chlorophenylene, methoxyphenylene, Phenylphenylene, naphthylene, biphenylene, isopropylidenebisphenylene group and the like or a xylylene group, e.g. Xylylene, chlorxylylene, ethoxyxylylene group and the like.

Both R ^ or Rp can also be a divalent group having about 30 or less carbon atoms so that a bis-pyrazolone coupler is formed.

The pyrazolone compound in which the 4-position is substituted with a carbonic acid ester group or an oxalic acid ester group and which is used in the present invention provides various properties depending on the substituents at the 1-, 3- and 4-positions, and this feature is applicable to various photographic purposes . If at least one of R ^, Rp, R * and R, contains a hydrophobic group having 8 or more carbon atoms, the coupler associates in a hydrophilic colloid and becomes nondiffusible in the hydrophilic colloid layer of the light-sensitive material. Such couplers can be incorporated in the silver halide emulsion layer. If R, or R ^ contain a hydrophobic group with 8 or more carbon atoms and at least one of the radicals R ^ and R _{2 contains} a water-solubilizing group, for example a sulfo or carboxyl group, the coupler as such is not diffusible, but can be a diffusible dye by the oxidative coupling reaction with the aromatic primary amine as a developing agent. Such a diffusible dye-providing coupler is useful for diffusion transfer color photography.

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The method of forming a color image by the oxidation and coupling reaction with the aromatic primary amine as a developing agent can be mainly divided into two types according to the method of adding the coupler. In one type, the so-called internal type, the coupler is incorporated into the emulsion during the preparation of the light-sensitive material. The suitable amount of the pyrazolone compound according to the invention which can be incorporated in the emulsion layer is in the range of about 2 10 to 1 10 mol / m of the support. In the other type, the so-called external type, the coupler is dissolved in a developer and enters the emulsion layer by diffusion during development. The appropriate amount of the pyrazolone compound according to the invention, which can be used in the developing solution is in the range of about 5 ~ χ 10 ² to 5 x 10 "^ mol / l of developer solution.

The coupler used in the internal type must be in the emulsion layer be fixed, i.e. it must be resistant to diffusion. If the coupler is not diffusion resistant, it will migrate the coupler in the photosensitive material and the color is formed in the wrong photosensitive emulsion layer, so that the color rendering suitability of the light-sensitive material is markedly damaged.

In order to make the coupler diffusion-resistant, a group containing a hydrophobic radical having 8 to 32 carbon atoms is introduced into the coupler molecule 1. This residue is generally referred to as "ballast group ^11. The ballast group can be linked to the coupler structure directly or via an imino, ether, carbonamide, sulfonamide, acid, ester, imide, carbamoyl or sulfamoyl bond .

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Some examples of ballast groups that can be used are suitable in the couplers according to the invention are the following:

(I) alkyl groups and alkenyl groups, e.g.

/ C ₂ H ₅
-CH ₂ CH ^, -Ci ₂ H ₂₅ , -CTeH ₃₃ , -Ci ₇ H ₃₃

(II) alkoxyalkyl groups, e.g. 3.

- (CH ₂ ) ₃ O (CH ₂ ) ₇ CH ₃ , - (CH ₂ ) 3 OCH ₂ -CH- (CH ₂ ) ₈ CH ₃

C ₂ H ₅

as disclosed, for example, in Japanese Patent Publication 27563/1964.

(III) alkylaryl groups, e.g.

C ₁₁ H ₉ Ct)

\ - -J

(IV) alkylaryloxyalkyl groups, e.g.

y- \ y-CsHndO, -CH ₂ O- / Vc ₅ H ₁₁ Csec)

C ₅ HnCsec)

C ₅ HnCt) -CH ₂ O - / "" ^

■ C ₂ H ₅
C ₅ HnCt) -CHO- / VC ₅ HnCt)

- (CHz) ₃ O

-CH ₂ O

C ₅ Hn (t)

CH ₃ -C-CH ₃

CH ₂ -Ci ₁ H ₉ Ct)

C ₅ HnCt)

c ₅ HnCt)

C ₅ HnCt)

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(V) acylanidaikyl groups, ζ.Β,

• COC15H31

-CH ₂ CH ₂ N;

., COCi ₃ H ₂₇

-CH ₂ CH ₂ N ^

-CH ₂ CH ₂ NHHCOCh ₂ CH ₂ N ^

C ₃ H ₇

'As stated e.g. in U3-PS 3 337 344 and 3 413.

(VI) alkoxyaryl and aryloxyaryl groups, e.g.

-0CieH ₃₇ (n)

VC ₁₂ H ₂

(n)

(VII) Long-chain aliphatic groups, such as alkyl or alkenyl groups, with water-soluble groups, such as Carboxyl or sulfo groups, e.g.

-CH-CH = CH-C ₁₆ H ₃₃ , -CH-C ₁₆ H ₃₃ CH ₂ COOH SO ₃ H

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2U7945

(VIII) Kit of an ester group substituted alkyl groups, ^Ζ · ^Β · -CH-C ₁₆ H ₃₃ Cn) ,. -CH ₂ -CH ₂ -COOCi ₂ H ₂₅ Cn)

COOC ₂ H ₅

(IX) With an aryl group or a heterocyclic group Group substituted alkyl groups, e.g.

-CH ₂ -CH ₂

O I »

- C

-CH ₂ CH ₂ -V \ -N Ι

= / \ _r ^ Ap 'tr

C wen ₃ s

Il

(X) Substituted with an aryloxyalkoxycarbonyl group Aryl groups, e.g.

C5H11

COOCH ₂ CH0 - </ ^X ) -C 5 H 3 C ₂ H ₅

Examples of preferred couplers for use in the photographic light-sensitive materials according to the invention are given in the following. However, the invention is not limited to these specific examples.

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- 37 -

Coupler 1

1- (2-Chloro-4,6-dimethylphenyl) -3- (3- (J * - (2,4-di-tert-amylphenoxy-ethylamidoibenzamido) -5-pyrazolonyl- (4) -benzyl carbonate.

Coupler 2

l- (2,4,6-trichlorophenyl) -3- (oC - (3-n-pentadecylphenoxy) -butylamido) -5-pyrazolonyl- (4) -benzy! Carbonic acid ester.

Coupler 3

l- (2,4,6-trichlorophenyl) -3- (3 - (^ - (2,4-di-tert-amylphenoxy) -acetamido) benzamides ») -5-pyrazolonyl- (4) -benzyl carbonic acid esters.

Coupler 4

1- (2,4,6-Trichlorophenyl) -3- (3- ( oC- (2,4-di-tert-amylphenoxy) -acetamido) benzanido) -5-pyrazolonyl- (4) -ethy! carbonic acid ester.

Coupler 5

1- (2,4,6-Trichlorophenyl) -3- (3- (OC- (2,4-di-tert-amylphenoxy) -butylamido) benzamido-5-pyrazolonyl- (4) -4-nitrobenzyl carbonate.

Coupler 6

1- (2,6-Dichloro-4-methoxyphenyl) -3- (3 - (^ - (2,4-di-tert-amylphenoxy) butylamido) phenylureido) -5-pyrazolonyl- (4) -4-phenylazobenzy ! carbonic acid esters.

Coupler 7

1- (2,4,6-Trichlorophenyl) -3- (3- (X- (2,4-di-tert-amylphenoxy) -acetamido) benzamido) -5-pyrazolonyl- (4) -phenyl carbonate . _{A0g847 / 1025}

■ · 18

Coupler 8

1- (2,4,6-Trichlorophenyl) -3- (2-chloro-5 - (- 3C - (2,4-di-tert-amylphenoxy) butylamido) anilino) -5-pyrazolonyl- (4) -benzy ! carbonic acid esters.

Coupler '9

1- (2,4,6-Trichlorophenyl) -3- ((2-chloro-4-n-liexadecylamido) -anilino) -5-pyrazolonyl- (4) -cyclohexyl carbonic acid ester.

Coupler Io

l- (2,4j6-trichlorophenyl) -3- ((2-chloro-4-n-dodecyloxycarbpnyl) -anilino) -5-pyrazolonyl- (4) -4-nitr opiieny! carbonic acid ester .

Coupler 11

1- (2,4,6-Trichloroplienyl) -3- (3- (oC - (2,4-di-tert-amylphenoxy) -acetamido) benzamido) -5-pyrazolonyl- (4) -ethyloxalic acid ester.

Coupler 12

1- (2,4,6-Srichxlorophenyl) -3- (2-cliloro-5- (oC - (2,4-di-tert-amylphenoxy) butylamido) anilino) -5-pyrazolonyl- (4) -phenyloxalic acid ester.

Coupler 13

1_ (4_ (oC - (2,4-Di-tert-amylphenoxy) acetamido) phenyl) -3-methyl-5-pyrazolonyl- (4) -bencyclic acid ester.

Coupler 14

1-Pheny 1-3-C "* -carboxymethyl-n-2-eicosananido) -5-pyrazolony1- (4) -ethy / carbonic acid ester.

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Coupler 15

1- (3-Potassium sulfonate-4-phenoxyplienyl) -3-n-OGtadecyl-5-pyrazolonyl- (4) -tetrahydrofury! carbonic acid ester.

Coupler 16

1- (4-Carboxyphenyl) -3- (2-methoxy-5-carboxyanilino) -5-pyrazolo-ethyl- (4) -octadecyl carbonate.

Coupler 17

1- (3-Sulfo-4-phenoxyphenyl) -3-benzamido-5-pyrazolonyl- (4) -β- (2,4-di-tert-amylphenoxy) ethycarbonic acid ester.

Coupler 18

1- (2,4,6-Trichlorophenyl) -3- (3- (- <- (3-n-pentadecylphenoxy) -butylamido) benzamido) -5-pyrazolonyl- (4) -ethy! carbonic acid ester.

Coupler 19

1- (2,4,6-Trichlorophenyl) -3 - ((2-chloro-5-n-tetradecylamido) -anilino) -5-pyrazolonyl- (4) -ethycarbonic acid ester.

Coupler 2o

1- (2,4,6-Trichloropheny1) -3- (3- (ος- (2,4-di-tert-amylphenoxy) acetamido) benzamido) -pyrazole-4,5-dipheny / carbonic acid ester.

Coupler 21

l-Phenyl-3- (3,5-di carboxyanilino) -5-pyrasolony1- (4) -4 - (= £ - (2,4-di-tert-amylphenoxy) buty! Amidο) -benzyl carbonic acid ester.

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~ ^2o ~ 2417345

Coupler 22

1,4- bis (1- (4- (o ^ - (2,4-Di-tert.-amylphenoxy) buty! Amido) -phenyl) -5-pyrazolonyl- (4) -ethy! Carbonic acid ester) -terephthalamide.

Coupler 23

l- (2,4,6-trichlorophenyl) -3- (2-chloro-5- (r - (2,4-diter t-amylphenoxy) pro pylsulfaraoyl) anilino) -5-pyranolonyl- (4) -benzy! carbonic acid ester.

Coupler 24

1- (2,6-I) chloro-4-methoxyphenyl) -3- (3- (oc - (3-n-pentadecylphenoxy) acetamido) benzamido) -5-pyrazolonyl- (4) -4-pyridy! Carbonic acid ester.

Coupler 25

cx ', ^' - bis (1- (2,4,6-trichlorophenyl) -3- (3 - (^ - (2,4-di-tert-amylphenoxy) acetamido) benzamido) -5-pyrazolonyl- (4 )) - p-xylylenedicarbonic acid ester.

Coupler 26

1- (2,4,6-Trichlorophenyl) -3- (2-chloro-5- (' ^{:: i} ·· -ethoxycarbonyl-n-pentadecyloxycarbonyl) anilino) -5-pyrazolonyl- (4) -benzyl carbonate.

Coupler 27

l- (2,4,6-trichlorophenyl) -3 - ((3 - (^ - methyl-ß-n-octyloxy) propylamido) benzamido) -5-pyrazolonyl- (4) -benzy! carbonic acid ester.

Coupler 28

l- (2-chloro-4,6-dimethylphenyl) -3- (2-chloro-4- (y'-C2,4-di-tert-amylphenoxy) propylsulfamoyl) anilino) -5-pyrazolonyl- (4) -benzy! carbonic acid ester.

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Coupler 29 .

1- (2,4,6-trichloropheny 1) -3- ((3-n-oetadecylsuccinimido) benzamido) -5-pyrazolynyl- ( 4) -benzy! Carbonic acid ester ,.

A feature of the couplers used in the present invention is that a hydrogen atom of the active methylene group is in the 4-position of the pyxazolone with a carbonic acid ester group or oxalic ester group is replaced. This coupler is a so-called two-equivalent coupler, which reacts with the oxidation product of an aromatic primary amine as a color developing agent and the errteprechendeii leucoazcriethin dye and a pyrazolone azomethine dye forms when the carbonic acid monoester or oxalic acid monoester group is released. Only 4-acyloxy-5-pyra2olone compounds were previously considered to be 5-pyrazolones with an ester group in the 4-position of the pyrazolone are known. In US Pat. No. 3,311,476 there is an example of manufacture for l- (2,4,6-trichlorophenyl) -3- (3- (c < - (2,4-di-tert-aniylphenoxy) acetamido) -benzamido) -4-acetoxy-5-pyrazolone described, but the implementation process is long and no characteristic values are given there.

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When carrying out the preparation example, the The compound indicated above was obtained only in low yield. In the context of the invention it was attempted the compound indicated above in a manner other than indicated in the US patent to prepare. if 1 - (2,4,6-0? Richlorphenyl) 3- (3- (<* .- (2,4-di-tert-amy! Phenoxy) acetamido) benzamido) -4-hydroxy-5-pyrazolone with acetyl chloride was reacted in excess, it was found that that derived from the enol body of 4-hydroxy-5-pyrazolone 4,5-diacetoxypyrazole compound was initially formed as an intermediate and ".then into the 4-acetoxy-5-pyrazolone was converted by rapid and selective hydrolysis of the enol ester moiety at the 5-position when at Room temperature was allowed to stand in the reaction solution. However, this 4-acetoxy-5-pyrazolone was so unstable that while cleaning it to 4-hydroxy-f? -pyrazolone in the presence was hydrolyzed by water, rapidly oxidized and isolated as a stable pyrazole-4,5-dione body.

In contrast, those used according to the invention differ Couplers which have a carbonic acid ester group or an oxalic acid ester group in the 4-position of the pyrazolone, clear from the coupler described above with regard to the chemical structure, show a much higher stability, and their manufacture is very simple as indicated below.

The pyrazolone couplers used according to the invention have the following valuable properties:

The coupler according to the invention is a two-equivalent coupler, theoretically only two equivalents of silver halide as an oxidizing agent to form a molecule a colored dye required. The required silver halide can be reduced to about half that when the previous 4-equivalent couplers of the pyrazolone type were used be, thereby not only in the photosensitive material contained silver halide is halved and the manufacturing

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the cost of the photosensitive material can be reduced, but also light scattering due to the emulsion grains is reduced and the sharpness of the image is improved.

The coupler of the 4-substituted 5-pyrazolone type, as it is used according to the invention, can in an azomethine dye in high yield by oxidation and Coupling reaction using exposed silver halide as an oxidizing agent. Some of the 4-equivalent couplers used so far have a low one Conversion yield in the dye, since the leuco dye formed as an intermediate product has side reactions such as azine ring formation, gives. In contrast to this, the 5-pyrazolone type substituted in the 4-position used according to the invention Azomethine dye can be converted in high yield, since the reaction process does not have such a reactive Intermediate takes place. As a result, it is the photosensitive one Color material according to the invention possible to reduce the amount of the magenta-forming coupler, the content of silver halide and the thickness of the emulsion layer to humiliate. This easily reduces the cost of the photosensitive material and improves the sharpness and favors development.

The coupler used according to the invention is in the 4-position substituted 5-pyrazolone type generally has a strong Coupling activity for an oxidized aromatic primary amine as a color developing agent and rapidly removes the the color developing oxidized product of the color developing agent, so that the development of the silver halide emulsion is accelerated.

With the inventive coupler used in the 4-position substituted 5-pyrazolones is the process for Formation of the dye in a color developing bath ended, and there is no need to go into a bleach bath that contains a strong oxidizing agent such as potassium ferricyanide or potassium dichromate, contains, apply. Therefore a treatment with

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Bleaching and fixing bath which is a silver complexing salt forming agent and a weak oxidizing agent, for example a ferric iron chelate of EDTA or a bleach bath, which contains a mercury-II-salt like mercury-II-chloride, possible, and as a result, it is easy to shorten the time for all the color development treatments, as well as the problem of environmental pollution from treatment solution delivery to solve.

In contrast, with some 4-equivalent couplers, wherein the position of the coupling reaction is not substituted, the color forming reaction is not in the color developing bath completed and a significant portion of the coupling reaction product remains in the colorless leuco form, whereby an additional treatment with an oxidizing agent, as stated above, becomes necessary to complete the color formation.

Those used according to the invention, in the 4-position substituted 5-pyrazolone couplers are formed by carbonyl compounds, such as aldehydes and ketones, inactivated to a small extent, while the known ones were unsubstituted in the 4-position 5-pyrazolone coupler, especially in an emulsion layer, to a compound with low color-forming reactivity, for example a methylol or methylene bis compound, can be changed by formaldehyde in the air, which often does not have sufficient color-forming property during color development results. This change in the coupler markedly reduces the color rendering of the color light-sensitive material, lin feature of the color light-sensitive material according to the invention is that the material is hardly affected by such chemicals.

The 5-pyrazolones substituted in the 4-position according to FIG Invention have the advantage if they are common photosensitive Color materials are used as indicated in the examples that stability over time in the emulsion film is high, and in particular, the color-forming properties

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24.U945

! Since with

shank to a lesser extent in the course of low temperature compared to high humidity reduced to the known couplers described above. In the case of a light-sensitive, color material, there is stability the durability of a fresh film is one of the most important factors in determining its properties. Furthermore, it was found that one developed from the couplers substituted in the 4-position according to the invention Color image has far better heat resistance as one of 4-position unsubstituted couplers and itself in comparison with the above known coupler which has a substituent on the 4-position on the same pyrazolone ring has, the couplers according to the invention have a higher heat resistance igke it.

The couplers according to the invention, wherein the 4-position with a carbonic acid ester group or an oxalic acid ester group Is substituted, as can be seen in the above general formulas I or II, are easily by reacting a 4-hydroxy-5-pyrazolones corresponding to the general formula III

R ₂ "

-OH

III

and an acid chloride corresponding to the general formula IV. R ₃ OCO (CO) _n C / or 0 / CO (CO) _n OR ₄ OCO (CO) _n Cf IV

obtained, wherein R .., E ^, R ,, R ^ and η have the same meanings as in the general formulas I and II.

The 4-ydroxy-5-pyrazolones according to the general Formula III can with high yield by reducing the corresponding pyrazolone-4,5-dione compounds in the usual way, for example a catalytic hydrogenation using

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r 26-

a metal catalyst such as palladium carbon or reduction using zinc acetic acid or sodium borohydride, as disclosed in U.S. Patent 3,419,391. The pyrazolone-4,5-dione compound can be obtained by conversion of the 5-pyrazolone in the corresponding az © methine dye followed by hydrolysis with sulfuric acid, as disclosed in US Pat. No. 3,311,476, or by conversion of 5-pyrazolone into 4-amino-5-pyrazolone and subsequent oxidation of the amino group, as in US Pat. No. 3,419 specified, -received.

The manufacturing processes for acid chlorides according to general formula IV are well known, and some acid chlorides are easily available.

Production examples of couplers according to the invention are given below. Unless otherwise stated is, all parts, percentages, ratios and the like are based on weight.

Production example 1

Preparation of 1- (2, / i, 6-trichlorophen3 / 'l) -3- (3- (k- (2, ^ - di-tert-amylphenoxy) acetamidc) benzamido) -5-pyrazolonyl - (^ -) -benzyl carbonic acid ester (Coupler 3).

32.4 g of 1- (2,4,6-trichlorophenyl) -3- (3- (a- (2,4-di-tert-amylphenoxy) acetamido) benzamido) -4-hydroxy-5-pyrazole were in 1000 ml of anhydrous diethyl ether dissolved Stickstcffatmosphäre mixed with 17.0 g Chlorkohlensäurebenzylester, stirred at 20 ⁰ C for 5 minutes and then mixed with 11.2 g of triethylamine. After reaction at the same temperature for 10 minutes, the precipitated triethylamine hydrochloride was filtered off and 6.0 g of triethylamine were further added to the filtrate. The precipitated solid was filtered off, washed sufficiently with diethyl ether and dissolved in 100 ml of acetic acid. This solution was poured into 1200 ml of ice water, the

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24179A5

precipitated white solid was filtered off and dried. The product was extremely pure Coupler 3 which did not require further purification. Yield: 33.8 g; Melting point: 109-110 ⁰ C.

IR spectrum (Nujol): vC = 0

1760cm ^"1 \> COC, 124Ocm ~ ^1, 1230 cm" ¹ NMR spectrum: ÄCDC /

525 ppm (2H, 6.68 - 8.10 ppm (14H) elemental analysis:

found: G 61.10; H 5.24; N 7, O2 # Calcd .: C 61.40; H 5.24; N 6.62%

Production example 2

Preparation of 1- (2,4,6-trichlorophenyl) -3- (3- (a- (2,4-di-tert-amylphenoxy) acetamido) benzamido) -5-pyrazolonyl- (4) -ethyl carbonate (Coupler 4).

This coupler was obtained in a manner analogous to coupler 3. That is, 46.2g 1- (2,4,6-trichlorophenyl) -3- (3- (α- (2,4-d i-tert-amylphenoxy) -acetamido) benzamido) -4-hydroxy-5- Pyrazolone were dissolved in 1200 ml of anhydrous diethyl ether, to which 15.2 g of ethyl carbonate and 16.1 g of triethylamine were added and the mixture was reacted. After the reaction, the precipitated triethylamine hydrochloride was filtered off, 7.3 g of triethylamine were added to the filtrate and the precipitated solid was removed by filtration. This was dissolved in 12C ml of acetic acid, poured into 1800 ml of ice water and the precipitated solid was removed by filtration and then dried. Yield: 42.3 g; Melting point: 115-121 ^° C

IR spectrum (Uuyol): \> C = 0
1760cm " ¹ , \? COC, 1250cm" ¹ (wide)

NMR spectrum: ^

4.30 ppm (2H, q, 8H _Z ), 8.45 ppm Elemental analysis:

Found: C, 58.22; H 5.43; N 7.14 bet .: - 58.50; H 5.40; N 7.38

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Production example 3

Preparation of 1- (2,4,6-irichlophenyl) -3- (3- (a- (2,4-di-tert-amylphenoxy) acetamido) benzanido) -5-pyrazolonyl- ( Δ ) -phenyl carbonic acid ester (Coupler 7 ).

This coupler was prepared in an analogous manner to coupler 3. That is, 43.8 g of 1- (2,4,6-trichlorophenyl) -3- (3- (a- (2,4-di-tert-amylphenoxy) acetamidc) T-benzamido) -4-hydroxy-5-pyrazolone became dissolved in 1000 ml of anhydrous diethyl ether, to which 20.9 g of phenyl chlorocarbonate and 14.3 g of triethylamine were then added, whereupon the G-emic was reacted. After the reaction, the precipitated triethylamino hydrochloride was filtered off, 7.2 g of triethylamine were added to the filtrate and then stirred overnight, and the precipitated solid was then filtered off . dried yield: 35,2g, melting point: 110-113 ⁰ C.

IR spectrum (NuJoI): OC = O
1755cm " ¹ , X) COC, 1240cm" ¹ (broad) NMR spectrum: iCDO ?,
6.52 - 8.30 ppm (14H)

Y / hen the hydrate at 20 ⁰ C for one day and night was allowed to stand, 5.8 g of colorless crystals were obtained which the 1- (2,4,6-trichlorophenyl) -3- (3- (a- (2, 4-di-tert-amylphenoxy) acetamido) benzamido) pyrazole-4,5 "-di-phenylkohlensäureest he (coupler 20) having a melting point of 126 - 13O ⁰ C corresponded.

NMR spectrum: £

6.46 - 6.29 ppm (19H)

Elemental analysis:

Found: C, 60.82; H 5.11; N, 7.11 Calculated: C, 61.0; H 5.08j N 6.95

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ο Λ 179Λ5

Preparation example 4 /. η ι ι ο t ο

Preparation of 1- (2,4,6-irichlophenyl) -3- (2-chloro-5- (a- (2,4-di-tert-araylphenoxy) butylamido) anilino) -5-pyrazolonyl- (4) - benzyl carbonate (Coupler S).

This coupler was made in a manner analogous to that of the coupler manufactured. 24.2g 1- (2,4,6-Trichlca? Phenyl) -3- (2-chloro-5- (a- (2,4-di-tert-aTnylphenoxy) - "butylamido) aniline) 4-hydroxy- 5-pyrazolone were dissolved in 800 ml of anhydrous diethyl ether, and 12.4 g of benzyl chlorocarbonate and 7.5 g Iriäthylarain was added and the mixture was reacted. That Precipitated triethylamine hydrochloride was filtered off and 4.0 g of triethylamine were added to the piltrate. The failed one Solid was filtered off, dissolved in 60 ml of acetic acid, poured into 700 ml of ice water and then the precipitated plague filtered off and dried. Yield: 20.4g; Melting point: 118-119 ° G

IR spectrum (Nujol): v? C = O

1761 cm " ¹ , vC-OC, 1241, 1230cm" ¹ KKR spectrum: ^ COCf,

5.12 ppm (2H), 6.47 - 8.15 ppm (13H) Elemental analysis:

Found: C, 60.32; H 5.46; N 6.68 Calculated: C 60.50; H 5.40; N 6.57

Production example 5

Preparation of 1- (2,4,6 ^ trichlorophenyl) -3- (3- (a- (2,4-di-tert-amylphenoxy) acetamido) benzamido) -5-pyrazolonyl- (4) -ethyloxalic acid ester (Coupler 11).

27.3 g of 1- (2,4,6-trichlorophenyl) -3- (3- (a- (2,4-di-tertamylphenoxy) acetamido) benzamido) -4-hydroxy-5-py3: azole were added in 1000 ml anhydrous diethyl ether dissolved, mixed ester with 11.8 g Chloroxalsäureäthyl and stirred at 20 ⁰ G for a few minutes. Then 6.9 g of pyridine was added dropwise to the

• A098A7 / 1025

■ - 30 -

The mixture was added, reacted for 10 minutes and the precipitated oily substance was removed. This was dissolved in 60 ml of acetic acid, poured into 1000 ml of ice cream and the precipitated pesticide was filtered off. After drying, the pesticide was dissolved in diethyl ether, mixed with 4.2 g of triethylamine and the precipitated pesticide was filtered off. Compartment of sufficient water before with diethyl ether the pest was redissolved in 5CmI acetic acid, poured into 800 ml of ice water and the precipitated pest was filtered off and then dried. Yield: 19, sg; Melting point: 126-128 ⁰ C.

IR spectrum (Nujol); oC-0

176.2cm ~ ¹ , 17 ^ £ cm ~ ¹ , vC-OC, 12-4Ccm ~ ¹ (wide) NKR spectrum: iGOC £ ^

4.53 ppm (2H, q, 7cps), 6.62 - 8.28 ppm (9H) Elemental analysis:

Found: C, 55.40; H 5.36; F 7.32 calculated: C 58.10; H 5.22; IT 7.13

As used herein, the term "aromatic primary amine developing agent" denotes a compound which has a primary amino group on an aromatic ring and which is capable of developing exposed silver halide, or a precursor which is capable of forming a such connection is suitable. In particular, F, F-phenylenediamines are suitable for the practice of the invention. Further examples of such amines are 4-amino-3-ynethyl-F-ethyl-F- (methoxyethyl) aniline, "^ -amino-3-methyl-N-ethyl-F- (ethoxyethyl) anil in, 4 -Am ino - ^ - ethoxy-L ", Fd iäthy lan il in, 4-amino-3,5 ~ dimethyl-F, li-diethy! aniline, 4-amino-3-methyl-F-ethyl-F- (ß- hydroxyäthy1) anil in, 4-amino-3-methyl-F, IT-diethylaniline, 4-amino-3-ethyl-F-ethyl-F- (ß-methanesulfonamidoethyl) aniline, ^ -amino-3- (ß- methanesulfonamidoethyl) -F, F-diethylaniline, A -amine oF-ethyl-F- (£ -hydroxy-ethyl) anil in, ^ -amino-F, 2T-diethy 1-aniline and 4-araino-2i-ethyl-F -6i-sulfobutylaniline. The photographic materials according to the invention are treated with a solution containing any of the above aromatic primary amines as a developing agent, an alkaline agent and optionally a preservative, antifoggant and

409847/1025

and containing sensitizer, developed after exposure. . Suitable examples of such additives are given in C.E.K. Mees and T.H. James, The Theory of the Photographic Process and U.S. Patents 2,592,364, 2193,015 and the like.

The silver halide emulsion according to the invention comprises a silver halide such as silver curl chloride, silver bromide, silver iodine or mixed silver halides such as silver chlorobromide, silver iodobromide or silver chloroiodobromide dispersed in a hydrophilic high molecular weight material such as gelatin. The grain size can range between a uniform grain size up to a grain size with a broad grain size distribution vary. Depending on the end use objects of the light-sensitive material, the emulsion becomes Conveniently chosen with an average grain size within a range of about 0.05 to about 3 microns. For example, the silver halide emulsion can be prepared using a mixing method such as a single nozzle or a Double nozzle process or using a ripening process, e.g. with ammonia, neutral or acidic processes, getting produced. In addition, the silver halide emulsion can undergo sensitizing treatment such as "sulfur sensitization, Gold sensitization or reduction sensitization using standard procedures. Suitable examples of chemical sensitizers are gold III compounds, like gold-III-chloride compounds accordingly U.S. Patent Nos. 2,399,083, 2,540,085, 2,597,656, 2,597 and the like, noble metal salts of platinum, palladium, iridium, rhodium or poithenium according to the US patents 2,448,060, 2,540,086, 2,566,245, 2,566,263, 2,598 C79 and the like, sulfur compounds which are formed with silver salts to form Silver sulfide react, as in U.S. Patents 1,574,9 ^, 2,410,689, 3,169,458, 3,501,313 and the like, reduction compounds of tin (II) salts or compounds containing amine groups corresponding to U.S. Patents 2,487,850, 2,518,698, 2 521 925, 2521 926, 2 694 637, 2 983 610, 3 201 254 and the like. The emulsion can also contain a sensitizer, such as polyoxyethylene

409847/1025

Compounds and onium compounds included. Raises emulsions only such that a latent image is mainly formed on the surface, but also from the internal, latent one Image type in which a latent image is mainly within the grain is formed, according to the invention verv / ends, as they are e.g. by C.E.K.Mees and T.H.James, The Theory of the Photographic Process.

Suitable hydrophilic high molecular weight materials for forming the photosensitive layer according to the invention proteins, such as gelatin, are high electrolytes Molecular weight, such as polyvinyl alcohol, polyvinyl pyrrolidone and polyacrylamide, acidic high molecular weight materials,

Polyacrylates and

such as alginates and amphoteric electrolytes of high molecular weight, such as polyacrylamides treated by Hofmann rearrangement reaction and acrylic acid-N-vinylimidazole copolymers. The one High molecular weight continuous phase-forming hydrophilic materials can be a dispersed hydrophobic material ν.η high molecular weight, for example a latex of butyl polyacrylate.

The silver halide photographic emulsions according to Invention are applied in a favorable manner on a carrier. Hard materials such as glass, metals and Ceramic and flexible materials used depending on the end use tasks. Typical flexible supports are ceilulose nitrate films, cellulose acetate films, polyvinyl acetal films, Polystyrene films, polyethylene terephthalate films, polycarbonate films and laminates therefrom, papers coated with baryta and papers coated with α-olefin polymers, for example Polyethylene, polypropylene and ethylene-butene polymers and Plastic films with a roughened surface, accordingly Japanese Patent Publication 19066/1972. Dependent on of the end uses of photosensitive materials the carrier can be transparent, colored by the addition of a dye or pigment, by the addition of, for example Titanium white, opaque or blackened by adding carbon black, for example.

409847/1025

The formation of the color image according to the invention can be performed in achieved photosensitive materials of various forms v / earth. One form is a photosensitive material with a silver halide emulsion layer having a contains diffusion-resistant couplers on a carrier, with an alkaline developer which is an aromatic primary 1min as a color developing agent, treated so thatS a water-insoluble or diffusion-resistant dye is formed in the emulsion layer. Examples of such systems are in U.S. Patents 3,419,391, 2,304,939,

2 322 027, 2 949 360, 2 S01 171, 2 801 170, 3 311 476, 3 271 152,

3,519,429 and the like. Another form is a photosensitive material having a silver halide emulsion layer in combination with a diffusion-resistant coupler on a carrier with an alkaline developer which contains an aromatic primary amine as a color developing agent, treated to form a soluble and diffusible dye in the aqueous medium and then to another Transferred receiving layer from a hydrophilic colloid. this is a diffusion and transfer color system. Examples of such S3 systems are given in US Patents 3,342,597, 3,227,551, 3,227,550, 3,227 55 ^, 3,644,498, 3,476,563, 3,352,672, 3 3? C 655 and the like.

Couplers 16, 17 and 21 can be used for the second form given above, while the other couplers can be used for the first form specified.

The 5-pyrazolone couplers according to the invention, v / or in the 4-position is substituted with a carbonic acid ester or oxalic acid ester group and which has a hydrophobic radical of S and more Carbon atoms are dissolved in an aqueous medium or organic solvent and then in a phctographic Dispersed emulsion.

The oil-soluble and diffusion-resistant couplers used in the internal _v type are incorporated into a photosensitive material in which the coupler is in an organic solvent.

409847/1025

solvent and then the solution r> id ^ r photcgrarhisruaen emulsion dispersed as fine colloidal grains we ^ .4 17

One coupler dispersion process suitable for the practice of the invention is detailed, for example, in U.S. Patent 3,676,137. Organic solvents for dissolving the coupler, which are hardly soluble in water, have a high boiling point, for example above 1.7O ⁰ Cj, and are present in the light-sensitive color material together with the coupler, are composed of substituted hydrocarbons, carboxamides, phosphoric acid esters and ethers, for example egg n-butyl phthalate, di-i-octyl acetate, di-n-butyl sebacate, iricresyl phosphate, tri-n-iiexyl phosphate, Ν, ΐί-diethylcaprylamide, butyl-n-pentadecylphenyl ether and chlorinated paraffins. Besides these high boiling point solvents, auxiliary solvents for dissolving the coupler, which can be removed during the preparation of the light-sensitive material, are preferably used, for example, ethyl acetate, butyl acetate, cyclohexanol, tetrahydrofuran and cyclohexanone.

Surfactants are preferably used as adjuvants for dispersing the oil-soluble internal type coupler finely in the hydrophilic one used as a photographic emulsion High molecular weight material used. Examples of such surfactants are anionic surfactants Agents, for example Imtriumcety! Sulfate, liatrium p-dodecylbenzenesulfonate, Sodium nonylnaphthalene sulfonate and sodium di (2-ethylhexyl) -a-sulfosuccinate and nonionic surfactants Agents such as sorbitan sesquioleic acid esters and sorbitan monolauric acid esters.

For dispersing an oil-soluble coupler suitable Emuigierhomogenisatoren, colloid mills and Ultraschallwellenemulgiergeräte. A diffusion-resistant coupler having a ballast group and a carboxylic acid group or sulfonic acid group in the same molecule is soluble in neutral and weakly alkaline aqueous solutions. The coupler can be incorporated into the photographic emulsion by adding the aqueous solution containing the coupler to the photographic emulsion. The coupler is believed to be resistant to diffusion through the formation of micelles in the hydrophilic high molecular weight material. 409847/1025

ORIGINAL INSPECfED

The 2-equivalent couplers according to the invention can along with one or more of the magenta couplers, such as see them in U.S. Patent Nos. 2,439,098, 2,369,489, 2 600 788, 3 558 319, 2 311 081, 3 419 391, 3 006 759, 2 292, 2 908 573, 3 519 429, 3 152 896, 3 062 653, 3 311 476, British Patent 956,261, Japanese Patent Publication 19032/1971, Japanese Patent Applications 114445/1972 and 114446/1972 are described, the magenta-colored Couplers such as those described in U.S. Patents 2,983,608, 2,455,170, 2,725,292, 3,005,712, 3,519,429, 2,688,539, British patents 800 262, 1 044 and Belgian patents 676 691 are given, the so-called DIR-type couplers, which are used to release a compound imagewise development during the Development suppressed, for example, the monothio-type couplers such as those described in US Pat. No. 3,227,554 and the United Kingdom Patent 953 454 are described in the O-aminophenylazotype couplers described in U.S. Patent 3,148,062; the couplers described in U.S. Patent 3,006,759 of the 4-halo-pyrazolone type and those in Japanese Patent Publication 8750/1972 and the German OLS 2 163 811 described couplers and the hydroquinones) for the release a compound that suppresses development are capable of development during development, as described in U.S. Patent 3,297,445 and British Patent Specification

1 058 606 are given.

In order to increase the stability of the color photographs, it is advantageous if the light-sensitive material according to According to the invention, a p-substituted phenol derivative in the emulsion layer or in a layer adjacent thereto contains. Particularly suitable p-substituted phenol derivatives can be derived from one or more of the hydroquinone derivatives, as described in U.S. Patents 2,360,290, 2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,710,801, 2,728,659

2,732,300, 2,735,765, 2,816,028 are given, the gallic acid derivatives, as they are in the US patents

409847/1025

3,457,079, 3,069,262 and Japanese patent publication are given 13496/1968, those described in U.S. Patents 2,735,765 and 3,698,909 mentioned p-alkoxyphenols and in the US patents 3432300, 3573050, 3,574,627 and 3,764,337 specified p-oxyphenols can be selected.

For the purpose of image stability, the light-sensitive material according to the invention may preferably be an ultraviolet absorber the emulsion layer or an adjacent layer, as in U.S. Patents 3,250,617 and 3,253,921 are given.

The hydrophilic colloid layer in the photosensitive Materials according to the invention, in particular the gelatin layer, can be prepared using conventional methods cured using various crosslinking agents. Examples of such hardeners are aldehyde group end compounds such as formaldehyde, glutaraldehyde, ketone compounds such as diacetyl, cyclopentadione and the like., reactive, halogen-containing compounds such as "bis (2-chloroethylurea), 2-Hydroxy-4,6-dichloro-1,3,5-triazine, as described in U.S. Patents 3,288,775 and 2,732,303 to U.K. Patents 974 723 and 1 167 207 and the like., active compounds containing vinyl groups, such as divinyl sulfone, 5-acetyl-1,3-diacryloylhe ^ hydro-1,3,5-triazine correspondingly U.S. Patent Nos. 3,635,718 and 3,232,763 to U.K. Patent specification 994 869 and the like, N-methylol compounds, such as N-hydroxymethylphthalimide according to the U.S. Patents 2,732,316 and 2,586,168 and the like containing isocyanate groups Compounds as disclosed in U.S. Patents 3,017,280, 2,983,611, and the like, organic sulfuric acid or carboxylic acid derivatives according to US Pat. No. 3,100,704, epoxy compounds, for example as indicated in US Pat. No. 3,091,537, the one Isooxazole group-containing compounds as described in the

409847/1025

U.S. Patents 3,321,313 and 3,543,292 are cited are, the compounds containing a halocarboxyaldehyde group, such as mucochloric acid, dioxane derivatives such as dihydroxydioxane, Dichlorodioxane or inorganic hardeners such as chrome alum, zirconium sulfate and the like.

In addition, alkali bisulfite-aldehyde adducts, methylol derivatives of hydantoin and primary, a fatty acid group containing nitro alcohols can be used as curing agents. Non-aldehyde type crosslinking agents, for example Compounds having a plurality of epoxy rings as described in Japanese Patent Publication 7133/1959, Poly (1-aziridinyl) compounds. as described in Japanese Patent Publication 8790/1962, and active Halogen compounds as in U.S. Patents 3,362

and 3,325,287 are particularly suitable for use in the light-sensitive materials according to FIG Invention.

The following examples serve to further aa. Explanation of the invention in detail.

example 1

A mixture of 23 g of 1- (2,4,6-trichlorophenyl) -3- (3- ( ^c ^ - 2,4-di-tert-amylphenoxy) acetamido) benzamide) -5-pyrazolonyl- (4) -benzyl -Kohlcnsäureester (coupler 3) 1 20 ml of tricresyl phosphate and 40 ml Ithylacetat were heated to 60 ⁰ C to prepare a solution and the resulting solution to 250 ml of an aqueous solution containing 25 g of gelatin and 0.75 g _E S Sodium dodecylbenzenesulfonate of 60 ^° C. were added, whereupon vigorous mechanical stirring was carried out

09847/1025

^"38 -. ■ 2417345

and an emulsified Kujpler dispersion was obtained. The resulting coupler emulsion was added with 200 g of a photographic emulsion containing 11.2 10 "mol of silver chlorobromide (silver bromide 45 mol%, silver chloride 55 Mo 1%) and 20 g of gelatin, and after 10 ml of a 3% solution of triethylenephosphamide when hardener in acetone had been added to this _v the final pH had been adjusted to 6.5, the mixture was drawn down on a cellulose siriacetate film base to a pilm thickness of 4.3 microns on a dry basis (PiIm A)

ρ
Lielt each 1m, an amount of 1.55

and 6.2 10% ol silver chlorobromide.

2 -3

each contained 1m, an amount of 1.55 x 10 -'Mol of the coupler

For comparison, 18.9 g of 1- (2,4,6-trichlorophenyl) -3- (3- ( ^{c <} - (2,4-di-tert-amylphenoxy) acetamido) benzamido) -5-pyrazolone (coupler (A)) as a corresponding comparative coupler in which the coupling position was not substituted, instead of the coupler indicated above, dispersed in a manner analogous to that of the coupler described above, and mixed with 400 g of the same emulsion as indicated above and absorbed onto a PiIm so that a Pilm thickness of 5/1 microns on a dry basis was obtained

2 (PiIm B). This PiIm contained 1 m each, a quantity of

1.57 x 10 " ¹ mole of the coupler and 12.6 χ 10" ⁵ moles of silver chlorobromide.

These pilms were subjected to stepwise exposure and then subjected to the following development treatments.

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- 39 - I) color development • 21 ⁰ G 24Ί7945 1..Color development ti 2. Water wash It 12 min. 3 · First fixation Il 30 see. 4. Water washing ti 4 min. 5. Bleaching It 4 min. 6. Water wash Il 8 min. 7 · Second fixation Il 4 min. 8. Water washing 4 min. 6 min.

II) Liquid composition of color development

Sodium hexainetaphosphate 2 g

Sodium sulfite (anhydrous) 2 g

Benzyl alcohol 5 ml

Sodium carbonate (monohydrate) 27.5 g

Potassium bromide 0-5 g

Hydroxylammonium sulfate 2.5 g 4-amino-3-methyl-N-ethyl-N- (ß-methane

sulfonamidoethyl) aniline sesquisulfate 2.5 g

III) fixing solution

Sodium thiosulfate (hexahydrate) to 80 g Sodium sulfite (anhydrous) (pH = 5 g borax 6 g Glacial acetic acid 4 ml Potassium alum .7 g water 1000 ml 4.5)

40 9-8 47/1025

IV) bleach bath to 100 S. Kai iume is en-III-cyanide (pH = 5 ε Potassium bromide 10 S. Boric acid 5 ε borax 1000 ml water 7.2)

After the treatments, the films were subjected to the determination of the optical density with green light, whereby the photographic properties listed in the following table were obtained. A sharp color image was obtained with an absorption maximum of 548 m Ai .

Table 1

Photographic properties of AgX /
Coating quantity coupler _rel *

^ ^{3 (} ig stlrL sole eggs gamma

1.55x 6.2x 4 4.3 0.03 3.9 100 3.61

B a 1.57x 12.6x 8 5.1 0.02 2.25 96 2.48

■ * Relative sensitivity describes the amount of exposure required to get a fog density of +0.1.

Table 2 Development time for maximum color density

Film * J min 8 min 12 min 16 min

A 3.52 3.59 3.61 3-61

B 2.36 2.45 2. * i8. 2.51

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ORfGlMAL INSPECTED

After the stepwise exposure, Films A and B were subjected to the above treatments 1-4 and dried, and the amount of developed silver per unit area was measured by fluorescent X-rays. Then, the films were subjected to the above treatments 5 to 8, and the magenta color images were obtained. From these films, the dyes were mixed with a mixture of dimethylformamide and water ^; The volume ratio of 85 x 15 was extracted and subjected to quantitative determination using an absorbance method. When the molar ratios of developed silver / colored dye at the various density levels were calculated, film A gave an amount of 2.8 to 3.4 and film B an amount of 8 to 0.5, as shown in the accompanying drawing evident.

It is clear from these values that the inventive Coupler, i.e. the 2-equivalent coupler, with a carbonic acid ester group in the 4-position with respect to the 4-equivalent coupler with the corresponding skeleton is superior to various properties.

As can be seen from the values in Table 1, brings the coupler according to the invention has a higher sensitivity and gradation as well as a maximum developed density, itself when the silver halide / coupler ratio drops to about 1/2, and it is evident from the values in the table 2, that the application of the coupler according to the invention results in a marked shortening of the development time. Furthermore shows from the accompanying drawing that when using the coupler according to the invention, the necessary amount of developed silver to obtain a color image having a certain density can be reduced to a greater extent can. These values show that the amounts of coupler and

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mounted silver halide ^ which are necessary to produce a obtain certain maximum developed density can be reduced and the development time can be shortened,

Example 2

Using "Film A" and "Film B" as indicated in Example 1, the following treatments were carried out carried out:.

V) color development

1. Color development 30 ⁰ G 4- min 2. Bleaching and Fixation It 2 min 3- Water washing 2 min 4th Stabilizing bath 2 min

The photographic properties of the films obtained are shown in Table 3.

With regard to Treatment 4, the stabilizing bath, two types of stabilizing baths, viz. Stabilizing bath (a), which contained no formaldehyde, and a stabilizing bath (b), which contained 1% of 40% formaldehyde, were prepared. The films were each treated with these baths, left to stand at 80 ^° C. for 1 week, and the density decrease ratio, based on the initial density, was measured. The results are shown in Table 4.

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VI) Liquid composition of the color development

Sodium metaborate 25 B Sodium sulfite 2 g Hydroxylamine (SuIfat) "2 g Potassium bromide 0.5 g 6-nitrobenzimidazole (nitrate) 0.02g Sodium trium hydroxide 4 g Benzyl alcohol 15.8 ml Diethylene glycol 20 ml ^ -Amino ^ -methyl-N-ethyl-N- (ß- methanesulfonamidoethyl) aniline sesquisulfate ö S Water too 1000 ml VII) Bleaching and Fixing Solution

Iron (III) ethylene diamine tetraacetate 45 g

Ammonium thiocyanate 10 g

Sodium sulfite 10 g

Ammanium thiosulphate (60%) 100 ml

Sodium ethylenediamine tetraacetate 5 g

1000 ml of water

VIII) Stabilizing bath (a)

Tartaric acid
Zinc sulfate
Sodium metaborate
water

to

10 g 10 g 20 g 10Ö0 ml

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Stabilizing bath

Tartaric acid zinc sulfate sodium metaborate formalin (40%) water too

10 g 10 g 20 g 10 ml ml

Coupler

Tabel Photographic properties

Stabilizing bath (a)

veil gamma

maximum developed density

0.04

0.03 3.12

2.30

3.65

2.45

Movie

Tabel

Durability of the developed color image (80 ⁰ C, leave to stand for one week)

Stabilizing bath initial density O ₁ J? 1.0

2.0

away

away

15% 10% 7% 12th 8th 7th 70 53 15th 13th 9 8th

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The values in Table 3 show that the use of film A gives sufficient photographic properties even if a strong oxidizing agent is not used, as in the development according to Example 1, and film A far better properties than film B Has. The results of Table 4 show that Film A shows sufficient heat durability even if it has not been subjected to any stabilizing bath treatment which contains formaldehyde as is known.

Example ^

A mixture of 10 g of 1- (2,4,6-trichlorophenyl) -3- (3- £ x- (3-n-pentadecylphenoxy) butylamido) benzamido) -5-pyrazolonyl- (4) -ethyl-carbonic acid ester ( Coupler 18) 0.8 g of 2,5-di-tert-octylhydroquinone, 0.8 g of 6.6 ^l -dihydroxy-7,7'-dimethyl-4,4.4 ^l , 4 ^l -tetramethyl-bis- 2,2'-spirochroman, 10 ml of dioctylbutyl phosphate and 30 ml of ethyl acetate was heated and dissolved on a steam bath and to an aqueous solution which 10g

Gelatin and 0.5 g of sodium cetyl sulfate was added, which was followed by vigorous mechanical stirring and the emulsified coupler dispersion was obtained. This emulsion was mixed with 100 g of a photographic emulsion with a content of 4.7 χ 10 " ² mol silver chlorobromide (silver chloride 50 mol% silver bromide 50JDlol%), and 9 g.gelatine, then 3 ml of a 4% aqueous solution of 2-Hydroxy-4,6-dichloros-triazine-sodium salt was added as hardener and the pH-value was adjusted to 6.3 The resulting mixture was drawn up on a polyethylene resin-coated baryta paper and gave a coating thickness of 1.6 microns

—4 on a dry basis (film C). This movie was 5.2 χ 10

Moles of coupler and 2.0ö χ 10 "" ^ moles of silver halide per 1 m raised.

40 9847/1025

For comparison, another emulsified dispersion was made in the same manner as above, however using 9.0 g of one unsubstituted in the 4-position corresponding matching coupler, namely 1 - (2,4,6-trichlorophenyl) -3- (3- (ot- (3-n-pentadecylphenoxy) butylamido) benzamido) -5-pyrazolone (coupler b) instead of the coupler of film C, with 200 g of the emulsion the same composition mixed and soaked up to give a coating thickness of 2.8 microns dry basis (film D)

—4 was obtained. In this film there were 7.6 10 moles des

Coupler and 6.08 χ 10 "^ moles of silver halide per 1 a ² drawn up.

When these samples were subjected to development (stabilizing bath a) in the same manner as in Example 2 and The reflection density was determined with green light, the photographic properties given in Table 5 obtain. A sharp color image with a principal wavelength of 54-1 m / rev was obtained.

Table 5 Photographic feature

Film coupler amount (mol / m ² ) coupler
KX (

g (/) pp ^ ΐ ?? ίΓ ^ ίί

Coupler AgX (Molar Ratio) Veil Gamma £? G £ eit Density

5.2 ₄ x 2.08 ^ χ 4 0.07 2.53 100 2.35 b 7.6 ^ x 6.08x 8 0.05 2.59 98 2.40

It follows from the values in Table 5 that d, as under Using the coupler according to the invention, the light-sensitive material produced the same photographic properties as already known materials, even if the coating amounts of the coupler and silver halide are decreased will.

409847/1025

Table 6 shows the light permanence when the developed films thus obtained were exposed to a sunlight fluorescent lamp of 10,000 lux through a filter capable of absorbing virtually all ultraviolet rays having a wavelength of 400 myu or less for 12 days , the heat durability when these films were allowed to stand at 80 ⁰ C in the dark for a week, and the moisture durability when these films were stored in the dark at 60 ⁰ C and 75% relative humidity for 2 weeks by the reduction ratio of the density (% ), based on the initial figure.

Table 6

Resistance of the color images (thickness decrease ratio%)

Fluorescence- 60 ⁰ C, 75% relative humidity-FiIm Coupler lamp-12 days- 80 C, 1 week 2 weeks starting density starting density starting density

0.5 1.0 2.0 0.5 1.0 2.0 0.5 1.0 2.0 C 18 17 14 8 12 8 6 5 3 0

D b 25 21 14 64 54 18 7 5 2

It follows from these values that when using the. Coupler according to the invention, an image can be obtained which is far more resistant to heat, light, high Temperature and high humidity compared to using a 4-equivalent coupler with a scaffold accordingly the coupler of the present invention can be obtained.

409847/1025

Example 4

A blue-sensitive silver chlorobromide emulsion, which was ty-pivaloyl-c <- (2,4-dioxc-5,5 dimethyloxazolidinyl) -2-chloro-5- (K- (2,4 -di-teit.-ramjl phenoxy) butylamido) acetanilide, to a thickness of 3.0 microns ( amount of silver _{coating 3?} 53 x 10 ^ mol / m; amount of coupler drawn: 1.2 10 mol / m) and further as the second Layer a 2-tert-octylhydroquinone-containing gelatin layer drawn to a thickness of 1.5 microns. Furthermore, an emulsified dispersion of a coupler was prepared in the same way, but using 8.25 g of the coupler 19 according to the invention, namely 1- (2,4,6-trichloro) -phenyl-3 - ((2-chloro- 5-n-tetradecanamido) anilino) -5-pyrazolonyl- (4) -ethyl-carbonic acid ester instead of the coupler 18 of Example 3 and using tricresyl phosphate instead of the dioctylbutyl phosphate, added to a green-sensitive photographic emulsion with the same composition as in Example 3 and drawn up to a coating thickness of 1.7 microns as the third layer (amount of silver drawn: 2.08 χ 10 -4 mol / m;

—4 2 absorbed amount of coupler 5 ₅ 2 χ 10 mol / m) and furthermore a gelatin layer with a content of 2,5-di-tert-octylhydroquinone and as an ultraviolet absorbent 2- (5-chlorobenzotriazol-2-yl) -4- methyl-6-tert.-butylphenol and 2- (benzotriazol-2-yl) -4-tert.-butylphenol to a coating thickness of 2.5 microns as a fourth layer, a red-sensitive emulsion with a content of 2- ( o (- (2,4-di-tert-amyl-phenoxy) butylamiio) -4,6-dichloro-5-methyl-phenol to a coating thickness of 2.5 microns as the fifth layer

(Amount of silver drawn up 2.94 χ 10 ~ ^ mol / m ·, drawn up

_-z ρ
Coupler amount 1.1 χ 10 -4 mol / m) and then gelatin was made to a thickness of 1.0 micron as the top layer

409847/1025

drawn up so that a color reproducing paper was obtained.

This color reproduction paper was made by, a color negative exposed and developed in a manner analogous to Example 2. The color reproduction obtained was sharp color photographic Image of very excellent color rendering, which is a magenta color image with an absorption maximum at 541 m / rev.

When this color rendering was directly exposed to sunlight for a week, the decrease was Density of the magenta image at an initial reflection density of 1.0 is only 0.0 ^ and even if it is under conditions of high temperature and high humidity, e.g. 60 ° C and 75% relative humidity, while After standing for 2 weeks, no substantial decrease in density was observed. In each case it was found that the non-image area hardly clouded.

Example 5

1.4 10 mol of each of the various couplers according to the invention was mixed with 10 al of triejesyl phosphate and 30 ml of ethyl acetate, heated to dissolve and added to 100 ml of an aqueous solution containing 10 g of gelatin and 0.5 of sodium dodecylbenzenesulfonate, whereupon was emulsified and dispersed. The emulsified dispersion was mixed with 100 g of a photographic emulsion which χ 5.6 10 ^-2 mole of silver bromide and 10 g of gelatin, mixed, and 3 ml of a 4% aqueous solution of 2-hydroxy-4,6-dichloro-s Triazine urodium salt hardener was added and then applied to a film of cellulose triacetate to a coating thickness of 2.5 microns.

409847/1025

- 50 -. 2-17945

The film thus obtained was exposed to light and then subjected to the same development treatments as in FIG Subjected to Example 1, however, the following color developer was used solution used and the treatment effected in 14 minutes, so that a sharp magenta color image is obtained became.

IX) Color Development Solution

4-Amino-3-methyl ~ N, N-diethylaniline - 2.5 g hydr.ochlorid

Sodium sulfite (anhydrous) 10 g

Sodium carbonate (monohydrate) 47 g

Potassium bromide. 2 g

1000 ml of water

(pH = 10.5)

The wavelength of the absorption maximum of each film is shown in Table 7.

409847/1025

Table 7

Coupler and absorption maximum of the developed color image

Coupler ITr. Wavelength coupler no. WelÜsilänge coupler no. WeHe:

1 length in / U τα. Ai m / U

2,551 3,552

4 552 5 552 6 546

7 552 8 545 9 .545

10 546 11 552 12 545

13 531 14 548 15

16 17 18

19 545 20 552- 21

22 23 547 24 54-5

25 552 26 543 27 552

28 540 29

Example 6

A red-sensitive silver iodobromide emulsion was applied as the first layer to a transparent cellulose triacetate carrier containing 1-hydroxy-2-tetradecylnaphthamide to a thickness of 5 ^ 0 microns (amount of silver absorbed

—P P —3

• 2.12 χ 10 mol / m, absorbed cupolene amount 1.8x10 Mol / m) and as the second layer a gelatin layer with a content of 2,5-di-tert-octylhydroquinone to one Drawn thickness of 1.0 micron.

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17 g of coupler 23 according to the invention, 2.0 g of 1- (2,4,6-trichlorophenyl) -3 - ((2-chloro-5-tetra4ecyloxycarbonyl) anilino) -4- (C <-naphthylazo) -5 -pyrazolon, 12 ml Trieresylphosphat and 50 ml of ethyl acetate were heated at 60 ⁰ C and dissolved. The resulting solution was added to 150 ml of an aqueous solution containing 15 g of gelatin and 0.4 g Katriumdodecylbenzolsulfonat added at 60 ⁰ C, and stirred the mixed solution vigorously and mechanically using a homogenizer, so that the coupler emulsified dispersion was obtained. The emulsion obtained was mixed with 500 g of a green-sensitive photographic emulsion containing 3 × 10 mol of silver iodobromide (silver «] odide 6 mol%, silver bromide 94 mol%) and 30 g of gelatin, including 5 ml of a 3% solution of the sodium salt of 2-hydroxy-4,6-dichloro-s-triazine in acetone was then added as a hardener - and the pH was finally adjusted to 70. This emulsion came in third

-? ? Layer (applied amount of silver 1.85 x 10 ~ mol / m; extended Coupler amount 1.74 χ 10 "" ^ mol / m including 1.59 x 10 ~ ^ mol / m of the coupler 23) to those given above Coating to a coating thickness of 5 * 1 micron Raised dry basis.

409847/1025

Furthermore, a gelatin gel was applied to the resulting coating. mixture containing yellow colloidal silver and 2,5- & i-t-octy! hydroquinone in a thickness of 1.5 microns and a blue-sensitive silver photographic emulsion containing a- (p-methoxybenzoyl) -a- (5th , 5-diinethyl-3-hydantoinyl) -2-chloro-5- (Y- (2 ", 4" -di-t-aray! Phenoxy) -butylamido) -acetanilide, as a fifth layer (amount of silver absorbed 1.0 χ 10 "mol / m, absorbed amount of coupler 1 χ 10" x ⁵ mol / m) in a thickness of 5.0 microns and a gelatin protective layer in a thickness of 1.0 micron as the top layer, so that a light-sensitive earbnegativ material obtained v / urde.

When this PiIm is exposed and the following development was subjected to an excellent color negative with a high sensitivity and good graduation and image quality obtain. The density of blue light was practically constant and independent of the extent of exposure to green light, and the color correction was satisfactory.

X) color development

1. Color development

2. Stop treatment? V / ater laundry

4. Bleaching

5. Viasser wash

6. Fixation

7. Wash basins

8. Stabilizing bath

XI) color developing solution

Sodium hydroxide Sodium sulfite potassium bromide sodium chloride

Borax 409847/1025

38 ° C 2 G 3 Wed It 2 G 1 Il η O, 4th 1 Il Il 1 G 2 Il ti 4th G 1 Il Il 2 Il η 1 Il It 1 It G

Hydroxylammonium sulfate 2 g

Ethylenediaminetetraacetic acid 2 g 4-Amino-3-methyl-II-ethyl-IT- (ßhydroxyäthy1) aniline-honosulfate monohydrate . ' 4 g

1ΌΟΟ ml of water

XII) stoppage

Sodium Thiosulfate Ammonium Thiosuli'ate (£ 70) Sodium acetate

acetic acid

Potassium alum

water

10 G 30th ml 5 G 15th G to 1Ö00 nl

XIII) Verification

Iron-ill-sodium-ethylenediamine- 100 g .tetraacetate ^ dihydrate. ·

Potassium bromide 50 g

Ammonium nitrate 5Cg

Boric acid 5 g

Ammonia water to adjust the

pH value on water to 1000 ml

XIY) fixing solution

Sodium Thiosulfate '15Cg

Sodium sulfite 15 6

Borax 12 g

Glacial acetic acid 1-5 ^ lL

Potassium alum 20 g

1000 ml of water

409847/1025

XY) stabilizing bath

Boric acid 5 g

Sodium citrate. 5 g

Sodium metaborate (tetrahydrate) 3 g potassium alum - 15 g

1000 ml of water

Example 7

On a film base made of polyethylene terephthalate with a thickness of 0.15 microns, a first layer of an n-hexyl half-ester of a copolymer of vinylraethyl ether and maleic anhydride (molar ratio 1: 1 ~ i molecular weight about 50,000) with a thickness of 20 microns, a second layer of a 50% hydrolyzate of polyvinyl acetate (molecular weight about 100,000) and with a thickness of 12 microns, a third layer of "1 part by weight of an acid-treated gelatin and 1 part by weight of poly-Nn-butyl-6-methyl-3 vinylp3 ^r ridinium chloride (molecular weight about 50,000) 7 microns thick, a fourth layer of 10 parts by weight of rutile type titanium oxide and 1 part by weight of gelatin to a thickness of 12 microns, and then a fifth layer of 1 part by weight of carbon black and 5 parts by weight of gelatin in one thickness · Pulled up by 3 microns.

5 g of the sodium salt of coupler 16 were dissolved with heating in a mixed solvent of 70 ml v / ater and 30 ml 2-methoxyethanol and the resulting solution was stirred into "250 g of an aqueous solution containing 0.1 g of finely dispersed colloidal silver and 30 g of gelatin at 50 ⁰ C.zugesetzt. The mixture was cooled to 5 ⁰ C and solidified VCN into square rods about 5 mm cut with an aqueous solution containing 0.6 g of magnesium sulfate containing 1000 ml, at 5 ° C v / ash for 5 hours, heated to re-dissolve at 40 ⁰ C, with 10 ml of a 3% methanol

409847/1025

solution of triethylenephosphamide and 15 ml of a 3 / ^ igen aqueous Solution of saponin mixed and then as a sixth layer on the above-described coating in a pick of 7.5 microns grown on a dry basis.

After an intermediate layer of 1 part by weight of 2,5-di-t-cctylhydroquinone and 20 parts by weight of gelatin to form a starch of 1 micron on the resulting coating was optically with the sodium salt of anhydro-5,5'-diphenyl-3,3 '-disulfopropyl-9-ethyloxacarboeyanine hydroxide; 7d sensitized green-sensitive emulsion as eighth layer applied to the intermediate layer to a thickness of 4 microns. This emulsion contained 0.28 mol of silver iodobromide (iodine content ? MoI-Js !, average grain size 0.6 Ilikrpn) and 72g Gelatine per kg. Finally, a 1 micron layer of gelatin was applied as the top layer, making it photosensitive Material received. The obtained photosensitive Material gradually became sensitometry through a Covering a sheet of cellulose triacetate with a starch exposed for 0.1 min.

Was between the "cover sheet and the emulsion surface a viscous treatment solution of the following composition in spread out to a thickness of 0.15 ^:

developer

distilled water / water 1000 ml

Ascorbic acid. 0.2 g

4-amino-IT-ethyl-iT-ß-hydroxyethyl 25 g aniline sulfate

Potassium hydroxide 35 g

Benzotriazole 0.02 g

Hydroxyethyl cellulose 30 g

Carbon black 45 g

! laugh appeared about 30 seconds after the spread gradually the kagenta image, and it was found from the side of the terephthalate base that the image formation was in finished about 4 minutes.

409847/1025

The invention has been described above on the basis of preferred embodiments described without the invention being limited thereto.

409847/1025

Claims (1)

, - 58 - Claims /! - / Light-sensitive silver halide emulsion containing Ky a coupler of the general formula I or II, -OCO (CO) OR ₃ η (D or OCO (CO) _n OR ₁₁ OCO (CO) 0- (II) Rl R ₁ in which it ... a '., hydrogen & tor: cder a -G-rupce nit 1 tis about 50 carbon atoms from straight or branched chain Alkyl groups, an ilkenyl group, a cycloalkyl group, a su "substituted | alkyl group or a substituted cycloalkyl group, the as a substituent an Ealogenatom or a nitro, Cyano, aryl, alkoxy, aryloxycarboxy, alkoxycarbon yl, Aryloxycarbonyl-, SuIfO-, sulfamoyl-, carbamoyl-, acylamino-, Ureidoi Tiet'erocyclic group, aryl sulfonyl oxy or Cxo groups contain a substituted aryl group which contains at least one of the following groups: alkyl, alkoxy, aryloxy, Carboxy-, alkoxycarbonyl-, acylamino-, carbamoyl-, alkylca ^? Bamoyl-, Dialkylcarbamoyl, arylcarbamoyl, alkylsulfonamido, Arylsulfonamido, sulfamoyl, alkylsulfamoyl, cyano or nitrile groups or contain a halogen atom as a substituent, a heterocyclic group which is a nitrogen, Oxygen and / or sulfur atom contains a substituted heterocyclic group with those above for the aryl group specified substituents, a carbamoyl group or a 409847/1025 ORIGINAL INSPECTED Ihice &rberncylruppe; - Rp a group with 1 to about 50 / a carbon atoms the same alkyl, substituted alkyl, aryl, substituted Aryl, heterocyclic, or substituted heterocyclic Groups, as indicated for IL, an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, an alkoxy group, an aryloxy group, an alkythio group, an arylthio group, a carboxy group, an amino group, an alkylamino group, a cycloalkylamino group, an N, N-I) ialkylamino group, an IT-alkyl-H-arylamino group, a N-arylamino group, an amido group, an N-alkylacylamino group, an N-arylacylamino group, an ureido group, a K-arylureido group, an N-alkylureido group, a thioureido group, a ii-alkylthioureido group, an N-arylthioureido group, a carbamoyl group, a sulfamoyl group, a Piperidino group, a pyrrolidino group, a guanidino group, an N-alkylguanidino group. or an N-arylguanidino group, R, a group with 1 to about 30 carbon atoms straight-chain or branched-chain alkyl groups, an alkenyl group, a cycloalkyl group, an alkyl or cycloalkyl group which is halogenated or a nitro, cyano, aryl, Alkoxy, carboxyester, sulfoester, amide, sulfonamide, Ureido, carbamyl or SuIfamy! Group is substituted, a Aryl group having one or more halogen atoms or one Kitrc, cyano, alkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, Acyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, sulfcester, Amide, sulfonamido, ureido, carbamyl or sulfarayl group is substituted, a heterocyclic group known as Heteroatom contains a nitrogen, oxygen and / or sulfur atom or a substituted heterocyclic group, the contains the substituents given above for the aryl group, Typically a divalent group of 1 to 30 carbon atoms as an alkylene group or arylene group, 409847/1025 where either B .. or R _? can also form a divalent group with about 3G or fewer carbon atoms, which connects zv / ei 5-pyrazolone units of the general formulas I and / or II; and η are the numbers 0 or 1, which form a dye on coupling with the oxidation product of an aromatic primary amine is capable as a color developing agent. 2. A photosensitive silver halide emulsion according to claim 1, characterized in that the photosensitive Silver halide emulsion a p-substituted phenol in one effective length to stabilize the development with the dye image formed with the aromatic primary amine as a color developing agent. 3. A photosensitive silver halide emulsion according to claim 2, characterized in that the p-substituted phenol is made from a hydroquinone derivative, a gallic acid derivative, a p-alkoxyphenol or a p-cxyphenol. 4. A photosensitive silver halide emulsion according to claim 3, characterized in that the p-substituted phenol consists of p-Cxyphenol. 5. A photosensitive silver halide emulsion according to claim 3, characterized in that the p-substituted phenol from a hydroquinone derivative with a hydrophobic Remainder which contains about 5 to 18 carbon atoms. 6. A photosensitive silver halide emulsion according to claim 3, characterized in that the p-substituted phenol from a 5-HydroxycUmaran, a 6-Hydroxycumaran or a 6,6'-dihydroxyspirochroman. 7. Photosensitive silver halide emulsions according to claim 1-6, characterized in that the light-sensitive Silver halide emulsion contains a hydroquinone derivative 409847/1025 NAOHQeLCHT 2U7945 8. Photosensitive silver halide emulsion according to claims 1 to 7, characterized in that the silver halide emulsion additionally a 4-equivalent 5-pyrazolone compound in which the 4-position is unsubstituted, and / or a contains colored magenta coupler. " 9. A photosensitive photographic element comprised of a support having at least one thereon light-sensitive layer comprising a silver halide emulsion having a hydrophilic colloid with a dispersed therein 2-equivalent couplers of the general formulas I or II N. -OCO (CO) OR ₃ η (D OCO (CO) OR ₁₁ OCO (CO) 0 κ η (II) ^ O Ri Contains, wherein R _{1 is} a hydrogen atom or a group with 1 to about 50 carbon atoms from straight-chain or branched-chain alkyl groups, an alkenyl group, a cycloalkyl group, a substituted alkyl or substituted cycloalkyl group, the substituents are a halogen atom or a nitro, cyano, aryl , Alkoxy, aryloxycarboxy, alkoxycarbonyl, aryloxycarbonyl, sulfamoyl, carbamoyl, acylamino, ureido group, a heterocyclic group, arylsulfonyloxy or oxo group, a substituted one 409847/1025 Aryl group which contains at least one of the radicals alkyl, alkoxy, aryloxy, carboxy, alkoxycarbonyl, acylamino, carbanoyl, Alkylcarbamoyl-, dialkylcarbamoyl-, arylcarbaEcyl-, alkylsulfonamido-, Arylsulfonamido, sulfamoyl, alkylsulfamcyi-, Cyano or nitro groups or halogen atoms as substituents contain a heterocyclic group which contains a nitrogen, oxygen and / or sulfur atom as a hetero atom, a substituted heterocyclic group having the substituents given above for the aryl group, one Carbainoyl group or a thiocarbatnoyl group, Rp is a group having 1 to about 50 carbon atoms the same alkyl, substituted alkyl, aryl, substituted aryl, heterocyclic, or substituted heterocyclic groups Groups as indicated above for R ^, an alkoxycarbony! Group, an aryloxycarbony! Group, "an aralkyloxycarbony! Group, an alkoxy group, an aryloxy group, an alkythio group, an arylthio group, a carboxy group, an amino group, an alkylamino group, a cycloalkylamino group, a Ν, Ιί-Malkylamino group, an N-Alkyl-IT-arylarainogruppe, an N-arylamino group, an amide group, an N-alkylacylamino group, an iT-arylacylamino group, an ureido group, an N-arylureido group, an N-alkylureido group, a thioureido group, an N-alkylthioureido group, a N-arylthioureidc group, a carbamoyl group, a sulfamoyl group, a piperidino group, a pyrrolidino group, a Guanidino group, an F-alkylguanidino group. Or a ii-arylguanidino group, .Rj is a group with 1 to about 30 carbon atoms from straight-chain or branched-chain alkyl groups, an alkenyl group, a cycloalkyl group, an alkyl or cycloal> yl group, which has a calogen atom or a nitro, cyano, aryl, alkoxy , Carboxyester, sulfoester, amide, sulfonanido, ureido, carbaniyl or sulfamyl group, an aryl group which is substituted with one or more halogen atoms or a nitro, cyano, alkyl, aryl, alkoxy, aryloxy -, alkoxycarbonyl, 409847/1025 Acyl, aryl carbonyl, alkylsulfonyl, arylsulfonyl, Sulfoester, amide, sulfonamido, ureido, carbamyl or Sulfarayl groups is substituted, a heterocyclic group which, as a hetero atom, is a nitrogen, oxygen and / or contains sulfur atom or a substituted heterocyclic Group which contains the substituents given above for the aryl group, Typically a divalent group of 1 to 30 carbon atoms as an alkylene group or arylene group, wherein either R ₁ or Rp can form a monovalent group of about 30 or fewer carbon atoms which connect two 5-pyrolytic units of the general formulas I and / or II and η are the numbers 0 or 1. 10. A photosensitive photographic element according to claim 9, characterized in that the photosensitive Element a p-substituted phenol in to stabilize the development with an aromatic primary amine color image formed as a color developing agent more effectively Amount contains. 11. Photosensitive photographic clement according to claim 10, characterized in that the p-substituted phenol is derived from a hydroquinone derivative, a gallic acid derivative, a p-alkoxyphenol or a p-cxophenol. 12. A photographic photosensitive element according to claim 11, characterized in that the p-substituted phenol consists of p-oxyphenol. 13. A photosensitive photographic element according to claim 11, characterized in that the p-substituted phenol from a hydroquinone derivative with a hydrophobic radical consists of about 6 to 18 carbon atoms. 14. A photosensitive photographic element according to claim 11, characterized in that the p-substituted 409847/1025 Phenol from a 5-hydroxy coumaran, a 6-hydroxy coumaran or a 6,6'-dihydroxyspirochroman. 15. Photosensitive photographic element according to Claim 14, characterized in that the light-sensitive photographic element containing a hydroquinone derivative. 16. The light-sensitive photographic element of claim 9 to 15, characterized in that the silver halide emulsion in addition, a 4-equivalent ^5-r p5 razolonverbindung wherein the 4-position is unsubstituted, and / or a colored magenta coupler contains. 17. A method for forming a color image, characterized in that a photographic silver halide emulsion with an aromatic primary amine as a color developing agent in the presence of a 5-pyraz oil on compound, in which the 4-Pitch with a carbonic acid ester group or an oxalic acid ester group substituted. is, developed v / ird. 16. A method for forming a Parbbildes, characterized in that an exposed photographic silver halide emulsion with an alkaline aqueous solution containing an aromatic primary amine as a color developing agent contains, in the presence of a coupler forming a magenta color according to the general formulas I or II -OCO (CO) OR ₃ (D 0C0 (C0) _n 0R _% 0C0 (C0) 0- (ID / Si ^Rl A09847 / T025 ^R where R ^ is a hydrogen atom or a group having 1 to about 50 carbon atoms from straight chain or branched chain ones Alkyl groups, an alkenyl group, a cycloalkyl group, a substituted alkyl or substituted cycloalkyl group which is substituted by a halogen atom or a nitro, cyano, aryl, alkoxy, aryloxycarboxy, alkoxycarbonyl, Aryloxycarbonyl, sulfo, sulfoamoyl, carbamoyl, acylamino, ureido group, a heterocyclic group, Arylsulfonyloxy or oxo group, a substituted aryl group containing at least one of the radicals alkyl, alkoxy, Aryloxy, carboxy, alkoxycarbonyl, acylamino, carbamoyl, alkylcarbamoyl, dialkylcarbamoyl, arylcarbamoyl, alkylsulfonamido, Arylsulfonaraido, sulfaraoyl, alkylsulfamoyl, Contain cyano or nitro groups or halogen atoms as substituents, a heterocyclic group which acts as a heteroatom contains a nitrogen, oxygen and / or sulfur atom, a substituted heterocyclic group with the above substituents specified for the aryl group, a carbamoyl group or a thiocarbamoyl group, *
Rp is a group having 1 to about 50 carbon atoms the same alkyl, substituted alkyl, aryl, substituted aryl, heterocyclic, or substituted heterocyclic groups Groups as stated above for R ^, an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, an alkoxy group, an aryloxy group, an alkythio group, an arylthio group, a carboxy group, an amino group, an alkylamino group, an Oycloalkylaminogruppe, an N, N-I) ialkylainino group, an N-alkyl-IT-arylaraino group, an N-arylamino group, an Araid group, a K-alkylacylamino group, an IT-arylacylaiaino group, a ureido group, an N-arylureido group, an H-alkylureido group, a thioureido group, an N-alkylthioureido group, a N-arylthioureido group, a carbamoyl group, a sulfamoyl group, a piperidino group, a pyrrolidino group, a Guanidino group, an N-alkylguanidino group. Or an N-arylguanidino group, 409847/1025 R, a group with 1 to about 30 carbon atoms of straight-chain or branched-chain alkyl groups, an alkenyl group, a cycloalkyl group, an alkyl or cyeloalky group, those with a calogen atom or a nitro, Ö2 / an, aryl, Alkoxy, carboxy ester, sulfoester, amide, sulfonamido, Ureido, carbamyl or sulfamyl group is substituted, a Aryl group, which with one or more halogen atoms or a Kitro-, Cyano-, "alkyl-, aryl-j alkoxy-, aryloxy-, alkoxycarbonyl-, Acyl, aryl carbonyl, alkylsulfonyl, arylsulfonyl, Sulfoester, amide, sulfonamido, ureido, carbamyl or SuIfany! Groups is substituted, a heterocyclic group, v / which as a hetero atom is a nitrogen, oxygen and / or contains sulfur atom or a substituted heterocyclic group, v / like those above for the aryl group contains specified substituents, R. 6 is a divalent group of 1 to 30 carbon atoms as an alkylene group or arylene group, wherein either R., or Rp is a zv / monovalent group of about 30 or fewer carbon atoms can form the two 5-pyrazolone units ßer general formulas I and / or II connect and η mean the numbers 0 or .1. 19 · The method for forming a lartbildes, characterized cc indicates that a lichtempfind ¹ iehes material is exposed, which comprises a support having thereon a photographic silver halide emulsion layer comprising a magenta color forming coupler corresponding to the general formula I or II -OCO (CO) OR ₃ (D ^Rl . 409847/1025 OCO (CO) _n OR ^ OCO (CO) _n O- -Ra (II) N ^X 0 0 N ¹ · L contains, wherein R _{1 is} a hydrogen atom or a group with 1 to about 50 carbon atoms from straight-chain or branched-chain alkyl groups, an alkenyl group, a cycloalkyl group, a substituted alkyl or substituted cycloalkyl group, the substituents are a halogen atom or a nitro, cyano , Aryl, alkoxy, aryl oxy carboxy, alkorcycarbonyl, arylgxycarbonyl, sulfo-, sulfoamoyl, carbamoyl, acylamino, ureido group, a heterocyclic group, arylsulfonyloxy or oxo group, a substituted aryl group containing at least one of the Radicals alkyl, alkoxy, aryloxy, carboxy, alkoxycarbonyl, acylamino, carbamcyl, alkylcarbamoyl, dialkylcarbamoyl, arylcarbamoyl, alkylsulfonamido, arylsulfonaraido, sulfanbyl, al, sulfamoyl or nitro, cyano groups Containing halogen atoms as substituents, a heterocyclic group which contains a nitrogen, oxygen and / or sulfur atom as a hetero atom, a substituted heterocyclic group e with the substituents given above for the aryl group, a carbainoyl group or a thiocarbamoyl group, Rp is a group with 1 to etv / a 50 carbon atoms from the same alkyl, substituted alkyl, aryl, substituted aryl groups, heterocyclic or substituted heterocyclic groups, as indicated above for R .., an alkoxycarbonyl group, an ary1 oxy carbonyl group, a Aralkyloxycarbonyl group, an alkoxy group, an aryloxy group, an alkythio group, an arylthio group, a carboxy group, an amino group, an alkylamino group, a cycloalkylaEino- 409847/1025 - ft! ~ group, a Ν, Ν-dialkylamino group, an N-alkyl-U-arylamino group, an N-arylamino group, an amide group, an N-alkylacylamino group, an N-arylacylamino group, an ureido group, an N-arylureido group, an N-alkylureido group, a thioureido group, an N-alkylthioureido group, a N-arylthioureido group, a carbamoyl group, a sulfamoyl group, a piperidino group, a pyrrolidine group, a guanidino group, an N-alkylguanidino group. or an N-arylguanidino group, R, is a group having 1 to about 30 carbon atoms straight or branched chain alkyl groups, an alkenyl group, a cycloalkyl group, an alkyl or cycloalkyl group, those with a halogen atom or a nitro, cyano, aryl, alkoxy, car "boxyester, sulfoester, amide, sulfonamido, Ureido, carbamyl or sulfamyl group is substituted, a Aryl group with one or more halogen atoms or a nitro, cyano, alkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, Acyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, sulfoester, amide, sulfonamido, ureido, carbamyl or Sulfanyl is substituted, a heterocyclic group, which as a heteroatom is a nitrogen, oxygen and / or contains a sulfur atom or a substituted heterocyclic group which is those described above for the aryl group contains specified substituents, R, a divalent group of 1 to 30 carbon atoms as an alkylene group or arylene group, wherein either R ₁ or R _{2 is} a divalent group having about 30 or fewer carbon atoms which connect two 5-pyrazclone units of the general formulas I and / or II and η are the numbers 0 or 1, wherein the coupler has at least one hydrophobic group of 8 or more carbon atoms in the molecule, and the material having an alkaline aqueous solution containing an aromatic primary amine as an ear developing agent. 409847/1025 20. Method for forming a .Farbbildes, thereby marked that. a photosensitive material which a support having a silver halide photographic emulsion layer thereon in combination with a a magenta color forming coupler of the general formulas -I or II -OCO (CO) _n OR ₃ (D Rx OCO (CO) _n ORIiOCO (CO) _n O- (ID Ri wherein A ^ is a hydrogen atom or a group with 1 Ms'etv / a 5C carbon atoms from straight-chain or mixed Zwelgt.kettigen alkyl groups, an alkeny! group, a cycloalkyl group, a substituted alkyl or substituted cycloalkyl group, the substituents are a halogen atom or a nitro, cyano, aryl, alkoxy, aryloxycarboxy, alkoxycarbonyl, aryloxycarbonyl, Sulfo, sulfamoyl, carbanioyl, acylamino, ureido group, a heterocyclic group, arylsulfonyloxy or oxo group, a substituted one 409847/1025 Aryl group which contains at least one of the radicals alkyl, alkoxy, Aryloxy, carboxy, alkoxycarbonyl, acylamino, carbamoyl, alkylcarbamoyl, dialkylcarbamoyl, arylearbamoyl, alkylsulfonamido, Arylsulfonamido, sulfamoyl, alkylsulfasioyl, Contain cyano or nitro groups or halogen atoms as substituents, a heterocyclic group which acts as a hetero atom contains a nitrogen, oxygen and / or sulfur atom, a substituted heterocyclic group with the above for the ary! group specified substituents, a Carbantcyl group or a thiocarbamoy group, Rp is a group with 1 to about 50 carbon atoms from the same alkyl, substituted AIkJ ⁷ I-, aryl, substituted aryl groups, heterocyclic or substituted heterocyclic groups, as stated above for R ^, an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbony group, an alkoxy group, an aryloxy group, an alkythio group, an arylthio group, a careoxy group, an amino group, an alkylamino group, a cycloalkylanino group, a Ν, Ν-dialkylamino group, an N-alkyl-17-ary 1 amino group, an N-alkyl-17-ary 1 amino group -Arylamino group, an amide group, an N-alkylacylaraino group, an N-arylaeylamino group, an ureido group, an N-arylureido group, a li-alkylureido group, a thioureido group, an N-alkylthioureido group, an N-arylthioureido group, a carbamamoyl group, a carbamamooyo group a piperidino group, a pyrrolidino group, a guanidino group, an N-alkylguanidino group. or an N-arylguanidino group, R, a group with 1 to about 30 carbon atoms consisting of straight-chain or branched-chain alkyl groups, an alkenyl group, a cycloalkyl group, an alkyl or cyeloalky group, which is formed with a calogen atom or a nitro, cyano, aryl, alkoxy, carboxy ester , Sulfoester, amide, sulfonanido, ureido, carbamyl or sulfamyl group, an ary! Group which is substituted with one or more halogen atoms or a nitro, cyano, alkyl, aryl, alkoxy, aryloxy , Alkoxycarbonyl, acyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, sulfoester, amide, sulfonamido, ureido, carbamyl or sulfany! Groups is substituted, a heterocyclic group which, as a heteroatom, is a nitrogen, oxygen and/ 409847/1025 NAGl! DISHED or contains a sulfur atom or a substituted heterocyclic group which is those described above for the aryl group contains specified substituents. R ^ is a divalent group of 1 to 30 carbon atoms as an alkylene group or arylene group, wherein either R ^ or Rp is a divalent group of about 30 or fewer carbon atoms can form the two 5- ^ pyrazolone units of the general formulas I and / or Il connect and η are the numbers 0 or 1, wherein at least one of the radicals R ^ or R _{2 contains} a water-solubilizing sulfo, carboxyl or sulfonamido group and Rz is a hydrophobic group of eight or more carbon atoms, developed with an alkaline aqueous solution containing an aromatic primary amine as a color developing agent and then transferring the obtained magenta dye onto a receiving layer containing a basic polymer. 409847/1025 Blank page