DE2263875A1 - PROCESS FOR THE PRODUCTION OF YELLOW PHOTOGRAPHIC IMAGES - Google Patents

Description

PATENT LAWYERS

DR-E. WIEGAND DIPL-ING. W. NI ¹ SMANN DR. M. KOHLER DIPUNG. C. GERNHARDT

MÖNCHEN HAMBURG TELEPHONE: 55547 «8000 MO N CH EN 15, TELEGRAMS: KARPATENT NUSSBAUMSTRASSE10

December 28, 1972

W. 414-34- / 72 - Ko / Ne

Photo Jj ¹ Hm Co., Ltd. Minami Ashigara-shi, Kanagawa (Japan)

Process for the production of yellow photographic images

The invention is concerned with and relates to a method for producing color photographic images in particular, a method for producing color photographic images using a new one yellowing coupler.

A method of forming a color image by developing an imagewise exposed photograph Silver halide emulsion by an aromatic primary Amine as a color twic kl ungsaiittel in the presence of a yellow

309827/1087

forming coupler of the general formula

0 0

R ¹ - C - CH - C - N ^ 2

Λ 2

where R is an aromatic group, R is an aromatic group or a heterocyclic group and Z is the one to form a 4-membered ring, a 5-membered ring

Ring or 6-membered ring along with the rest O 0

Il Il

-C-N-C- mean atoms necessary in the above formula is specified according to the invention. Another This invention provides a photographic element containing such a yellowing coupler.

To form a color photographic image according to the subtractive color process, a stage is used in which the silver halide grains in the exposed, silver halide photographic emulsion layer by a developing agent, generally an aromatic primary Amine compound, especially an N, N-di-substituted one p-phenylenediamine compound, and the oxidation product of the developing agent formed at the same time to a coupling reaction with the color-forming couplers with the formation of cyan, magenta and yellow images.

Any coupler used in the color development process is a compound having a phenolic hydroxyl group, an anilinic amine group, or an active one

309827/1087

Methylene group, which in the oxidative coupling with the aromatic primary amine as a developing agent gives a dye which is capable of absorbing light in the visible Wavelength range is suitable.

A yellow dye image absorbs the blue light component in a wavelength range from about 400 nm to about 500 mu. Include known yellow-forming couplers ß-Ketoacetoessigsäureester, beta-diketones, Ν, Ν-malondiamides _v a-Aeylacetamide and similar materials.

Of these yellow-forming couplers, benzoylacetamide-type compounds are widely recognized as good yellow-forming ones Couplers used in the field of color photography. Virtually all of these yellowing couplers are 4 equivalent couplers; H. Coupler that uses 4 moles of exposed silver halide as an oxidizing agent need to form 1 mole of the azomethine dye. However, the incorporation of a large amount of silver halide in the light-sensitive emulsion layer is difficult Accompanying disadvantages, d. H. the light scattering in the emulsion layer increases and reduces the sharpness of the formed image and the thickness of the emulsion layer increases, so that the processing speed of the photographic photosensitive material is reduced. In addition, these have types of yellowing couplers also the error that the formation of the dye by the coupler is not terminated in the color development, but rather requires a strong oxidizer in the subsequent treatment step.

In order to improve these defects, it has been proposed to use so-called yellow couplers of 2 equivalents, i.e. a coupler which requires only 2 moles of exposed silver halide to form 1 mole of the methine dye.

309 8 27/1087

A yellow coupler with 2 equivalents has a structure where one of the hydrogen atoms of the active methylene group is substituted by a group to be coupled off or split off is. Examples of such coupling-off groups are fluorine atoms in US Pat. No. 3,277,155 Substituted phenoxy groups in the US patent 3,408,194, acyloxyl groups in U.S. Patent 3,447,928, Sulfoxyl groups in U.S. Patent 3,415,652 and U.S. Patent No. 3,415,652 by the formula below

\ o - - ^J

specified group in the German Offenlegungsschrift 2,057,941.

The in the above patents and in the

U.S. Patents 3,265,506 and 3,253,924 also own

1 2
Groups analogous to R and R according to the invention and serve to explain the broad class of groups that

12th
can serve as acceptable groups R and R according to the invention.

However, many of these known couplers have defects d. H. they are inadequate in terms of coupling reactivity, result in a strong haze of color, the coupling activity of the couplers in the photographic light-sensitive materials gradually increases Because of the instability of the couplers themselves, they decrease, they cause staining from such couplers yellow dyes formed show a weak dis-

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Currency stability and / or are not easily formed. Many of these couplers are therefore general, unsatisfactory.

A first object of the invention is therefore to provide a new yellow-forming coupler which is used for color photographic Purposes when using the dye subtraction method suitable is.

Another object of the invention is one. A method of forming a dye image by developing a silver halide photographic emulsion layer in the presence of these new yellow-forming couplers.

The third object of the invention is a color photographic light-sensitive material having a Silver halide emulsion layer containing the new tanning couplers.

Another object of the invention is a color developer using these new yellow-forming couplers contains.

Another object of the invention is a method for reducing the content of the photographic material Silver halide containing silver halide emulsion by using these new yellowing agents Coupler so that the sharpness of the obtained photographic Image is enhanced.

Further, it is an object of the invention to provide a color photographic light-sensitive material suitable for a rapid color development treatment using a Blixbades containing a weak oxidizing agent and a silver salt complexing agent.

Another object of the invention is a method for forming a yellow color image with spectral absorption properties that are important for the color

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Reproduction by the subtractive color method are suitable, this image having excellent stability.

The above objects are achieved according to the invention by the formation of a photographic element and by a process for the formation of dye images, wherein a photographic silver halide emulsion using an aromatic primary amine as a developer in the presence of an (aromatic acyl) acetamide compound which is contained in the α- Position is substituted with a diacylamino group is treated.

In particular, the process of the present invention comprises treating a silver halide photographic emulsion containing an aromatic primary amine developing agent in the presence of the novel yellowing coupler having a diacylamino substituent at the α-position thereof represented by the following general formula

0 OH

HI"

1 H I »2

R-C-CH-C-N-R

ο = σ c = o

1 2

wherein R is an aryl group, R is an aryl group or a heterocyclic group and Z is to form with the unit .N in the formula of a 4-membered,

O = C X3 = 0

5-membered or 6-membered substituted or unsubstituted Ringes necessary non-metal atoms r ~ D ± e

309827/1087

Λ 2

R, R and Z radicals have the same meaning in all of them The formulas given below, unless otherwise stated.

In the general formula (I) given above

/ ι
the group R represents an aryl group, for example a phenyl group or a substituted phenyl group. The substituents which may be present on the phenyl group include, in addition to the monovalent substituents specified below, divalent units which, together with the phenyl nucleus, form a fused ring system

k , where A is responsible for the formation of an aromatic

condensed ring system means necessary atoms. Such aryl groups with a fused ring system include naphthyl, ohinolyl, isoquinolyl, chromanyl, Coumarinyl and tetrahydronaphthyl groups. Under the-general Formula CI) also include those derivatives in which two remaining groups each have the same formula

-CHCONHR ²

N
O = C Ct = O

are either bonded to an arylene group or two aryl groups are linked through a divalent group. In these cases, the couplers can be made by the following reflect general formula:

3 0 9 8 2 7 / T 08 7

(C0CHC0NHR ² ) ₂

O = C C «0

Λ Ι

where R is an arylene group or a -YY ¹ -Y- moiety, where Y is an arylene group and Y ^{1 is} a divalent group.

Examples of such divalent groups are

-CH ₀ -, -0-, -NHCONH- and similar groups.

■ 2

The group R means an aryl group, for example a phenyl group or a substituted phenyl group. The substituents that may be present on the phenyl group include those listed below monovalent substituents divalent units which, together with the phenyl nucleus, form a condensed ring-I A form, where A is the one to form a

aromatic condensed ring system indicating necessary atoms. Such aryl groups with a fused ring system include naphthyl, quinolyl, isoquinolyl, Chromanyl and coumarinyl and tetrahydronaphthyl groups. The general formula (I) also includes those derivatives in which two remaining groups are each the same formula

R ¹ COCHCONH-

O = C Q = O

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either attached to an arylene group or two Aryl groups are connected via a divalent group. In these cases the couplers can be represented by the following general formula:

(R ¹ COCHCONH) ₂ R ² '

O = C

wherein R 'represents an arylene group or a -X-X'-Y- group, wherein X represents an arylene group and X ^{1 represents} a divalent group. Examples of such divalent groups are -CH ^ -, -0-, -KHCOHH- and similar groups. The monovalent substituents on the phenyl nuclei of the groups R and R can be selected from a wide range of groups. Such substituents include, for example, halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkyl sulfonyl groups, arylsulfonyl groups, carboxyl groups, thiocyanine groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfonamido groups, acylamido groups, acylamido groups, amineamido groups, acylamino groups, acylamido groups, amine groups, acylamino groups, amine groups, amine groups and hydroxyl groups, acyl groups, aryl ο xycarbonyl groups, alkoxysulfonyl groups, aryloxysulfonyl groups and sulfonamino groups. The positions in these groups which are occupied by a hydrogen atom or other atoms can furthermore be substituted, for example a hydrogen atom or several hydrogen atoms can be created by substituents which result in a substituted group.

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Ί 2 sets eein. The phenyl groups of groups B and H Bind are preferably substituted by one or more of the substituents given above.

A phenyl group according to the following formula is the preferred group H:

where I ₁ . and Yo each represent a hydrogen atom, an alkyl group with 1 to 32 carbon atoms or an alkoxy group with 1 to 32 carbon atoms and Yr, Y ^ and Yr, each a hydrogen atom, an alkyl group with 1 to 32 carbon atoms, an alkoxy group with 1 to 32 Carbon atoms, an aryloxy group such as a phenoxy, toiyloxy, amylphenoxy, diaraylphenoxy, nonylphenoxy, methoxyphenoxy, chlorophenoxy, naphthoxy group and the like, an amino group, an alkylamino group having 1 to 32 carbon atoms or an acylamino group having 1 to 32 Mean carbon atoms.

Phenyl groups according to the following formula

p
len the preferred groups E:

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wherein X is a halogen atom, an alkoxy group having 1 "to 32 carbon atoms, an aryloxy group having 1 to 32 carbon atoms, a di-substituted amino group having 1 to 32 carbon atoms and Y ^, Y ₂ ¹ ^ ¥ 3-a hydrogen atom, a halogen atom, a Alkyl group with 1 to 32 carbon atoms, an alkynyl group with 1 to 32 carbon atoms, an alkoxy group with 1 to 32 carbon atoms, an aryl group, for example a phenyl, tolyl, atnylphenyl, diamylphenyl, nonyl- 'phenyl-, methoxyphenyl-, chlorophenyl- , Naphthyl group and the like., An aryloxy group such as a phenoxy, • tolyloxy, amylphenoxy, diamylphenoxy, nonylphenoxy, methoxyphenoxy, chlorophenoxy, naphthophenoxy group and the like., An alkylcarbonyl group having 1 to 32 carbon atoms, an arylsulfonyl group, alkyl having 1 to 32 carbon atoms, an arylsulfonyl group, carboxy group, alkoxycarbonyl group having 1 to 32 carbon atoms, carbamyl group having Λ to 32 carbon atoms, S ulfo group, sulfamyl group with 1 to 32 carbon atoms, acylamino group with 1 to 32 carbon atoms, ureido group with 1 to 32 carbon atoms, sulfonamide group with 1 to 32 carbon atoms, amino, nitro or cyano group. The heterocyclic group which can be represented by the group E is attached to the remainder of the group R through a carbon atom of the heterocyclic ring

COCHCONH-

o = c 9 = 0

309827/1097

bound. This carbon atom is part of the conjugated electron system of Binge, ie a carbon atom, which in this way shows an aromatic character. Such heterocyclic groups include those of the thiophenyl type such as 2-thiophenyl, 3-thiophenyl, 2-benzothiophenyl, 3-benzothiophenyl, 2-naphthothiophenyl, 3-naphthothiophenyl, or 3-thiophenyl> those of the furan type such as 2-furyl, 3-furyl , 2-benzofuranyl, 3-benzofuranyl, 1-isobenzofuranyl or 3-isobenzofuranyl, those of the pyrane type such as 3 ~ I ^: 'y ^ a ⁿ yl »4-pyranyl, 5-pyranyl or 6-pyranyl _r those of the chromium type such as 3-chromenyl or 4-ghromenyl, those of the pyrrole type such as 3-pyrrolyl, those of the pyrazole type such as 3-pyrazolyl or 4-pyrazolyl, those of the pyridine type such as 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-quinolyl , 3-quinolyl, 4-quinolyl, 1-isoquinolyl, 3-isoquinolyl or 4-isoquinolyl, those of the pyrazine type such as 2-pyrazinyl or 2-quinoxalinyl, those of the pyrimidine type such as 2-pyriraidinyl, 4-pyrimidinyl, 5-pyrimidinyl , 2-quinazolinyl or 4-quinazolinyl, those of the pyridazine type such as 2-pyridazinyl, 3-pyridazinyl, 3-cinnolinyl, or 4-cinnolinyl, which are the same indolidine type such as 1-indolidinyl, 2-indolidinyl, 3-indolidinyl, 5-indilidinyl, 6-indolidinyl or 7-indolidinyl, perimidine type such as 2-perimidinyl, thiazole type such as 2-thiazolyl, 2-benzothiazolyl , 3-isothiazolyl, 4-1sothiazolyl or 5-isothiazolyl, those of the imidazole type such as 2-benzoimidazolyl, those of the oxazole type such as 2-oxazole, those of the 1,3> 5-triazine type, the 1,3,5-triazinyl and those of the oxazine type such as 2-oxazinyl. These heterocyclic groups can also be replaced by any suitable substituents, for example halogen atoms, alkyl groups, alkylcarbonyl

309827/1087

groups, alkenyl groups, alkoxy groups, alkylsulfonyl groups pen, aryl groups, aryloxy groups, aryl carbonyl groups, Arylsulfonyl groups, carboxyl groups, alkoxycarbonyl groups, Carbamyl groups, sulfo groups, sulfamyl groups, Acylamide groups, ureido groups, sulfonamide groups, amino groups, Nitro groups, cyano groups, thiocyanate groups, Hydroxyl groups, acyl groups, aryloxycarbonyl groups, acylamino groups, akoxysulfonyl groups, aryloxysulfonyl groups and sulfoamino groups may be substituted.

Another embodiment of the general formula (I) includes those derivatives in which two remaining groups

E ¹ COGHCONH-

O = C C = O

to a heterocyclic group, to two heterocyclic groups directly connected to one another or to two via one divalent group linked heterocyclic groups are bonded. In this case the couplers can go through the following general formula can be reproduced:

(R ¹ COCHCONH) ₂ R ²

^v C = 0

30 9827/1087

2 '
wherein R represents a divalent heterocyclic group.

The general formula (I.) also includes up to

Compounds, for example those in which two coupler

12th
groups K COCHOGNHR are connected to each other via Z,

for which reference is made as an example to the yellow-forming coupler (43) given below.

In a preferred embodiment, the diacylamino group is selected from dicarboximido groups of the following general formulas CH) to (XIII):

I ( ^χΙΙ) Js ■ / ^ ^N \ ₀ o = c ^XX c = o

309827/1087

(IV)

ϊ ■ ΐ

.10

R- ¹

(VI)

O = C

R ¹⁹ - C. R ²⁰

= 0

(V)

O = C. C = O

I ■

15 J ₀

R ¹⁶

(VII)

A ₀

O = C C =

_R 2J__ c W

(VIII) ' ^N

. (MT 0 = 0

, 24 ^

(IX)

f—— W

, 28

C = O

R ¹

25th

O = C

0.

- Ϊ

= O

(XII)

C = O (XI)

O = C

, 33

, (XIIi) - I.

309827/1087

In the above general formulas (II) to (XIlX) the radicals E ³ , E ⁴ , E ⁵ , E ⁶ , E ⁷ , E ⁸ , E ⁹ , E ¹⁰ , H ¹¹ , E ¹² , E ¹ ', E are ¹⁴ , E ¹ 5, E-IS _{1 H} 17 _{f R} W _f "1 ^ ^ ^

B ² 5, E ²⁴ , Ε ² ?, E ² ?, E ²⁸ , E ²⁹ , H *>, B ⁵¹ , E? ² , R ??, E? \ R ^ and R * each have monovalent substituents such as hydrogen atoms, Ilalogen atoms such as fluorine, chlorine or bromine atoms, alkyl groups, for example substituted or unsubstituted alkyl groups with 1 to about J2 carbon atoms, preferably with ί to about 20 carbon atoms, alkoxy groups, aryl groups, aryloxy groups, sulfo groups or carboxyl groups.

In the formulas VI, VIII, XI and XII, B ²¹ , R ²⁶ , R *, R * and R? ' each represents a hydrogen atom, an alkyl group, for example a substituted or unsubstituted alkyl group having 1 to about 32 carbon atoms, preferably 1 to about 20 carbon atoms, or an aryl group.

Furthermore, the groups R ^ and R ^ in the general

7 Q

mean formula (II), R and R in the general formula (III), R ^ and R ¹¹ as well as R ¹² and R ¹ ^ in the general formula (IV), R ¹ ^ and R ¹⁶ as well as R ¹⁶ and R ¹⁷ in of the general formula (V), R · and R ^ in the general formula (VIII) and R ^ and R ^ in the general formula (X) be connected to one another to form a 5- or 6-membered ring which is both saturated as can also be unsaturated. Examples of such rings include a benzene ring, a pyridine ring, a cyclohexane ring, a furan ring, a bicycloheptane ring, a Βίο ycloheptene ring or a cyclonexene ring.

W in the general formula (VII) indicates an oxygen atom or a sulfur atom.

Specific examples for the rest of the group

309827/1087

O = C C = O

in the general formula (I) include the following Eeste:

The couplers with 2 equivalents according to the invention corresponding to the general formula I are derived from the couplers with 4 equivalents according to the following general formula (I ¹ ) and are linked at the coupling position by a single bond with a cyclic diacylamino group

Ci ¹ )

in which R and R have the meaning given for formula I. The couplers corresponding to formula CI ¹ ) with 4 equivalents are in the photographic art

1 2

well known. Numerous substituents for R and R were made proposed the characteristic properties of the couplers as such and those of the couplers to improve formed dyes. Examples of such couplers can be found in the following literature references: "Messages from the research laboratories of the AGFA" by V. Pelz, Volume 3, pages 112 to 126 (1961), U.S. Patents 3,409,439, 3,551,555, 3,551,156 and 3,649,276, British Patents 1,961,156 and

1,286,411, Japanese Patent Publications 39-2,839 and 40-6,030, U.S. Patents 2,319 4-26,

2,331,326, 2,350,138, 2,359,332, 2,376,679, 2,407,210,

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2 464 297, 2 472 913, 2 868 829, 2 875 057, 2? 53 576,

3 056 674, 3 056 675, 3 077 403, 3 3 ^ 1 331, 3 369 899, 3 393 041, 3 615 606, 3 619 190, 3 623 876, 3 645 742, 3,660,095 and 3,669,671 and British patents 805 505 and 1 187 860.

Since the couplers for 2 equivalents of the formula (I) give the same azomethine dyes as the couplers for 4 equivalents of the l'Orrael (I '), the groups E. and Rp, which provide dyes with the desired properties, are also in the Couplers according to the present invention are useful and valuable. Since the couplers for 2 equivalents of the formula (I ) are modified only by substituting the diacylamino group instead of a hydrogen atom in the α-position, all groups Ii ^ and I? 2 of the formula (I ' ) can also be used as radicals R ^ and Rp can be used in the couplers according to the present invention.

However, it was surprisingly found that when the diacylamino group is replaced instead of a hydrogen atom in the α-position, the remaining hydrogen atom in the α-position receives an electronic effect and the coupler generally shows a decrease in its pKa value of about 3 to 4. Consequently, the radicals R, in _t the couplers according to the invention - and R _0, very

1 2

whether they are an aryl group (R and R) or a

2
heterocyclic group (R ) may be substituted with an electron donating group which does not reduce coupling activity such as an alkoxy group, amino group or N-substituted amine group, and retain their sufficient coupling reactivity. Under the remainders R ^. and Rp do not fall into any groups which adversely affect the photographic emulsion,

309827/1 087

for example mercapto groups, disulfide groups or peroxyc arboxy groups.

Typical specific examples of such dicarboximide residues are given below:

309827/1087

-N

22) 53875

H,

CH - CH,

Il

fi

f - ° 2 ^H 5

, CH,

I!

.CH,

?H

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Il, c.

CH - Br

-N

.CJH,

-N:

■ / ■

-N.

CH - SO ₃ H

-CH ₂ 827/1087

2260875

-N

C-

Il ο -CH,

-CH-CH - COOH

CH ₂ - COOH

- CH

C-

Il

-CH CH

CH,

-ir

Il ο

■ β

CH

CH

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-N '

O ii

¹ C

U ο

II

, C

CH

Il

CH

- C - CH

- CH

-ν;

- CH,

Il

.σ

CH

CH JB ₃

η)

I.

- CH

CH-CH

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-ν;

-N '

ο
I!

JC - CH,

O Br

Ii i

C - C

P - CH

C Br .CH,

CH ₂

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J-

CH -

6 5

■ \

C- CH

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COOH

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-Cl

-Cl

NHCOCH ₅

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NHSO,

NHCONH-

NHCOCHO—

NHCOCH ₂ CH ₂ N '

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Il ο

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-ν:

ο Il

, C-NH

Il

-C-CH, I Ctt »

-N.

- NH

CH

-N '

O Il

C-NH

CC-C _O H _C O

-N

O -

CH

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- NH

CH,

-ο

- C - CH,

il C-NH

C-CH-CH -N

Ii c

\ π-

■ C - NH

C-CH-C ₅ II ₇ (Ii) 0

-N.

- NH

-C-

C-CH ₃ CH ₅

C ₂ H ₅

309827/1087

The method for forming yellow images according to the invention can be divided into two embodiments, namely one where the couplers are in the photographic emulsion layers of the photographic photosensitive Material are present, and one where the couplers are present in the color developers. In the first embodiment the couplers are usually incorporated into the photographic silver halide emulsion layers during the manufacture of the color photographic light-sensitive Materials and in the other embodiment the couplers are usually in the color developers dissolved and they diffuse into the. photographic silver halide emulsion layers of color photographic photosensitive materials during the development treatment.

If the couplers are in the emulsion layer, each coupler must be in a specific emulsion layer be fixed. In other words, these couplers must have diffusion resistance, otherwise the couplers diffuse into other silver halide emulsion layers of the photographic light-sensitive materials and a coupling reaction in emulsion layers that have different spectral sensitivities than the emulsion layer, in which the coupler was originally present, cause so that the color reproducibility of the photosensitive material is severely damaged.

In order to obtain diffusion resistance properties for the couplers, a hydrophobic group is used with 8 to 32 carbon atoms are introduced into the molecule of the coupler. Such groups are commonly called "Ballast groups". The ballast group can be connected to the framework structure of the coupler directly or via a

309827/1087

Amino bond, an ether bond, a thioether bond, a carboamido bond, a sulfonamide bond, a urea bond, an ester bond, an imide bond, a carbony bond or a sulfonyl bond in all of the R ₁ , Rp or Z groups.

All known ballast groups can be used in the yellow-forming couplers are used according to the invention. Typical examples of such ballast groups are given below:

(1) Alkyl groups and alkenyl groups, for example

and -O ₁₇ H ₅₅ , for which purpose

1ΊΑΤ Final Report No. 934- is referred to.

(2) Alkoxyalkyl groups as described, for example, in Japanese Patent Publication No. 27 563/1964. "Typical examples thereof are: - (CH ₂ ) ₅ O (CH ₂ ) ₇ CH ₅ and ^ - (CH ₂ ) OCH ₂ -CH- (CH ₂ ) ₈ CH ₅

(3) alkylaryl groups, such as

^C ₄ H ₉ (t) ^C 9 ^H 19 ^and

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(4) alkylaryloxyalkyl groups, for example

-CH ₂ O

11

(sec),

CH ₂ O

^C 5 ^H li ^(t)

C ₂ H ₅

-CH ₂ O CH ₃ -C-CH ₃

C ₂ H ₅

-CHO

^C 5 ^H ll ^(t)

309827/1087

- 55 -

Eb is also referred to the British patents 562,205 and 1,149,514 and U.S. patents 2 589 004 and 2 908 575. Examples of this are:

C ₃ H ₇

-CH ₂ CH ₂ HHCC-Ä

and

COC ₁₃ H ₂₇

^C 3 ^H 7

(6) alkoxyaryl groups and aryloxyaryl groups, "for example

/ \ —OC ₁₈ H ₃₇ Cn) and

-f \ o

3 098 27/1087

refer to the Japanese patent publication 29 414/1966 and British Patent 969 921 is referenced.

(7) residues that are both a long-chain aliphatic Alkyl or alkenyl group, preferably with 12 to 32 Carbon atoms, and a water-solubilizing carboxyl or contain sulfo group, for example

-CH-CH = CH-C ₁₆ H ₃₅
C.

CH ₂ CCOH

and

SO ₂ H
3

A coupler having a ballast group in the molecule is carried into the silver halide photographic emulsion Dissolving in an organic solvent and dispersing the solution in the emulsion as fine particles introduced according to known procedures. A specific example of a method for dispersing the coupler in a photographic emulsion that is particularly useful for practicing the present invention is disclosed in Japanese Patent Publication 67 797/1969 given. The ones used to dissolve the couplers organic solvents include organic solvents that are only slightly soluble in water, have high boiling points (higher than 170 ° C) and the with the coupler together in the photographic emulsion layers of the color photographic photosensitive Materials exist and consist of substituted ones

309827/1087

Hydrocarbons such as α-dodecynaphthalene and chlorinated Paraffins, carboxylic acid esters! ', Carboxamides, phosphoric acid esters and ethers. Specific examples such materials are di-n-butyl phthalate, di-isooctyl azelate, di-n-butyl sebacate, tricresyl phosphate ,. Trin-hexy! Phosphate, ϊΤ, Ιϊ-diethylcaprylamide, butyl-m-pentadecylphenyl ether and chlorinated paraffins such as chlorocosan. It is preferred in addition to these high-boiling solvents the use of "up to 10% by weight of the coupler, most preferably no more than 5%" an auxiliary solvent which is used during the preparation of the photosensitive Material can be removed to accelerate the dissolution of the coupler in the solvent. Examples of such auxiliary solvents are propylene carbonate, Ethyl acetate, butyl acetate, cyclohexanol, tetrahydrofuran, Cyclohexanone and the like.

It is also preferred to be a surfactant for finely dispersing the oil-soluble coupler in the hydrophilic polymer for photographic emulsion apply. In particular, anionic surface-active agents such as ITatriurneetylsulphate, latriump-dodecylbenzenesulphonate, Sodium nonylnaphthalene sulfonate, sodium di (2-ethylhexyl) α-sulfosuccinate and the like surfactants or nonionic surfactants such as sorbitan sesquioleic acid ester, sorbitan monolauric acid ester and the like. Suitable. The surfactant (s) are usually used in an amount from 0.01 to 3% by weight based on the weight of the coupler, more preferably 0.02 to 0.15%, is used. Attractively priced A homogenizer for emulsification, a colloid mill, is also used to disperse the oil-soluble couplers of ultrasonic emulsifying devices and the like.

30982 771087

Diffusion-resistant couplers or couplers having a ballast group with a carboxylic acid group or a sulfonic acid group in combination with the ballast group in the JIoIekül are soluble in neutral or slightly alkaline aqueous solutions with a hydroxyl ion concentration of

fr _s \

10 to 10 mol / liter, equivalent to a pH value of 8 to 13 · By adding the aqueous solution of the coupler as a silver halide emulsion, the coupler can be incorporated in the photographic emulsion. It will believed that this made the coupler diffusion resistant by forming a micelle in the hydrophilic polymer.

Couplers without such a ballast group, d. H. Couplers of the above kind for incorporation in the color developer, are used in color developers together with an aromatic primary amine as a color developing agent used.

Typical examples of compounds of yellow-forming couplers corresponding to the general formula I are following:

309827/108 7

COCHCONH
, Ν «

OC

NHCOCHO C

■ ν ^ V-COCHCONH

OC

co

«HHC0CH0 C

2 ^H 5

309827/1087

Cl

COCHCONH

ocr co

NHCOCHO- / ^ SC ₂ H ₅

COCHCONH-

oc \ o

) - / \ -C0CHC0NH

/ N

OC CO

, COOCH ₂ CHC ₄ H ₉

OOCHoCHC

^: 2? ^HC 4 ^H 9

C ₂ H ₅

309827/1087

COCHCONH

OQ CO

0OCH ₂ CHC ₄ Hg

2 ^H 5

Cl

COCHCONH-

COOC ₁₂ H ₂₅

OC CO

OCH,

COCHCONH

OC

COOC ₁₄ H ₂₉

309827/1087

f ~ \

oc

COCHCONH

COOC ₁₄ H ₂₉

Cl

«\ - COCHCONH

~ Λ

OC CO

f ~ \

'COCHCONtI-

ϊ · ϊ

-NH COOCH ₀ CHCc ₁ H ₁

^C 6 ^H 13

COOC ₁₄ H ₂₉

309827/1087

(14)

Cl

-TV

COCHCONH

OC CO

σ NH

NHCOCHO C ₂ H ₅

^C 5 ^H ll ^(t)

(15)

H CO- / V-COCHCONH-

"A.

OC CO

H 1 C -C NH

• C ₄ H ₉ (sec)

> MHDO (

(16)

COCHCONH

NH

. ^C _v 5 ^H ll ^(t)

309827/1087

(17)

H _x CO -f V-COCHCONH

OC ^{7 x} C0

■ NHCOCHO—

COCHCONH

S0 ₂ N (C

(tJH

OC

H ₃ CO

OCHCONH

O ₂ H ₅ "- COCHOONH— ff \

"LJ ⁰

309827/10

-Λ5 -

Cl

H ₅ CO

CONHCHCONH

I *

OC CO

NHCOCH ₀ O

Cl

H ₃ CO-

COCHCONH

) 'C CO

CH ₂

Cl

H ₃ CO- / \ -COCHCONH

OC CO C O

Q ^H ll ^(t)

NHCO (CH ₂ ) -0

C. C.

309827/1087

(23)

(24)

CO

COCHCONH

OC CO -C-S

COCHCONH

• NHCOCH-O ^ C ₂ H ₅

O ₅ H _{ll (} t)

NHCOCHO

H ₃₅ C ₁₇ CONH

COCHCONH

COOH

COOH

309827/1087

H ₅ CO

COCHCONH

OC CO

NHCOCHCh = CHC-,, H CH ₂ COOH

COCHCONH

DC "CO

H ₅₅ C ₁₆ CH = CHCHCO

COCHCONH

CH ₂ COOH

H ₅ C- od co

JJA-Z

3 0 982 7/1087

Cl

_CH

COCHCONH I N

OC CO

NHCO (CH ₂ ) ₅ 0 - // _ Μ- C ₅ H ₁₁ (t)

Cl

COCHCONH

, N ₁ C ₂ H ₅

OC OO

NHCOCHO

° 15 ^H 51 ⁽ⁿ⁾

COCHCONH

OC CO

309827/1087

(52)

OCH,

COCHCONH

OC CO

(55)

Cl

_Η CO-

COCHCONH—

oc co

NO,

(34)

H ^ CO

-cochconh ■

co

Cl

'NH

309827/1087

(55)

COCHCOM

OC CO

L, C-C Nile

NHCOCH,

(56)

(37)

CH., J

Cl

JC-C N-CJL

CH.,

f V-COCHC

ONH -

CO OCH,

C ₂ H

309827/1087

-.51 -

Cl

tV-COCHCONH

ocr co I

NHCOCHO I

C ₂ H ₅

C ₅ H ₁₁ Ct)

N CH.

CH,

(39)

Cl

H ₅ CO

—COCHCONH—

NHCOCHO-

HN

^C 5 ^H ii ^(t)

(40)

CH O-f ^ V-C OCHCONH-

oc ^xx co

COOH COOH

L ₇₇ in)

309827/1087

COCHCOMl
ι

/ Λ

SO ₅ K

OC

OCIL

NJICOCHCO

^CH -

\ J

^C 18 ^H 37

COOC ₁₂ H ₂₅

COCHCOM-I- 1! \ .N _x Cl

r ^x co

OC CO

- C OCIIC ONII-

Cl COOC ₁₀ IL

309827/1

COCHCONH

H ₃ C

OC - C

co

NHCOCHCO- / Λ

NH

C ₄ H ₉ (ISo)

(t) H.

C ₂ H ₅

OCHCOMI-iJrpNHCOCHCO- < C II (t) Cl -N COCHCONH-:

-Li-

HC - C

⁵ · I

CH ₇ Cl

NH

ρ -

NH

_r H -; -

309827/1087

The yellow-forming couplers according to the invention can be prepared by reacting a coupler for 4 equivalents in which one of the hydrogen atoms of the active methylene group is substituted by a halogen atom , preferably a bromine atom, and an imide compound as defined in the above general formula (I)

N

O = C c = o residue, and where the

free imide or the salt thereof can be used, in the presence of an inorganic basic material, preferably potassium hydroxide or sodium hydroxide or

en
of an organic basic material, preferably triethylamine or 1,4-diazabicyclo-2,2-octane, in an organic solvent. In the above-mentioned reaction, a salt of the corresponding imide compound with an inorganic

en
or organic basic / material can be used in place of the free imide compound. In this case, the inorganic or organic basic / material used in the above reaction may not be necessary.

The amount of basic material is not overly critical, but the best results will be achieved when about 1 to about 2 moles of the basic material per one mole of the imide compound can be used. However, larger and smaller amounts of basic material can also be used can be used successfully.

An anide solvent such as dimethylformamide, dimethylacetamide, Hexamethylphosphoramide etc. are used,

te with a dielectric constant of more than 30, N-methyl-2-pyr ^ lidon and tetramethyl horn, and an oxide solvent such as dimethyl sulfoxide. The GE-

309827/1087

SS

the exact amount of solvent used can be within can be varied over a wide range and is not unduly critical so long as it is sufficient Amount of solvent is present so that the reaction can go on smoothly. Excellent Results are obtained using from about 5 to about 20 parts by weight of solvent per 1 part by weight of imide.

The reaction takes place at a low temperature and at high speed, taking the desired coupler in high purity and in high yield Use of such solvents is achieved.

On the other hand, the desired coupler can only be insufficiently obtained when synthesizing couplers for 2 equivalents by refluxing with heating and using acetonitrile as a solvent, as described in Japanese Patent Hr. 26 133/72 and US Pat. No. 3,408,194 is carried out for the preparation of the coupler according to the invention. This is due to the fact that there is an excessive amount of by-products, and their separation and purification of the desired product are very difficult. The main by-product is a dimer of the coupler attached to a coupling position of the coupler.

The imide compound will prove to be desirable in molar Excess with respect to the coupler used, preferably in a molar excess of 1.5 to 3 x

The reaction may proceed within a wide temperature range in front of, preferably within ⁰ ° C to '80 ⁰ C.

3098 27/1087

Sf

The amide solvent and the sulfoxide solvent can be used alone or as a mixture of two or more thereof be used. The solvent can be used to regulate the rate of conversion or the extent of conversion with commonly used solvents such as alcohols such as methanol, ethanol and isopropanol,

with halogenated hydrocarbons such as chloroform and methyl chloroform; with hydrocarbons such as ligroin and hexane, aromatic hydrocarbons such as benzene, toluene and xylene; with acetonitrile and others are diluted.

Production example 1

Preparation of 2'-chloro-5'- _i /a-(2,4-di-tert.-amylphenoxy)-butylamido-4-methoxy-a-phthalimidobenzoylacetanilide (coupler 2):

A mixture of 70 g of 2 ^l -chloro-5 '- / ä- (2,4-di-5-tert-amylphenoxyj-butylamido ^^ - methoxy-a-bromobenzoylacetanilide and 55 »5 S potassium phthalimide were in 500 ml of dimethyl sulfoxide The reaction product was poured into 2 liters of water and extracted with 1 liter of ethyl acetate. The ethyl acetate layer formed was collected, washed with dilute hydrochloric acid solution (5% HCl, washed with water and then dried over Glauber's salt). By distillation of ethyl acetate under reduced pressure (15-30 mm Hg) and recrystallization of the product from a mixed solvent of ethyl acetate / hexane (1: 4), 55 g of coupler 2 having a melting point of 155-157 ° C. were obtained.

309827/1087

Production example 2

Preparation of 2'-chloro-5 ^l -tetradecyloxycarbonyl-a-phthalimido-benzoylacetanilide (coupler 6):

A mixture of 16.5 S 2 ^l -chloro-5'-tetradecylocycarbonylchlorobenzoylacetanilide and 18.5 g of potassium phthalimide was stirred in 300 ml of dimethylformamide for 3 hours at room temperature. The reaction product was treated as in Preparation Example 1. After recrystallization of the product from methanol, 12 g of coupler 6 with a melting point of 81 to 82 ° G were obtained.

Production example ^

Production of 3 ~ Ζά- (2,4-di-tert-amy! Phenoxy) -butylamido7-5 ' -N, N-diethylsulfamyl-4,2 · -dimethoxy-cc-phthalimidobenzoylacetanilide (Coupler 18):

A mixture of 16.5 S 3 ~ / ä- (2,4-di-tert-amylphenoxy) -butylamiod-5 ^l -N, N-diethylsulfamyl-4,2'-dimethoxy-abrombenzoylacetanilide and 11 g of phthalimide were in 250 ml of dimethylformamide for 3 hours at room temperature. The reaction product was treated as in preparation example 1 and the product obtained was recrystallized from a solvent mixture of ethanol and ligroin in a ratio of 1: 1. On recrystallization of the product from acetonitrile, 11.5 6 ^ s of coupler 18 with a melting point of 197 "to 200 ° G were obtained.

309827/1087

SB

Production example 4

Preparation of 2'-chloro-5 '- / ä- (2,4-di-tert-aminophenoxy) -butylamidoZ - 4-methoxy-oc-succinimidobenzoylacetanilide (coupler ^):

A mixture of 50 g of 2'-ChIOr ^ ¹ -, {£ - (2,4-di-tert-amylphenoxy) -butylamido7-4-metlioxy-a-bromobenzoylacetanilide and 50 g of potassium succinimide were in JOO ml of dimethylformamide for 3 hours stirred at room temperature. The reaction product was treated as in Preparation Example 1. After recrystallization of the product from a mixture of ethyl acetate and hexane (1: 4-), 36 g of coupler 5 with a melting point of 138 to 139 ° C. were obtained.

Manufacturing example 5

Production of 2'-chloro-5'-Z- (2,4 ~ di-tert-amylphenoxy) - "butylami do7-4-methoxy-a- (5 »5-dimethyl-J-hy dantoinyl) benzoylacetanilide (Coupler

A mixture of 35 g 2
amylphenoxyj-butylamido- ^ methoxy-a-bromoacetanilide and 25 ß of the potassium salt of 5> 5-dimethylhydantoin was stirred in 250 ml of dimethylformamide for 3 hours at tree temperature. The reaction product thus obtained was treated as in Preparation Example 1. On recrystallization of the product from ethanol, 18 g of coupler 14 with a melting point of 112 to 125 ° C. were obtained.

309827/1087

-Pt -

Production example 6

Preparation of 2'-chloro-4-metho: xy-5-nitro-a-phthalimidobenzoylacetanilide (Coupler 33) >

A mixture of 30 S 2'-Chlor-A-methoxy-5-nitro-ocbrombenzoylacetanilide and 39 S was potassium phthalimide in 400 ml of dimethylformamide for 3 hours at room temperature touched. The reaction product was treated as in Preparation Example 1. After crystallization of the product from methyl cellosolve were 1: 4 g of des 'Coupler 33 with a melting point of 203-205 ° C obtained.

Production example 7

Preparation of 5 ^l -amino-2 ^l -chlor-4-mevthoxy-a-phthalimidobenzoylacetanilide (coupler 34):

10 g of 2'-chloro-4-methoxy-5-nitro-a-phthalimidobenzoylacetanilide, prepared according to preparation example 6, were added to 100 ml of 90% acetic acid. The mixture was heated on the steam bath and then 5 S were reduced Iron slowly added to the mixture with stirring. The reaction product was filtered, the oil poured into 1 liter Poured water and filtered off the crystals formed, washed with water and recrystallized from ethanol, wherein 4 g of coupler 34 having a melting point of 105 to 107 ° C were obtained.

In the above, some preparation examples according to the invention have been described, while in the following the photographic elements as obtained in accordance with the present invention are shown individually. will.

309827/1087

- sr «- 2263875 60 Production example 8

Preparation of 2'-chloro-5 ^l -a-2,4-di-t-amyl-phenoxybutylamide-4-methoxy-a-phthalimide-benzoylacetamilide (coupler 2):

The procedure was the same as in Preparation Example 1, except that 4-00 ml of dimethylacetamide were used instead of 500 ml of dimethylformamide and the mixture was stirred for 30 minutes. The reaction mixture was treated as in preparation example 1, 60 g of coupler 2 having a melting point of 155 ^° C. to 157 ^° C. being obtained. -

Production example 9

Preparation of 2'-chloro-5 ^l -y- ^, ^z l- di-t-amylphenoxy) butylamide-A-methoxy-2 (5.5-dimethyl-3-hydantoinyl) -benzoylacetanilide (coupler 22):

32 g of 2'-chloro-5'-y- (2,4-di-t-amylphenoxy) butylamide-4-methoxy-a-bromoacetanilide were dissolved in 200 ml of hexamethylphosphoramide. This solution became a solution of 25 g of 5 _I 5-dimethylhydantoin

■ and 12 g of potassium hydroxide in 30 ml of methanol were added, and the combined solution was stirred for one hour at room temperature. The reaction mixture was treated in a manner similar to Preparation Example 1, except that the recrystallization started from acetonitrile, and 26 g of Coupler 22 having a melting point of 142 ^° C. to 143 ^° C. was obtained.

309827/1087

Preparation example 10,

Preparation according to preparation example 8, but using a mixed solvent of 200 ml of dimethylformamide and 100 ml of acetonitrile. There were obtained 23 g of coupler 22 having a melting point of 142 ⁰ C to 14-3 ^0C.

Production example 11

Preparation of 2 ^l -chloro-4'-dodecyloxycarbonyl-2-methyla-phthalimide-beiizoylacetanilide (Coupler 9) J.

^{29 g of 2 l} -chloro-4'-dodecyloxycarbonyl-2-methyl-a-bromo-benzoylacetanilide, 29 g of phthalimide and 20 g of triethylamine were stirred in 200 ml of dimethylformamide for 3 hours at room temperature. The reaction mixture was treated in a manner similar to Preparation Example 1, except that ligroin was used for recrystallization. There were obtained 20 g of coupler 9 with a melting point of 100T to 101 ⁰ C.

09827/108

The photographic silver halide emulsion used in the present invention consists of a dispersion any photosensitive silver halide as used in the art, e.g. silver chloride, Silver bromide, silver chlorobromide, silver iodobromide or silver chloroiodobromide, in a hydrophilic polymer as colloidal grains. The grain size of the used Silver halide according to the invention is not critical and can vary within wide limits as with the materials currently used in the art. The average grain size is about 0.5 to 5/1 »more preferably 0.1 to 2».

The photographic emulsion can be according to various Processes are generated as they are, for example, in "Chimie Photographique" 2nd edition 1957 »Paris von-P.Glafkidis are described. Inner image type direct positive emulsions are in "The Theory of the Photographic Process "3rd Edition 1966, N.Y. by Mees and James and can also be used in the context of the invention.

Typical examples of hydrophilic polymers used for forming the silver halide photographic emulsion are proteins such as gelatin, high molecular weight non-electrolytes such as polyvinyl alcohol, polyvinylpyrrolidone, Polyvinyl acrylamide, and the like. High molecular weight amphoteric electrolytes, such as polyacrylamide, according to the Hoffman decomposition reaction is dealt with (see A. M. Schüler and T. J. Suen, Ind. Eng. Chem., Volume 48, pages 2132 to 2137 (1956)) and copolymers of acrylic acid and N-vinylimidazole. Other useful hydrophilic polymers include polyvinyl acrylamides such as polyacrylamide cellulose derivatives, polycinyl alcohols or hydrolyzed

309827/1087

Polyvinyl acetates, as indicated in US Pat. No. 2,286,215, hydrolyzed cellulose esters, such as cellulose acetate, which is hydrolyzed to an acetyl content of 19 to 26%, as indicated in US Pat. No. 2,327,808, water-soluble ethanolamine cellulose acetates, as in US Pat. Patent 2,322,085 specified, and polyacrylamides with a bound acrylamide content of from 30 to 60 ° / o and a specific viscosity of 0.25 to 1.5 or imidized polyacrylamides with a similar acrylamide content and viscosity similar, as described in US Patent 2,541 474- indicated, zein as indicated in US Pat. No. 2,563,791, vinyl alcohol polymers containing urethane carboxylic acid groups of the type described in US Pat. No. 2,768,154, vinyl alcohol polymers containing cyanoacetyl groups, e.g. the vinyl alcohol-vinylcyano-acetate copolymers, the in US Pat. No. 2,808,331 contain and polymeric materials that are used in the polymerization of a Protein or a saturated acylated protein with a monomer having vinyl groups, as disclosed in U.S. Patent 2,852,382.

The photographic silver halide emulsions according to the invention can furthermore contain various additives, as they are usually added to the usual color photographic silver halide emulsions, for example Sensitizers, stabilizers, hardeners, surface active agents and the like.

Examples of these are sensitizers, such as (a) speed-increasing compounds according to the U.S. Patents 2,271,623, 2,288,226, 2,334,864, and 2 7O8 162 and (b) compounds serve to increase photosensitivity of the silver halide corresponding to

309827/1087

British Patent 1,221,875, German Offenlegungsschrift 2,137,559 and Japanese Patent Applications 19 93V7O and 30 023/71, stabilizers such as benzotriazole, 5-nitrobenzimidazole, 1-phenyl-5-mercaptotetrazole and 4-hydroxy-6-methyl-1,3 , 3 ^a , 7-tetrazaindene, hardeners as disclosed in U.S. Patent Nos. 3,325,287 and 3,362,827 and Japanese Patent Nos. 257,564 and 3O9,487, surface active agents, corresponding to U.S. Patent 3,441,413 and British Patents 1,164,095 and 1,012,495 and anti-oxidants corresponding to U.S. Patents 2,360,290 and 2,403,721-

The above-mentioned silver halide photographic emulsion s containing the yellow-forming coupler according to the invention as an embodiment of the invention, can be applied to various photographic supports. Typical examples of such Carriers are cellulose acetate films, polystyrene films, polyester films, Polycarbonate line, papers, papers coated with polyalkylenes such as polyethylene, and glass plates.

The aromatic primary amines used as developing agents in the invention include compounds with a primary amine group on the aromatic input and have the ability to develop the exposed Silver halides and also include precursors useful in forming such compounds. In the practical implementation of the invention are o-aminophenol, p-aminopheno, N, N-di-substituted O-phenylenediamines and especially N, N-p-phenylenediamine most preferred. Specific examples of such primary aromatic Amines as developing agents are 4-amino-3-dimethylamino-N, N-diethylaniline, 4-amino-3-ethoxy-N, N-diethylaniline, 4-amino-3,5 ~ dimethyl-N, N-diethylaniline, 4-amino-

309827/1087

it

3-methyl-N-ethyl-N- (ß-hydroxyethyl) aniline, 4-amino-3-methyl-N , IT-diethylaniline, 4-amino-3-methyl-N-ethyl-N- (ß-methylsulfonamidoethyl) -aniline, 4-Amino-3- (ß-niethylsulfonami doäthy1) -N, N-diethylaniline, 4-amino-N-äthy1-N- (ß-hydroxyethyl) -aniline, 4-Amino-N, N-diethylaniline and 4-Ainino ~ N-ethyl-N- <w - sulfobutylaniline.

Additional examples of useful materials are given in Liees-James "The Theory of the Photographic Process" 3rd edition, 1966, N.I. in Table 134 on pages 294 "to 295, in particular those compounds which are marked with "++" in table 134. The development agent concentration is not critical and is usually about 0.5 g to 50 g / liter, -uro at 1 to 20 g / l are most preferred.

The color developers used in the present invention can be various other than the above developing agent. Contain additives such as are commonly used in color developers. Examples are alkali sulfites, carbonates, iodides, bromides , benzyl alcohols and the like.

The couplers used according to the invention have the feature that a hydrogen atom on the carbon atom in the α-position of the aromatic α-(alkyl) acetamide is replaced by a cyclic K-carbonyl group, i.e. one by two Garbonjlenippes. activated nitrogen atom is bound to the carbon ε.-ho- ·: aor © position of the acylacetamide »- ^T 3a vlx-d sr-seiiomü'ier · _v that the oxidation product of the az-omal:! should :: primary amine as a developing agent with ai-isar · oc-Carboiasidacylaeetamid-connection with cleavage of the bond between the imide nitrogen atom and the Eoiilenstoffatom the ce-position reacts and forms the azomethia dye oiid © in Iiaidion.

309827/108 7

The couplers used in the present invention have the following valuable properties.

The α-imidoaeylaeetamide type coupler of the present invention is a 2 equivalent coupler; H. it only requires two equivalents of silver halide as an oxidizing agent to form a molecule of the dye. Compared with an acylacetamide type coupler for 4 equivalents, which is commonly used widely, becomes the amount of silver halide required to half when using the coupler according to the invention decreased so that the proportion of the contained in the photographic silver halide emulsion layers Silver halide it the photographic photosensitive Materials can be reduced. Thus, not only the manufacturing cost for the photographic photosensitive Materials can be reduced, but also the light scattering due to the in silver halide grains present on the photographic emulsion layer can be reduced, and thereby the sharpness of the image formed can be improved. Furthermore can according to the invention the thickness of the coupler-containing silver halide emulsion layer based on the reduced proportion of silver halide, so that thereby also the necessary for development Time can be reduced.

The imide type couplers used according to the invention have a high coupling reactivity with the oxidation product of aromatic primary amines as developing agents, so that the formed oxidation product of the developing agent is quickly removed during color development and promotes development of the silver halide emulsion will. This results in the formation of the color image

309827/1 087

carried out according to the invention within a short period of time. Due to the high responsiveness of the Couplers according to the invention will also obtain sufficient coupling or coloring even if the amount the solvent, especially the non-volatile one Solvent - for the dispersion of the oil soluble coupler in the silver halide emulsion, is greatly reduced.

By reducing the amount of solvent remaining in the silver halide photographic emulsion layer of the photosensitive material can further improve the mechanical strength of the emulsion layer increase.

In the case of using acylacetanilide type couplers, which are substituted by an imide group according to the invention, the dye formation step in the Color developing bath has ended and therefore a bleaching bath must be used in the subsequent treatments. which contains a strong oxidizing agent, such as potassium ferricyanide or potassium bichroxaate, is not necessary and The developed, photosensitive material can be put in a blixing bath, which is a weak oxidizing agent, such as a ferric chelate complex of ethylenediaminetetraacetic acid containing, are treated, thereby making it possible to shorten the total color development processing time and the problem of water pollution due to the waste treatment liquid, for example ferricyanide waste, to reduce. However, in the case of application the usual acylacetamide type couplers in which the coupling reaction site is unsubstituted, the Coupling reaction does not end in the color development "6ad, i.e. a considerable proportion of the product of the coupling reaction remains in the state of the colorless leuco form

309827/1087

and a strong oxidizing agent is required to completely color the colorless leuco form.

When the dye image formed from the imide-substituted acylacetamide type coupler according to the invention is kept under severe conditions for a long period of time, it shows at most a low one Tendency to fade.

The silver image formed as a by-product in the step of forming the dye image according to the invention is easily oxidized in the bleaching bath or the blixing bath and the reduced silver can completely during removed within a short period of time after treatment. As a result, a sharp, clear yellow Color image without staining due to remaining Silver according to the invention can be easily obtained.

The imide-substituted couplers of the acylacetamide type used according to the invention can be used in high yields using starting materials readily available in the industry.

The amount of the coupler to be used in the present invention depends on the type of the photographic photosensitive Material in which it is to be used or the type of development process is influenced, however, is a A range of from 0.02 to 1.0 moles of coupler per mole of silver halide in the silver halide emulsion is particularly useful and an amount of 0.1 to 0.5 moles of coupler per mole of silver halide is most preferred. If the amount is less than the lower limit, a large amount of silver halide is required to be sufficient for the light-sensitive material To give required color extinction coefficients, whereby an increase in the light scattering of the silver halide emulsion layer and adjusts a reduction in the sharpness of the image. That is, the increase in the amount

309827/1087

- fr * -

of the silver in the silver halide emulsion is of one An increase in the thickness of the emulsion layer and a decrease in the speed of the development processing Emulsion layer accompanied. On the other hand, if the amount of the coupler is larger than the upper limit, the Conversion of the coupler to the dye is insufficient, so that the effectiveness of the utilization of the coupler is reduced will. The use of such a large amount of coupler decreases and increases the economic benefits on the other hand, the thickness of the silver halide emulsion layer. Outside the above specified addition ranges the coupler, the advantages according to the invention cannot be sufficiently obtained.

In the embodiment where the coupler is in the developer, the coupler should be in the developing bath be present in an amount of Ο, Ί to 10, preferably 0.5 to 5 g / l of developer. As above indicated, if quantities outside the specified range are used, the advantages and tasks according to the invention cannot be obtained in a sufficient manner.

Me couplers of the general formula I can be used individually or as combinations. Furthermore Couplers of the general formula I can also be used together with other couplers.

The following examples further illustrate the invention on the basis of preferred embodiments of the invention.

example 1

A solution which can be obtained by heating a mixture of 28.8 g of coupler (2)., D. H. a-4'-Methoxybenzoyl-a-phthalimido-2-chloro-5- <£ a- (2 ", 4 - "- di-tert-amy! Phenoxy) -butylamido7-

309827/1087

acetanilide, 30 ml of di-n-butyl phthalate and 50 ml of cyclohexanone at 70 ° C was made 300 ml of an aqueous solution containing 30 6 Gelatin and 2.0 g of sodium dodecylbenzenesulfonate were added, followed by stirring. Then the mixture turned up Preheated to 45 ° C and passed through a colloid mill five times whereby the coupler was finely dispersed in the solvent.

The total amount of the emulsified dispersion of the coupler was added to 1.0 kg of a photographic emulsion containing 54% silver iodobromide (molar ratio I: Br = 3 ^: 97) and 60 g of gelatin, and after further addition of 30 ml of a 3% strength acetone solution from triethylenephosphamide to the mixture as a curing agent, the pH of the mixture was adjusted to 6.0. Then, the silver halide emulsion thus prepared was coated on a triacetyl cellulose film to a dry thickness of 7 »0 microns, and a photographic light-sensitive material called Sample A was obtained. The coupler content in the Sample A was 1.96 χ 10 ^"5 mol / m ^2.

A comparative sample of a photographic light-sensitive material was prepared by the same procedure as in the preparation of sample A, but using 23.5 g of a-4'-methoxybenzoyl-2-chloro-5- / a- (2 ", 4" -di-tert.-amylphenoxy) -butylamido / - acetanilide (Coupler a) prepared instead of coupler 2 and the comparative sample designated as sample B.

Each of these photographic light-sensitive materials was subjected to step exposure for sensitometry under a graduated optical wedge with a light of 50 CMS for 1/20 of a second (see Russell Campbell,

309827/1087

20 ° C. 15th Minutes 18 ° C. 1 Il 20 ° C. 4th Il 18 ° C. 5 It 20 ° C. 5 Il 18 ° C. 5 ti 20 ° 0 3 Il 18 ° C. 15th Il

Ϊ1

"Photographic Theory for the Motion Picture Cameraman"

1st edition, 1970, N.Y.) and then subjected to the following treatments:

1. Color development

2. Water wash

3 · First fixation

4. Water wash

5. Bleaching

6. Water wash

7. Second fixation

8. Water washing

The composition of the above color development The color developer used was as follows:

Color developer A

Water '1000 ml

4-amino-3-methyl-N, N-diethylaniline hydrochloride 2.5

Anhydrous sodium sulfate 3iO g

Sodium carbonate (monohydrate) 47.0 g Potassium bromide 2.0 g

The fixing solution used in the above treatment was an acidic aqueous solution with a Content of sodium thiosulfate and sodium sulfite, and the bleaching solution used above was a neutral one Solution containing potassium ferricyanide and potassium bromide:

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- fiö - (anhydrous) 2263875 6th L. U 6th 155.0 ml Fixing solution 15.0 6th Sodium thiosulfate (anhydrous) 15.5 G Sodium sulfite 7.5 Glacial acetic acid 15.0 Boric acid 1000 m] Potassium alum Water too

pH 4

Bleach solution

Potassium ferricyanide 50.0 g

Lalium bromide 20.0 g

1000 ml of water

pH 6.5 to 7.0 at 25 ° C

After the treatment, the optical density for blue light was measured for samples A and B, the results above are given in Table I. The color image of the two samples was a sharp yellow image with one Absorption maximum at 454 nm.

Coupler Table I. gamma Maximum
density sample (2)
(a) Veil sensitive
ability *
(relative) 2.57
1.65 5.24
2.51 A.
B. 0.18 100
0.12 96

(*) Required exposure amount to get one density of 0.10 above veil.

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69 -

Therein was the "maximum density for blue light" for Samples A and B that was obtained when the samples were changing the treatment time for color development were treated, the results of which are shown in Table II.

Coupler Tabel II 15 20 sample 3.24-3.27
2.51 2.53 (2)
(a) 5 Development time (minutes) A.
B. 2.66
1.69 10 3.25
2.32

These results show that the inventive Process used imide-substituted Coupler has a higher sensitivity, graduation and coupling density than the unsubstituted coupler (a), the was used in ver comparative sample, and that continues in the case of the application of the coupler according to Invention sufficient color was obtained in a shorter period of time, reducing the total treatment time is abbreviated. This clearly shows that the imide-substituted coupler has higher coupling reactivity than an unsubstituted one.

To further clarify the improved coupling reactivity of the coupler according to the invention, carried out the following experiment.

A silver bromide emulsion layer comprising a mixture of Coupler (2) or Coupler (a) and a cyan-forming coupler (b), namely 4,6-dichloro-5-methyl-2-Z-C2 ', V-ditert.-amy / phenoxy) -acetamido / -phenol contained was in

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- η »-IH

developed the color developer A at 21 ° C for 14 minutes, where the two couplers reacted competitively with the oxidized developing agent and gave a mixture of yellow and cyan dyes. By analyzing the
The formation ratio of the yellow dye to the cyan dye became the relative value of the reaction rate constant of the coupling reaction for the yellow-forming coupler based on the cyan-forming coupler (b)
obtain.

The coupling reactivity of a coupler is called
Relative value in color development of a silver halide emulsion containing two kinds of couplers A and B,
what different colors result, which are clearly separated from each other, and measuring the amount of each dye in the color image formed. If the coupler A
shows a color density D, the maximum value of which is (D ») max, and the coupler B shows a color density Dg, the maximum value of which
D-η max., The ratio Ra / ^ of the reactivities of the two couplers is given by the following
Equation reproduced:

Max

log (1 -

Max

That is, the coupling reactivity ratio
is derived from the gradient of the log (1-D ./ (D.))

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versus log (1- Eg / CD-g) ^^.) obtained line. As a result, the relative rate constant of the imide-substituted coupler (2) was shown in FIG of the invention 6.6, while that of the usual unsubstituted Coupler (a) had a value of 1.1. The results show that the coupling reactivity of the imide type coupler according to the invention was 6 times higher than that of the conventionally known unsubstituted one Coupler.

Example 2

Samples A and B, prepared according to Example 1, were subjected to a step exposure for sensitometry exposed to light of 100 CMS for 1/20 second using a graduated optical wedge and in the following manner treated: ·

1. Color development

2. Stop treatment 5 · Blixing

4. Water washing

That in the above color development treatment The color developer used was the same as in Example 1 and the compositions of the other processing solutions were the following:

24 ° C. B. Minutes 24 ° G 2 It 24 ° G 6th It 24 ° C. 5 ti

Stop solution 1000 ml * water 5.0 g Sodium sulfite anhydrous 15.0 ml Glacial acetic acid

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Blixing solution

Water 1000 ml ammonium thiosulphate 105.0 g

Sodium sulfite 80 g

E.D.T.A. (Disodium salt) 35.0 g

Ferric chloride (hexahydrate) 25.0 g

Potassium thiocyanate 10.0 g

After the treatment, the blue light optical density of each sample was determined. Then each sample in an aqueous 1.5% solution of potassium ferricyanide immersed for 2 minutes at 24 ° C, washed with water for 10 minutes and dried. Then was redetermines the optical density for blue light; the results are given in Table III.

Coupler Table III by ferricyanide solution sample Aftercare Then (2)
(a) before egg; (2; (5;
0.19 2.55 5-50
0.13 1.61 2.55 A.
B. (i; (2; (5;
0.19 2.52 5.28
0.12 1.24 1.96

(1): haze, (2): gamma (5) '> maximum density.

As can be seen from Table III, the formation of the color image in.JTaIl the use of the imide-substituted coupler (2) according to the invention in the steps of color development and blixing ended, while in the case of the use of the usual unsubstituted coupler (a) the formation of the The color image in these stages was only 3/4 complete and the remaining reaction product

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- 99- ■

was in the colorless state. To complete that
To convert the colorless reaction product into the dye, treatment with a strong oxidizing agent was required. It can be seen from the data that when the new imide-substituted yellow-forming couplers according to the invention are used, the number of color development treatments can be reduced.

Example 3

A mixture of 63.7 g of the coupler (19), α- £ 4'-methoxy-3 ¹ - ^ öc- (2 ", 4" -di-tert. ~ Amlyphenoxy) -butylamidofbenzoyl-a-suecinimido ~ 2- methoxy ~ 5-0tf, N-diethylsulfamoyl ·) acetanilide, 65 ml of tri-n-hexyl phosphate, 100 ml of ethyl acetate and 3v2 g of sodium dinonylnaphthalene sulfonate were added
heated in a steam bath to make a solution. After adding the solution to 700 ml of an aqueous solution of
50 g of gelatin, the mixture was stirred and then further vigorously stirred in a high-speed stirrer,
so that the coupler was finely dispersed in the solvent.

The total amount of the emulsified dispersion thus obtained became 1.5 kg of a photographic emulsion containing 0.30 mol of silver chlorobromide (molar ratio
Cl; Br = 30:70) and 100 g gelatin and after
Addition of 15 ml of a 4% aqueous solution of
1-Hydroxy-3 »5- <iichloro-S-triazine as hardening agent and
Adjustment of the pH of the mixture to 6.5 was
the mixture on a baryta-coated paper, both surfaces of which were coated with polyethylene, to one
3> 0 microns dry thickness drawn down to form a photographic light-sensitive material which
was designated as sample C. The coupler content of the sample

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C was 1.03 χ 10 " ⁵ mol / m ² .

For comparison purposes, an emulsified dispersion of a comparative coupler was prepared according to the same procedure as in the preparation of sample C using 56 »4 g of a- {4 ^l -methoxy-3'-Zic- (2", 4 ^tl -di-tert .-amylphenoxy) -butylamidoj ^ -benzoyl-2-methoxy-5- (N, N ₇ diethylsulfamoyl) acetanilide (Coupler C) instead of the coupler (19).

The total amount of dis- · persion became 3 »° kg of a photographic emulsion, which contained 0.60 mol of silver chlorobromide and 200 g of gelatin, added and after adding 25 ml of a 4%, aqueous solution of the sodium salt of 1-hydroxy-3 »5-dichloro-S-triazine to the solution and adjustment of the pH of the mixture to 6.5, the mixture was adjusted to a Barite-coated paper, as used in the -frobe C. was to a dry thickness of 4.0 microns to form of a photographic light-sensitive material, which was designated as Sample D. The salary the coupler in sample D was 1.01 10 "* mol / m.

The silver halide emulsion used to make these samples was made by dividing the same silver chlorobromide emulsion into two parts and diluting each one Partly made with an aqueous gelatin solution, if necessary. The coupler content was in each The same emulsion, but the silver content was different.

Each of the samples was subjected to a stepwise exposure for sensitometry as in Example 2 and then treated as in Example 1, except that development in a developer B of the following composition took place for 12 minutes at 24 ° C:

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Color developer B

water

Benzyl alcohol
Sodium hexametaphosphate Anhydrous sodium sulfite Sodium carbonate (monohydrate) Hydroxylamine sulfate

4-Amino-3-methyl-N-ethyl-IT- (ß-methanesulfonamidoethyl) aniline sesquisulfate (Monohydrate)

1000 ml
12.0 g 2.0 g 2.0 g

27.5 6 2.5 g

4.0 g

After the treatment, the diffraction optical density became each sample intended for blue light; the results are summarized in Table IV.

Coupler AgX / coupler
Molar ratio
nis Table IV Sensation
opportunity
Relative) gamma , 06
, 28 Maximum
density Sample, (19)
(C) A.
8th veil 100
87 2
1 1.63
1.47 C.
D. 0.15
0.10

From Table IV it is clear that the coupler (19) according to the invention has a higher degree of coloration than the unsubstituted coupler (C) exhibited the same structure even if less silver halide was used whereby the thickness of the emulsion layer could be reduced.

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so

Example 4

.A solution made by heating a mixture of 5 x 10 ^ moles of each of the above with carbonimide groups substituted coupler, 4.5 ml of di-n-butyl phthalate, 8 ml of cyclohexanone and 0.2 g of bis (2-ethylhexyl) - a-sulfosuccinate (Sodium salt) was prepared on a hot plate was added to 60 ml of an aqueous solution, γ containing 5 S gelatin was added and the mixture vigorous stirred in a homoblender for a fine dispersion of the coupler.

The total amount of the coupler dispersion obtained in this way was 15Ο g of a fine-grain silver halide emulsion, which contained 3.8 g silver bromide and 13 g gelatin, added and the mixture on a cellulose triacetate film to a dry thickness of 7 microns for purpose Formation of the photographic photosensitive film applied.

By exposing any photographic photosensitive Film and development as in Example 1 gave a yellow image. The spectral absorption properties of each yellow dye image were measured using a spectrophotometer and obtained the maximum absorbance values, which are given in the following table are specified.

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Table V

Coupler Absorption Coupler Absorption maximum (u) maximum (u) CD 44-6 (15) 455 (2) 454 (16) 454 (3) 447 (17) 453 W. 454 (18) 453 (5) 455 (19) 453 (β; 457 (20) 455 (7) 451 (21) 45Ο (8th) 456 (22) 454 (9) 455 (23) 446 (10) 448 (24) 448 (11) 449 (26) 455 (12) 457 (28) 45Ο (13) '448 (29) 454 454 (30) 454

The values in Table V show that the couplers according to the invention have absorption maxima im Range from 440 to 460 microns and thus for parb reproduction according to the subtractive color method have suitable spectral absorption properties.

Example l ^

A solution which, by heating a mixture of 26.5 g of the coupler (13) cc-benzoyl-a- (5 '»5 ¹ -dimethyl-3'-hydantoinyl) -2-methoxy-tert-tetradecylcarboxy-acet-

3 09827/1087

anilide, 25 ml of di-n-butyl phthalate and 55 ml of ethyl acetate had been prepared to 60 ° C., with stirring, was added to 400 ml of an aqueous solution containing 5 »O 6 sodium di- (2-ethylhexyl) -a-sulfosuccinate and containing 36 g of gelatin, was added and the resulting emulsion was passed twice through one Milk homogenizer guided so that the coupler was finely emulsified in the solvent.

The total amount of the emulsified dispersion thus prepared was added to 700 g of a photographic emulsion containing 22.6 g of silver iodide (2 col% iodide) and 50 g of gelatin, and after the addition, 20 ml was added to the mixture a y / oxgen acetone solution of triethylenephosphamide was added as a hardening agent and the pH of the mixture was adjusted to 6.5, whereupon the mixture was drawn up to a dry thickness of 3.5 microns on a baryta-coated paper which had polyethylene layers on both surfaces.

A gelatin solution was further applied to the thereby obtained silver halide emulsion layer to dry strength of 1.0 micron applied as a second layer and a green-sensitive silver halide emulsion, containing the magenta-forming coupler (d) of the following formula, then to a dry strength applied from 3.5 microns:

C ₉ H _R

/ ^ v

NHCOCHO - (' VC ₅ H ₁₁

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- ψ) -Sl

A gelatin solution that has a sufficient amount of

2- (2'-Benzotriazolyl) -4-, 6-dibutylphenol, to provide a coating

2
A concentration of 1.2 g / m 2 was applied to the green-sensitive emulsion layer to a thickness of 2.5 microns as a fourth layer. A red-sensitive silver halide emulsion layer containing the cyan forming coupler (s) of the following formula was then coated thereon as a fifth layer to a dry thickness of 4.0 microns:

COKH (CH ₂ )

Finally a gelatin solution was used on the red-sensitive Emulsion layer to a dry thickness of 0.5 microns as the top layer to form the color photographic Of paper applied.

The green and red sensitive emulsion layers had the following concentrations of the components:

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# 0 -

SH

Components

green-

sens-

Ag Br-Cl
50:50 moles

Coupler

gelatin

red sensitive
lich

cover 9, 0 χ 10 ~ 3
Mol / m ² 9.0 χ 1O ~ ⁴
Mol / m ² 3, Components Ag
50 ; Br-Cl
: 50 times Coupler , 1 g / m ² cover 5, 5x10 " ⁵
Mol / m ^ 1.1 χ 10 ~ ⁵
Mol / m ^ gelatin , 6 g / m

The color negative was optically printed onto the color photographic paper prepared in the above manner and the color paper treated in the color developer B and in the blixing solution according to Example 2. The color print thus obtained showed excellent color reproducibility and gave clear colors. The yellow dye image had the absorption maximum at 443 mti.

Example 6

A solution obtained by heating a mixture of 24.2 g of the coupler (9; i.e., 2'-chloro-5'-dodecyloxycarbonyl-2-methylbenzoylacetanilide, 50 ml of ethyl acetate and 25 ml of di-n-butyl phthalate have been prepared at 50.degree was added to 250 ml of an aqueous solution containing 25 g of gelatin and 1.25 g of sodium dodecylbenzenesulfonate contained, added and then vigorously using a homoblender zdr fine dispersion of the coupler touched.

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8S

The total amount of the emulsified dispersion of the coupler was added to 500 g of a photographic emulsion containing 28 g of silver bromide and 35 g of gelatin, and after further addition of 15 ml of a 2% aqueous solution of 1-hydroxy-3,5-ö- When adding chloro-s-triazine sodium salt to the mixture as a curing agent, the pH of the mixture was adjusted to 6.5. Then, the silver halide emulsion thus prepared was coated on a triacetyl cellulose film to a dry thickness of 5.0 Ji to form a photographic light-sensitive material, which will be referred to as sample E. The coupler content and the amount of silver of Sample E were 1.74 × 10 "^ mol / m ² and 0.76 g / m ^2, respectively.

To prepare a comparative sample, a solution prepared by heating a mixture of 18.8 g of 2 '-chloro-5 ¹ -dodecyloxycarbonyl-S-methylbenzoylacetanilide (Coupler b above) in place of Coupler (9) was added 35 ml of ethyl acetate and 20 ml of di-n-butyl phthalate heated to 50 ° C and added to 200 ml of an aqueous solution containing 20 g of gelatin and 1.0 g of sodium dodecylbenzenesulfonate and then vigorously stirred using a homoblender in the above manner to finely disperse the coupler.

^x CH ₃

-COCH ₂ CONH

/
'(Coupler b)

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The total amount of the emulsified dispersion of coupler b was added to 1 kg of the same silver bromide emulsion as above, and after further adding 20 ml of the same solution of the hardening agent as above, the pH was adjusted to 6.5. Namely, the silver halide emulsion thus prepared was coated on a triacetyl cellulose base to a dry strength of 6.0 / rev to form the photographic light-sensitive material, which was named Sample F. The coupler content and amount of silver of Sample F were 1.77 x 1C ³ mol / m ² and 1.54 g / m ^2, respectively.

Each photographic light-sensitive material was subjected to step exposure for sensitometric and then treated as in Example 1.

After the application, the optical density for blue light was determined for samples E and F; the results are given in table ΨΙ .

Table VI

Suitability for color formation sample coupler molecular fog sensitive γ

Ratio of AgVK couplers

4/1 8/1

speed (relative to the sample = 100)

0.25 0.22

100 98

Maximum density

2.56 3.04 2.17 2.93

Then the maximum density was determined for the sample E and the sample F against blue light, which was obtained when the samples were changed by changing the treatment time for

309827/1087

the color development processed according to Example 1 the results of which are given in Table VII

Table VII

Change in suitability for color formation with development time

Sample coupler molaryer-

ratio of AgX / coupler

(9)

4/1 8/1

Development time (minutes ) 5 10 15 20

2.80 5.03 3.04-3.00 2.41 2.82 2.93 2.98

These results show that the imide group-substituted Coupler (9) according to the process of the invention A high degree of sensitivity and coupling density results, although the amount of silver is halved the amount of the unsubstituted coupler (b) has been reduced and that there is still sufficient color in a shorter period of time, thereby shortening the total treatment time.

To investigate the equivalent property for clarification the fact that the amount of silver required to form 1 mole of the dye in the improved Coupler (9) exhibiting good color-forming property is only half that of the unsubstituted one Coupler Cb) having a corresponding structure is the necessary amount, the following experiment was carried out.

309827/1087

Each sample E and F was subjected to a step exposure and then subjected to the treatments up to treatment step 4 according to Example 1. Then, the amount of deposited silver in the samples containing the color-forming dye and the silver deposit was determined by means of a fluorescent X-ray quantometer. The samples were then subjected to the treatment steps 5 to 8 in Example 1. The color formed was then subjected from the behandelten.Proben with a mixed solvent of N ₁ N-dimethylformamide and water. (85: 15 based "volume) extracted and analyzed the results obtained are shown in Figure 1..

In Fig. 1 it is shown that the molar ratio of the amount of deposited silver amount of the colored Dye in the case of the unsubstituted coupler (b) is 5.5 to 6.0, while in the case of the coupler (9) according to the invention is 2.5 to 2.8, which clearly shows that the molar ratio in the coupler according to of the invention is less than half that obtained with the unsubstituted coupler for'-4 Equivalents is achieved.

Example 7

A solution which, by heating a mixture of 56.0 g of the coupler (14), namely 5 ¹ -Zu- (2,4-di tert -amylphenoxyj-butylami 3 ^ 7-2'-chloro-4-methoxy- ct- (5i5-dimethyl-3-hydantoinyl) -benzoylacetanilide, 100 ml of ethyl acetate and 50 ml of di-n-butyl phthalate had been prepared at 50 ° C., was added to 500 ml of an aqueous solution containing 50 g of gelatin and 2, 5 g

309827/1087

Sodium dodecylbenzenesulfonate was added and then touched. Then the mixture was passed through a preheated colloid mill five times, whereby the coupler was fine was dispersed in the solvent.

The total amount of the emulsified dispersion of the coupler was added to 1 kg of a photographic emulsion which contained 56 g of silver bromide and 70 g of gelatin, and after further addition of 30 ml of a 2% aqueous solution of 1-hydroxy-3, 5-ä-ichlör-s-triazine sodium salt as a hardening agent, the pH of the mixture was adjusted to 6.5. Then, the silver halide emulsion thus prepared was coated on a triacetyl cellulose film to a dry strength of 5 »0 yes to form the photographic light-sensitive material referred to as Sample G. Couplers and silver content of the sample G were 1.70 x 10 ^-5 mol / m ² and 0.75 g / m ^2.

A comparative sample of a photographic photosensitive material was prepared by the same procedure as in the preparation of Sample G using 61.5 g of Coupler Cc), ie, 5 ^l - _{: /a-(2.4-Di-tert.-} amylphenoxy) -butylamido7-2'-chloro-4-methoxy-a-benzosulfimido-benzoylacetanilide »a compound with a group to be coupled off according to the formula

Z, which is analogous to that of the present

Invention is and in the German publication 2 057 941 is made instead of the coupler (14). The comparative sample obtained is called Sample H.

30 9 827/1087

se - 30

NHCOi

(Coupler c)

Couplers and silver content of the sample H were 1.73 x 10 ^-5 mol / n ² and 0.77 g / m ² ·

To prepare another photographic light-sensitive material sample as a comparative sample an emulsified dispersion by the same procedure as that used in the preparation of Sample G using from 46.6 g of coupler (a), d. H. 5 '- ^ cc- (2,4-Di-tert-amylphenoxy) -butylainido / -2'-chloro-4-methoxy-benzoyl-' acetanilide, which is given in Example 1, prepared. The total amount of the emulsified dispersion became y 2 kg of the same emulsion as in the preparation of sample G was added and after the addition of 40 ml of the hardener the obtained coating solution was coated to a dry strength of 6.0 η and the photographic photosensitive Obtain material referred to as Sample I.

The coupler content and amount of silver of Sample I "were 1.77 x 10" ³ mol / m ² and 1.59 g / m ^2, respectively.

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- 9ft -

Each of these robes became a step lighting subjected to sensitometric and then subjected to the same treatments as in Example 3.

After the treatment, the optical density for blue light of these samples was determined; the results are included in Table VIII.

Table VIII Suitability for Color Formation

Sample Coupler Moly Contain- Schlei- Sens- γ Maximum

nis AgX / er ility density Coupler (relative)

G (14) 4/1 0.05 100 2.30 '2.8? H (c) 4/1 0.06 99 1.86 2.61 (a) 8/1 0.03 96 1.79 2.49

Furthermore, the samples obtained by the treatment in the same manner as above were attached to a 1.5 W xenon arc lamp (150,000 lux) for 80 hours exposed, with a UV filter in front of the samples to interrupt the light with wavelengths shorter than 400 mu was brought to determine the light fastness of the color images formed. The results are in Table IX contain.

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- peal

Table IX

Lightfastness of the colored images Sample Coupler Initial density before exposure

(14) 0.5 1.0 2.0 G Cc ") 28 25th 20th H (a) 76 69 61 I. 44 41 34

The numerical values in Table IX show the percentage reduction in density for blue light on the Base of the initial density for blue light.

Furthermore, with samples treated in the same way, the images formed were under for 20 days Conditions of constant temperature of 60 ° C and constant humidity of 70% EH stored and then compared the authenticity. The results are shown in Table X.

Table X

Fastness of the images formed under high humidity

and high temperature

Sample coupler initial density

0j3 1.0 2.0

5 3 48 45

5 5 5 '

The numerical values of the X table show the percentage of reduction in density to blue light based on the initial density to blue light.

6th (14) H Cc) I. (a)

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The values in Tables VIII, IX and X show that the coupler (14) according to the invention a greater color density compared to an unsubstituted coupler Ca) with a corresponding structure and a coupler (c) with an analogous coupling-off group corresponding to the formula

CO-- '

according to the German ^u ffenlegungsschriff 2 057 94-1 shows and that the uncoupling group also has a great influence on the authenticity of the light formed for light, heat and moisture, the coupler (14) according to the invention showing excellent authenticity.

To continue to study the equivalents properties, Samples G, H and I were treated in the same manner as in Example 7 ". Then, the amount of des deposited silver and the amount of colored dye is determined. The results obtained are shown in fig.

According to FIG. 2, the molar ratios of the amount of deposited silver amount to the colored dye in the case of the unsubstituted coupler (a) and in the case of the coupler (c) with an analogous coupling-off group according to the formula

309827/1087

-SB-

CO .... · - ₁ I.

according to the German Offenlegungsschrift 2 057 94-1 6.0 to 6.5 or 2.8 to 3>3> while in the case of the coupler (14) according to the invention the value is 2.2 to 2.5, which clearly shows that the molar ratio, ie the equivalency property, of the coupler according to the invention is less than half of the unsubstituted coupler (a) for 4 equivalents and less than in the case of the coupler (c).

In the foregoing, the invention has been described on the basis of preferred embodiments without being limited thereto.

309827/1 087

Claims (2)

Patent claims A photographic photosensitive element comprised of a support having at least one thereon coated silver halide emulsion layer, which is an a-diacylamino-substituted .aromatic acylacetamide contains as a coupler to form the yellow dye. 2. A photographic photosensitive element consisting of of a support with at least one silver halide emulsion layer coated thereon, the a coupler for forming the yellow dye according to the following general formula: ¹ ^ -C-CH-O-N R-C-CH O = C ^ " ^x. C = O _1 1 2 contains wherein R is an aryl group, R is an aryl group or a heterocyclic group, and Z is those to form together with the unit, N. in general O = C C = O 1 t mean formula of a 4-part, 5-part or 6-part Ringes mean necessary non-metal atoms. 3 · Photographic light-sensitive element, consisting of a support and at least one thereon a "coating a-qrSilberhalogenid-Emul-. sion layer, which contains a coupler to form the yellow dye contains the following general formula: 309 8 27 / VOfi-7- O O = C - CH - 0 ! R ¹ ~ C \
- ...-__ »... A. C - y C = O f wherein R is an aryl group, R is an aryl group or a heterocyclic group and Z together to form with the unit R in the general formula O = CC = O
a 4-membered, 5-Gli ^EDR ite ^s or 6-membered ring mean necessary non-metal atoms and in which at least 1 2
at least one of the radicals R, R or Z contains a hydrophobic group with up to about 32 carbon atoms as substituents. 4. Photographic photosensitive element according to claim 31, characterized in that the coupler has the following formula: _ C-CH-CNR ² O = C C = O wherein R is (1) a phenyl group, (2) a substituted one Phenyl group, in which the ßubstituenten from one or more the radicals halogen atoms, alkyl groups, 303827/1087 pen, alkoxy groups, aryl groups, aryloxy groups, alkylcarbonyl groups, A rylcarbonyl groups, alkyl sulfonyl groups, arylsulfonyl groups, carbonyl groups, alkoxycarbonyl groups, Carbamyl groups, sulfo groups, sulfamyl groups, Acylamino groups, ureido groups, sulfonamide groups, amino groups, nitro groups, cyano groups or Hydroxyl groups, or (3) a condensed aromatic king of the lormel where A represents the atoms necessary to form an aromatic fused ring system, H (1) a phenyl group, (2) a substituted phenyl group, wherein the substituents from one or more of the radicals halogen atoms, alkyl groups, alkenyl groups, Alkoxy groups, aryl groups, aryloxy groups, arylcarbamyl groups, Alkylcarbonyl groups, alkylsulfonyl groups, Arylsulfonyl groups, carboxyl groups, alkoxycarbonyl groups, Carbamyl groups, sulfo groups, sulfamyl groups, acylamino groups, ureido groups, sulfonamide groups, Amino groups, nitro groups, cyar groups or hydroxyl groups /, (3) a heterocyclic, attached to the group / \ C = O O = C / ι In the general formula, heterocyclic groups bonded via 3 in carbon atom in 'the heterocyclic group Group which is part of the conjugated electron system and from the group of thiphenes, furans, Pyrans, chromenes, pyrroles, pyridines, pyrazi- 309827/1087 Pyrimidines, pyradizines nen / indolidines, perimidines, thiazoles, imidazoles, oxazoles, 1,3,5-triazines and oxazines and the substituted derivatives thereof is selected, the substituents from halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups,. Alkylcarbonyl groups, arylcarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, carboxyl groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acylamino groups, ureido groups, sulfonamido groups, amino groups, nitro groups, cyai groups or hydroxyl groups of the formula (4) are selected with a fused ring ¹ V. where A represents the atoms necessary for the formation of an aromatic fused ring system. 5 · Photographic, light-sensitive element according to claim 3 or 4, characterized in that Z consists of one of the following groups 3 \ / c ^X R-C-C-Ir, C = C R ⁴ i ⁶ / \ β 309827/10 87 as ^P 7 \\ _r O / I! \ l2 \ , 14 13th R ¹⁵ - C = C - C - R ¹⁹ - C - Η - R ²¹ R ²⁰ R ²² _ G - W R ² ^ -C NO ^{26th 51} - R Rl JT - R 35 . _R. 37. 38 ^Λ _& 39 wcrin Ε ', 8 *. H ?, E ⁶ , E ?, E ^B , E ?, H ¹⁴ , , R ^, R ¹ ?, R ^ ⁸ , "^ _{1 E} 2 _{Qi R} 22 _? ^ ₁ ^ t ₁ p2? p28 _R 29 _Ώ 30 «51 _Ώ ^^ p ^> ο ^ r _Ώ - - _H ^, each a halogenated, a hydrogen atom »sine group, an alkoxy group, an aryl group, an i group, a sulfo group or, a carboxyl group, where 309827/1 Qg? R ⁵ and R ⁵ , R ⁷ and R ⁸ , R ⁹ and R ¹¹ , R ¹² and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ , R ²⁴ and R ²⁵ , R ⁵¹ and R ⁵² together to form of a saturated or unsaturated 5- or 6-membered ring, while R ²¹ , R ²⁶ , R ⁵⁵ , R ³⁶ and R ³⁷ each represent a hydrogen atom, an alkyl group or an aryl group and W an oxygen atom or a sulfur atom · 6. Photographic photosensitive element according to Claims 3 to 5, characterized in that R a group of the formula represents, and R is a group of the formula represents, wherein X represents a halogen atom, an alkoxy group, an aryloxy group or a tertiary amino group 12 3
represents Y, Y and Y, which may be the same or different, each hydrogen atoms, halogen atoms, alkyl, alkenyl, alkoxy, aryl, aryloxy, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, carboxyl -, Alkoxycarbonyl, carbamyl, sulfo, sulfamyl, acylamino, Ureido, sulfonamido, amino, nitro or cyano groups 4-8
mean, Y ^ and Y, which can be the same or different, each hydrogen atoms, alkyl or 5 6 7 alkoxy groups, Y, Y and Y, which are the same or can be different, in each case hydrogen atoms, alkyl, alkoxy, aryloxy, amino, alkylamino or acylamino groups, and Z is one of the groups 309827/1087 sn - 2? 63875 VO- E ⁵ C = C R '". R _ C - C - C J _] ^ 1? Vi R ¹⁶ R ¹⁸ rW -1 - B - E ²¹ 20th • 22 I C R ' 23 _25th ^25th ι ι ft .31 C I! O ¹¹ ll ^jb - Ν'- N and 309827/1087 fftf represents wherein R ⁵ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , _p 12 _p 13 pH p15 "16" 17 "18" 19 "20 _R 22 _R 23 R ²⁺ , E ²⁵ , H ²⁷ , E ²⁸ , R ²⁹ , B ³⁰ , E ³¹ , R ⁵² , R ³³ , R ³⁴ , R and R ^ - ⁷ each have a V / ater off atom, a halogen atom, a Alkyl, alkoxy, aryl, aryloxy, sulfo or a carboxyl group represent, where B ^ and R, R and R, R ⁹ and R ¹¹ , R ¹² and R ¹³ , R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ , R ²⁴ and R ²⁵ , R ³¹ and Έ? can be linked to one another to form a saturated or unsaturated 5- or 6-membered ring, and R, R, R, R, and R "^ each represent a hydrogen atom, an alkyl or an aryl group and W an oxygen atom or a sulfur atom * 7. A photographic photosensitive element comprised of a support having at least one thereon coated silver halide emulsion layer containing a coupler for the formation of the yellow dye of the general Formula: 309827/1087 - 99 - ο ο _/ η R ¹ - C - CH - C - N Λ ^ν O = C C-O contains, wherein R ^{1 is} an aryl group, R is an aryl group or a heterocyclic group and Z is one of the following groups 5 \ _ C - C - R ⁵ C = K '■ R-' R 7 \ P. '■ R' R ⁸ - R ^ ^x R ^^ - I p-j; R ^J - C - IT - R ^ ^x R ^^ - CW, 309827/1087 101 28 ^/ \ / \ 30 ROR J. i - r35 h * - i - i - R ³⁷ / Il R ^ ^{0 X} Where R ³ , R ⁴ , R ⁵ , 'R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹ ^, r' \ R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²² , R ²⁵ , R ²⁴ , R ²⁵ , R ²⁷ , R ²⁸ , R ²⁹ , R ⁵⁰ , R ⁵¹ , R ⁵² , R ³⁵ , R ⁵⁴ , R ⁵⁸ and R, respectively a hydrogen atom, a halogen atom, an alkyl, alkoxy, aryl, aryloxy, sulfo or a 'Τ C * ~ 7 Q Represent carboxyl group, where R ^ and R ^p , R and R, R ⁹ and R ¹¹ , R ¹² and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ , R ⁴ and R, R ³ and R ³ to form a saturated one 4— or unsaturated /? - or 6-membered ring can be connected to one another, and R, R, R, R ³ and R ". Each represents a hydrogen atom, an alkyl or a Aryl group and W mean an oxygen atom or a sulfur atom » 8 »Process for the production of dye images, characterized in that fine photographic see silver halide emulsion with an aromatic primary amine 309827/1087 1OS as a developing agent in the presence of an α-diacylamino substituted one aromatic acylacetamide compound is treated. 9. A process for the production of color images, characterized in that a photographic silver halide emulsion with an aqueous alkaline solution containing an aromatic primary amine as a developing agent contains, in the presence of a yellow 'color-forming coupler following general formula - COGHCOM - R ² O = C '"CO
ι / where B is an aryl group E is an aryl group or a heterocyclic group and Z is used to form together with the unit N
O = CC in the general formula of a 4-, 5- or 6-membered • Binges mean necessary non-metal atoms. tO. Process for the production of color images, characterized in that a photosensitive element having a photographic emulsion on a support 309827/1087 sion layer, the a / qt-diacylamino-substituted Geliybixdenden coupler of the general formula H ¹ - COCHCONÜ - R ² - O = C C = O 1 2 contains, wherein R is an aryl group, R is an aryl group or a heterocyclic group and Z is taken together with the unit N
O = CC = O in the general formula / a ^ f-, 5- or 6-membered Ringes mean necessary non-metal atoms, and in which 1 2
at least one of R, R or Z has a hydrophobic group having about 8 to 32 carbon atoms as a substituent, is exposed to light and the exposed element is treated with an aqueous alkaline solution containing an aromatic primary amine as a developing agent. 11. A process for the production of color images, characterized in that a photographic silver halide emulsion with an aqueous alkaline solution containing an aromatic primary amine as a developing agent contains, in the presence of a gel color-forming coupler following general formula 309827/1087 . ι ■ ^! R ¹ - C O = C O H • Il /. -CH-C-N-R ' C = O where R is (1) a phenyl group, (2) a substituted phenyl group, in which the substituents consist of one or more halogen atoms, alkyl groups, Alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, Alkyl carbonyl groups, aryl carbonyl groups, Alkylsulfonyl group D, arylsulfonyl groups, carboxyl groups, Alkoxycarbonyl groups, carbamyl groups, sulfo groups, SuIfamyl groups, acylamino groups, ureido groups, Sulfonamide groups, amino groups, nitro groups, Cyano groups or hydroxyl groups exist, or (3) a condensed aromatic ring of the ü'orniel where A represents the atoms necessary for the formation of an aromatic fused ring system, R (1) a ■ Phenyl group, (2) a substituted phenyl group wherein the substituents of one or more halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, Aryloxy groups, arylcarbonyl groups, alkylcarbonyl groups, Alkylsulfonyl groups, arylsulfonyl groups, carboxyl groups, Alkoxycarbonyl groups, carbamyl groups, 309827/108 7 - te * - Sulfo groups, sulfamyl groups, acylamino groups, ureido groups, Sulfonamide groups, amino groups, nitro groups, Cyano groups or hydroxyl groups exist, (3) a heterocyclic, with the group R ¹ COGHCOIm ' ^N \
O = CC = O in the general formula linked by a carbon atom in the heterocyclic group, the one Is part of the conjugated electron system and from the groups of thiophenes, furans, pyrans, chromenes, Pyrroles, pyridines, pyrazines, pyrimidines, pyridazines, indolidines, perimidines, thiazoles, imidazoles, oxazoles, 1,5,5-triazines or oxazines and substituted derivatives of which is selected, with -the substituents consisting of halogen atoms, Alkyl groups, alkenyl groups, alkoxy groups, Aryl groups, aryloxy groups, alkylcarbonyl groups, aryο arbonyl groups, alkylsulfonyl groups ^ irylsulfonyl groups, Carboxyl groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acylamino groups, Ureido groups, sulfonamide groups, amino groups, Nitro groups, cyano groups or hydroxyl groups consist of a condensed aromatic ring of the formula 309827/1087 where A represents the atoms necessary to form an aromatic fused ring system. 12. A method for producing color images, characterized in that a photographic Silver halide emulsion with an aqueous alkaline solution containing an aromatic primary amine as a developing agent contains, in the presence of a yellow 'color-forming coupler of the following formula 0 0 H ρ It R ¹ - C - CH - C - N C = O Λ 2 where E is an aryl group, R is an aryl group or a heterocyclic group and Z is one of the following groups 309827/1087 Flat share R ^ -O C - R ^b ν- "C R ¹ Y.8 \ 'IA c - C - C - R ^y _R J.0 _R .LL _R .U _R ± j R ^1D_ c -N- R ' ^: R ^U IC> / η _η R ^{± y} - C - C - C - R ¹⁷ Jl6] v / ^X C i « ₅ OCi c; O _{x Λ} 0 C. H 0 , R ³⁶ -A-Jt-H « 309827/1087 where Ε ?, r \ r5, r6, r ⁷ , r8, r9, ^ _e 11 _{? R} 12 _? ^ ₃ , 6 7 8 ₉ 20 22 ^ 2 ^ 2 ₅ because a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a sulfo group or a carboxyl group, where '. R ^ and R ^, R ⁷ and R ⁸ , R ⁹ and R ¹¹ , R ¹² and R ¹ ^, R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹ ^ R ² ^ and R ²⁵ , R ⁵¹ and R ⁵² with each other to form a saturated or unsaturated / ij-membered or 21 6-membered ring can be connected, while R, R ²⁶ , R ⁵⁵ , R ⁵⁶ and R ^{57 denote} a hydrogen atom, an alkyl group or an aryl group and V denotes an oxygen atom or a sulfur atom in which at least one i 2
the radicals R or R contains a hydrophobic group with about 8 to about 32 carbon atoms as ßubstituenten. 13 · Process for the production of color images, characterized in that daΪ3 is a photographic silver halide emulsion with an aqueous alkaline solution, which contains an aromatic primary amine as a developing agent contains color medium, in the presence of a gel / forming coupler the following general formula Xγ - ^ y_ _C0CHC0M - .N X ^ O = C C = O. 309827/1087 nz is treated; wherein Z is one of the following groups _ c - c - ir C ■ '«I ⁶ ' I- * V \ / u - | c \ '17 C - C - C - R ⁴ ^ 'R ⁵ - C = C - C - IT' 10ΊΓ1? T? '16' R- ^LU R ^{± J} -R ^ R- ¹⁰ Ο " ¹¹³ C 18th R ¹⁹ - C - H - R ²¹ R ²² - C Vl R ²⁰ R ² O iLr ²⁶ R ²⁷ . I IR ²⁹ L 'R ^{28 X} O ^ V ⁰ r ^{5; 5} 1 I ι ι \ / C. ^, N - R ^ R ^ ⁰ _ N - N - R ^ 'and R ⁵⁴ ^ j'r5 ⁸ 309827/1087 -m- where R 3 E ⁴ , E ⁵ , E ⁶ , E? , E ⁸ , H ⁹ . R ¹⁰ , R ¹¹ , E ¹² , R ^ 3 R ¹ \ R ¹ Ε " ¹ ?, R ²⁰ R ²² R ² ? , E ²⁴ ι R 25th R ²⁷ , R ² 8th
» _E 29 , R? ⁰ .H * ¹ , R ³² , r55 * R ³ ^ ' r5 ⁸ and : r39 In each case a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a sulfo group or a carboxyl group, whereby R ⁵ and E ⁵ , E ⁷ and H ⁸ , R ⁹ and R ¹¹ , R ¹² and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ , R ²⁴ and R ²⁵ , R ⁵¹ and R ⁵² can be connected to one another to form a saturated or unsaturated 5-membered or 6-membered ring, while R ²¹ , R ²⁶ , R ^, Έ? and R ^ ⁷ each represent a hydrogen atom, an alkyl group or an aryl group and W an oxygen atom or a sulfur atom, X a halogen atom, an alkoxy group, an aryloxy group or a tertiary amino group, and Y, Ύ and Y ^, which may be the same or different , in each case hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, carboxyl groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acy! Y and Y, which can be the same or different, each represent hydrogen atoms, alkyl groups or alkoxy groups, Y- ⁷ , Y and Y ', which can be the same or different, each represent hydrogen atoms, alkyl groups, alkoxy groups, aryloxy groups, amino groups, alkylamino groups or acylamino groups. 14. Process for the production of color images, characterized in that a photographic silver halide emulsion with an aqueous alkaline solution, 3Q9 827/1087 those using an aromatic primary amine as a developing agent contains, in the presence of a yellow'.color-forming coupler the following general formula 0 0 i \ r is treated, wherein ß an aryl group, R an aryl group or a heterocyclic group and Z is one of the following groups 309827/1087 as I. R ⁹ \
- C \
C.
I. - C - r5 k C. /
- C -R ¹⁴ C = C R ^ V R ³ ; ⁵ - C = O - O - R ¹⁷ iq 'I pi op R * -CN _r R ^ R ^ - C ¥ R ²⁰ - IP R ²⁴ -L ) -R ²⁶ R ² ^ i I, R ²⁹ I. I ₂₅ , R ²⁸ \ / V ° .N - R ^ R ^JO - N - JM - R- "and C R ^ V _'R 38 "\ _J 39 where r5, R ^, r5 _? r ⁶ , r ?, r ⁸ , R ^ R ^ ⁰ , e ¹¹ , R ¹² , R ^, E ¹⁴ , R ¹⁵ , R ¹⁶ ^ R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²² , R ²⁵ , ²⁴²⁵ R ² ?, R ²⁸ , R ²⁹ , r3 °, r3 \ RJa _{1 R} 33 _{r R} 3 \ _r5 8 veils a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a sulfo group or mean a carboxyl group, where R ⁵ and R ⁵ , R ⁷ and R ⁸ , R ⁹ and R ¹¹ , R ¹² and R ¹⁵ , R ¹⁵ and 309827/1087 R ¹⁶ , R- ¹⁷ and R ^'18 , R ²⁴ and R ²⁵ , R ⁵¹ and R ⁵² can be linked to one another to form a saturated or unsaturated 4-, 5-membered or 6-membered ring, while R ²¹ , R ²⁶ , R ^, R ^ ⁶ ^ a r37 j _ewe ii _se in Wasserstoffatorn, an alkyl group or an aryl group, and V is an oxygen atom or a sulfur atom. 15 Photographic light-sensitive element, consisting of a support with at least one silver halide emulsion layer thereon which contains a coupler for the formation of a yellow dye of the general formula: O OH η Il Il R- ¹ -C-CH -CN O = C Cr-O 1 2 wherein R is an aryl group, R is an aryl group or a heterocyclic group and Z those to form with the unit 0.0 _{c = 0} the general formula of a 75-membered or "6-membered Ringes mean necessary non-metal atoms. 16. Photographic, light-sensitive element, consisting of a carrier with at least one on it 309827/1087 located silver halide emulsion layer, the one Couplers for forming the yellow dye of the following general formula: '0 0 .H ! II II / R - C - CH - C - W O = CC = O
\ / Ί 2 contains where R is an aryl group, R is an aryl group or a heterocyclic group and Z which, together with the unit '· O = C C = O 4-in the general formula of a / '5-membered or 6-membered Ringes mean necessary non-metal atoms, 1 2 where at least one of the radicals R, R or Z is a substituent contains a hydrophobic group containing from about 8 to about 52 carbon atoms. 17 · Photographic light-sensitive element according to claim 16, characterized in that the coupler has the general formula 3 0 982 7/1087 O O H II I! / - C - CH - C - M - R " in which R (1) is a phenyl group, (2) a substituted phenyl group in which the substituents are composed of one or more halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, carboxyl groups, alkoxycarbonyl groups, carbamamyl groups , Sulfo groups, sulfamyl groups, acylamino groups, ureido groups, sulfonamide ⁰ " ο groups, amino groups, nitro groups, cyano groups or hydroxyl groups exist, or (5) a condensed one aromatic ring of formula wherein A represents the atoms necessary to form an aromatic fused ring system, R (1) represents a Phenyl group, (2) a substituted phenyl group wherein the substituents from one or more halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, Aryloxy groups, arylcarbonyl groups, alkylcarbonyl groups, Alkylsulfonyl groups, arylsulfonyl groups, carboxyl groups 309827/1 087 HS groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acylamino groups, ureido groups, Sulfonamide groups, amino groups, nitro groups, cyaiP groups or hydroxyl groups, C 3) one with the group R ¹ COcJHUOKH. = / Y = C O = in the general formula heterocyclic group linked via a carbon atom in the heterocyclic group ,, ■ which is part of the "conjugated E1,;, ktron system and from the group of thiophenes, furans, pyrans, chromenes, pyrroles, pyridines, pyrazines, pyrimidines, pyridazines, Indolidines, perimidines, thiazoles, imidazoles, oxazoles, 1,3,5-triazines or oxazines and substituted derivatives is
selected from these / where the substituents are selected from halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylcarbonyl groups, aryl carbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, carboxyl groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfonamino groups, sulfonamino groups, acreidoamyl groups, sulfonamyl groups, sulfo groups, sulfonamyl groups, Nitro groups, cyaiP groups and hydroxyl groups are selected, (4-) a condensed aromatic input of the formula where A represents the atoms necessary to form an aromatic condensed king system. 309827/10 87 - 1 * 6 - 18. A photographic photosensitive element according to claim 16, characterized in that the Group Z consists of one of the following groups I V R ⁴ R ⁶ ·· R ⁷ R ⁸ \ / 1-1 15 \ / COC- R ^iy) R ^lj -C = CCR ¹ ' - O - H - R Vt - OW R ^{20 h26} 25th Il O 309827/1087 wherein H *, R \ R ^, E ^6, R ?, R ^8, R ^9, E ^10, E ^11., E ^12, R ¹ \ R ^, R ^16, H ¹ 7, η ^18, R ¹⁹ , R ²⁰ 'R ²² , R ²⁵ , R ²⁴ , R ²⁵ , R ² ?, R ²⁸ , R ²⁹ , R? ⁰ , r3 \ r5 ² , r35 _{ma E} 34 _{each a} hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylox group, a whereby . -z c represent sulfo group or a carboxyl group, / R- ^ and R- ^ ₅ R ⁷ and R ⁸ , R ⁹ and R ¹¹ , R ¹² and R ¹⁵ , R ¹⁵ and R ¹⁶ , R "'" and R ¹ , R ²⁴ and R ² ^, R ^ and R ^ ² together to form a saturated one or unsaturated / 5-membered or 6-membered binges can be combined, while R ^21, R ²⁶ _v r55, r36 _{and R} 37 each, 'represents a hydrogen atom an alkyl group or an aryl group and W is an oxygen atom or a sulfur atom. 19 ·. A photographic photosensitive element according to claim 16; , characterized in that R is a group of the formula ^! represents, and R is a group of the formula represents, wherein X represents a halogen atom, an alkoxy group, an aryloxy group or a tertiary amino group, Y, Y ² and Y ^, which can be the same or different, each hydrogen atoms, halogen atoms, 309827/1087 Ui Alkyl, alkenyl, alkoxy, aryl, aryloxy, alkylcarbonyl, Arylcarbonyl, alkylsulfonyl, arylsulfonyl, carboxyl, Alkoxycarbonyl, carbamyl, sulfo-, sulfamyl, acylamino, Ureido, sulfonamido, amino, nitro or cyano groups A. R mean Y and Y, which are the same or different can be, each hydrogen atoms, alkyl or 5 6 7 Alkoxy groups mean Y, Y and Y, which can be the same or different, each hydrogen atoms, Alkyl, alkoxy, aryloxy, amino, alkylamino or acylamino groups and Z is one of the groups R ⁵ - V / - R ⁵ \ ^R. j -C-C C. - C /
7th \, " R ⁴ n ⁽ 1 / r ' \ I. »• 4
» I ₅ \ C. ■ " \ j * ·" Λ
I ₂ Il ₃ ¹⁵ - c ο -i ¹⁶ 19 '' 21 '?? `` R ³ - 0 - H - R ^ ^x H - α W - H ¹⁷ J ²⁰ [.Χ * ^ T ₁ ·, 29 I ί-Η » 55 I I ν, -. _? nd Ii ³⁶ - N - JJ - R ³⁷ , 309827/1087 ο - 1 * 9 - represents where R ⁵ , R ⁴ , R ⁵ JR ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , _p 12 _p 13 J4 t, 15 pi6 _p 17 _p 18 _p 19 _p 2O _p 22 ^ 23 E ²⁴ , E ²⁵ , E ²⁷ , E ²⁸ , E ² ^ ₁ E ³⁰ , E ³¹ , E ⁵² , E ³⁵ , E ³ *, E ³⁸ and R ^ each have a hydrogen atom, a halogen atom, an alkyl, alkoxy , Aryl, aryloxy, sulfo or a carboxyl group, where Ίτ and R, R and R, R ⁹ and R ¹¹ , R ¹² and R ¹³ , R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ , E and R , Έγ and Έ? forming a saturated or unsaturated 5- or 6-membered ring with one another which can be connected, and R, R, R, R and • 57
R ^ 'each represent a hydrogen atom, an alkyl or an aryl group and W an oxygen atom or a sulfur atom » 20. Photographic, photosensitive element, consisting of a support with at least one silver halide emulsion layer coated thereon, the a coupler for forming the yellow dye accordingly the following general formula ο O = C CH- O C = O ■ / \ H υ Ν _ν Il · ' H Il \ Il - c - C - R ² / .ν 1 2 contains, wherein R is an aryl group, R an aryl or denote a heterocyclic group and Z is selected from a of the following groups 309827/1087 , 1'I ₅ Il R-? _ CCR ⁵ C = C . R ⁴ R ⁶ R ⁷ R ⁸ r9 -CCC- r ¹ * R ¹⁵ - C = C - C - R ¹⁷ I ₉ '' 21 22 '·' H ^ly - C - H - ΈΓ ^Χ ■ Vt ^d - C - W R ²⁰ , i ²⁵ R ^24l -i NR ²⁶ R ² ^ l LR ²⁹ K ^ ⁰ - ^Ε _R 25 .R. . R. N - R ³⁵ and R ^v "- NN R ³⁴ " \ '
Il
O ; consists in which R ³ , R ⁴ , R ⁵ , 'R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , _p 12 _p 13 pH _R 15 «16 _R 17« 18 _R 19 _R 20 _R 22 _R 25 _p 24 p25 p27 p28 _R 29 _R 30 _p 31 _P 32 _p 33 34 and RT each have a hydrogen atom, a halogen atom, represent an alkyl, alkoxy, aryl, aryloxy, sulfo or a carboxyl group, where Έ? and R, Jl and R, R ⁹ and R ¹¹ , R ¹² and R ¹³ , R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ , R ⁴ and R, R ³ and R ³ to form a saturated or unsaturated 5- or 6-membered ring with one another P1 Pfi ^ R "^ (λ which can be connected, and R, R, R »R and 37 R is in each case a hydrogen atom, an alkyl or a Aryl group and W denote an oxygen atom or a sulfur atom «. 309827/1087 21 ο Process for producing color images, thereby characterized in that a photographic silver halide emulsion with an aqueous alkaline solution, containing an aromatic primary amine developing agent in the presence of a yellow color forming coupler the following general formula R ¹ - CGCHCOMI - R ² ι IL O = C ^ C = O is treated, in which B. an aryl or alkenyl group, 2
R is an aryl group or a heterocyclic group, and Z together with the unit O = C C = O I "I in the general formula that for the formation of a 5- or 6-membered ring means the necessary non-metal atoms, 22 · Process for the production of color images, characterized in that a light-sensitive element, which has a photographic emulsion layer on a support, which form a diacylamino-substituted yellow color Coupler of the general formula R ¹ - COCHCONH - R ² ■ ι ■ - O = C C = O V / 309827/1087 1 2 contains where R is an aryl group, R is an aryl group or a heterocyclic group and Z together with the unit O = C C = O I I in the general formula to form a 5- or 6-membered Ringes necessary non-metal atoms mean ", and in which at least one of the radicals R, R ^ or Z as Substituents has a hydrophobic group having about 8 to about 32 carbon atoms, is exposed and that exposed element with an aqueous alkaline solution containing an aromatic primary amine as a developing agent contains, is treated. 23 »Process for producing color images, thereby characterized in that a photographic silver halide emulsion with an aqueous alkaline solution, those using an aromatic primary amine as a developing agent contains, in the presence of a yellow color-forming coupler the following general formula 0 OH
* Il II a R ¹ - C - CH - C - N - R N
O = CC = O where R is (1) a phenyl group, "(2) a substituted phenyl group in which the substituents are selected from one or more halogen atoms, alkyl, alkenyl, alkoxy, aryl, aryloxy, alkylcarbonyl, arylcarbonyl, Alky! Sulfonyl, arylsulfonyl, carboxyl, alkoxycarbonyl, 309827/1087 Carbamyl, sulfo, sulfamyl, acylamino, ureido, sulfonamido, Amino, nitro, cyano or hydroxyl groups exist, or (3) a condensed aromatic ring of the formula wherein A represents the atoms necessary to form an aromatic fused ring system, R (1) represents a Phenyl group, (2) a substituted phenyl group, where the Substituents composed of one or more halogen atoms, alkyl, alkenyl, alkoxy, aryl, aryloxy, aryl carbonyl, . Alkylcarbonyl, alkylsulfonyl, arylsulfonyl, carboxyl, Alkoxycarbonyl, carbamyl, sulfo-, sulfamyl, acylamino, Ureido, sulfonamido, amino, nitro, cyano or hydroxyl groups consist, (3) a heterocyclic with the group ■ R ¹ COCHCONH - O = CC = O
* ".? ■ ' in the general formula by a carbon atom in the heterocyclic group, which is part of the conjugated electron system and consists of the groups of Thiophenes, furans, pyrans, chromenes, pyrroles, pyridines, pyrazines, pyrimidines, pyridazines, indolidines, perimidines, Thiazoles, imidazoles, oxazoles, 1,3,5-triazines, or oxazines and substituted derivatives thereof, where the substituents are selected from halogen atoms, alkyl, alkenyl, Alkoxy, aryl, aryloxy, alkylcarbonyl, aryl carbonyl, alkylsulfonyl ,. Arylsiflfonyl, carboxyl, alkoxycarbonyl, flarbamyl, sulfo, sulfamyl, acylamino, ureido, sulfonamido, Amino, nitri, cyano or hydroxyl groups exist, (4) a condensed aromatic ring of the formula 309827/1087 V * -VH- where A is the atoms necessary for the formation of an aromatic fused ring system and Z is the atoms together with the group I. η S ^ O = CT C = O I I of the general formula for the formation of a 5- or 6-membered ring mean non-metal atoms necessary " 24-e method of producing color images, thereby characterized in that a silver halide photographic emulsion with an aqueous alkaline solution containing an aromatic primary amine as a developing agent contains, in the presence of a yellow color-forming coupler the following formula P ⁰ H 'ι Il · Il / ^H R-C-CH-C-N I \ "2 N ^& O = C C = O 1 where R is an aryl group, R is an aryl group or a heterocyclic group and Z is one of the following groups 3 I I «ς Ί r -> _ C - C - R ⁵ 'C = ^4th I ⁶ ά 309827/1087 R ⁹ - C - "C - C - R ¹⁴ R ¹⁵ - C = CC- c _ υ _ r ²¹ ■ R ²² - CW T? ²⁰ R-- c ^ κ -.R ²⁶ R ² ^ ⁷ JI ^ R ²⁹ o. ^ - R ³² R ²⁸ 3 * 5 R ³⁴ N- R ³⁵ and R ³⁶ - H - H - R ³⁷ Il
.0 represent wherein R ³ , R ⁴ , R ⁵ ? R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ IO 1 ^ l Λ λ Λ £ \ Λ £ \ Λ * 7 Λ Q Λ Q *} C \ OO O ' _P 18 _p 9 _ppp 3 3O _p 31 _P 32 _p 33 "'■ \ md R- one hydrogen atom, one halogen atom, an alkyl, alkoxy, aryl, aryloxy, sulfo or a • χ 5 7 represent carboxyl group, vobol · R ^ and R, R and R, R ⁹ and R ¹¹ , R ¹² and R ¹³ , R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ , R ⁴ and R, R ³¹ and R ³² can be linked to one another to form a saturated or unsaturated 5- or 6-membered ring, and R, R, Br ₁ R and · R is in each case a hydrogen atom, an alkyl or the one Aryl group and W an oxygen atom or a sulfur atom mean" 309827/1087 - 126 - 25 "A process for the production of color images, characterized in that a photographic silver halide emulsion with an aqueous alkaline solution containing an aromatic primary amine as a developing agent," in the presence of a yellow color-forming coupler of the following formula y7 y8 Y ⁶ K V— COCHCONH f V Y ⁴ N _v X X O = C is treated, wherein Z is one of the following groups R3.-CC- R ⁹ ° R ⁴ R ⁶ , * ' ^R '' 9 \ η ή P ¹ ^ R ¹ ^ - C = C - C - R ^y - C - C - C - R a ZV ₁₂ \ ₁₃ Il6 il8 R ¹¹ R ¹² R ¹ ^, ^RK _R i9 J-Lr ²¹ R ²² ^ cW I o-z 23 _H 20, R ⁵ r o PR K R ²⁵ , _c π - r'5 and r ' ⁶ - N - N - 309827/1087 - is * - - · -., Where R ⁵ , R ⁴ , R ⁵ VR ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹ \ _p 12 .13 «Η« 15 «16.« 17 «18" 19 _R 20 «22 ■« 23 «25 p27« 28 _p 29 «30 _B 31 _R 32 _R 33 and R ^ - each represent a hydrogen atom, a halogen atom, an alkyl, alkoxy, aryl, aryloxy, sulfo or a carboxyl group, where E ^ and -Br, R and R, R ⁹ and R ¹¹ , R ¹² and R ¹³ , R ¹⁵ and R ¹⁶ , R ¹⁷ and R ^18,. R ^{2 /} ^ and R ² ^, R ³¹ and R ³² can be connected to one another to form a saturated or unsaturated 5- or 6-membered ring, and R, R, R, R ⁵ and R ^ ¹ each have a hydrogen atom, denotes an alkyl or an aryl group and W denotes an oxygen atom or a sulfur atom 26. Process for producing γοη color images, characterized in that a photographic silver halide emulsion with an aqueous alkaline solution, containing an aromatic primary amine developing agent in the presence of a yellow color forming coupler of the general formula · ■ 1 2 " is treated, wherein R. an aryl group, R "an aryl group or a heterocyclic group and Z is one of the following groups: 309827/1087 - I I ς \ / R ^ _ C - C - R ^p C = C ·. E * I ⁶ , ί V, R ^ -CCCR ¹⁴ R ¹⁵ - C = C - C - R ¹⁷ '? 1 22' ' C-N-R R - C - W S ²⁰ , R ²³ H ² "- O _n iR ²⁶ R ² ^ l I / R ²⁹ I « R? L I · Il N- R ³⁵ and R ⁵⁶ - N - N - R ⁵⁷ _v where R ³ , R ⁴ , R ⁵ ? R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ _{P p} 15 «14« 15 «16 _R 17 ^ 18 _R 19 _R 20 _p 22 '23 p p25 «27» 28 _p 29 «30 _P 31« 32 _P 33 34 and R * t each represents a hydrogen atom, a halogen atom, -an alkyl, alkoxy, aryl, aryloxy, sulfo- or a • ZC »7 D Represent carboxyl group, where "Br and R ^? , R and R, R ⁹ and R ¹¹ , R ¹² and R ¹³ , R ¹⁵ and R ¹⁶ , R ¹⁷ and" R ¹⁸ , R ²⁴ and R ²⁵ , R ⁵¹ and R ³² forming a "saturated or unsaturated 5- or 6-membered ring with one another 91 9fi IR 'ifi which can be connected, and R, R, R »R and R is in each case a hydrogen atom, an alkyl or a Aryl group and W mean an oxygen atom or a sulfur atom ». 309827/1087 27 x ¹ photographic photosensitive element according to Claims 3 to 5, characterized in that R ^{1 is} a group of the formula ρ
represents, and R is a group of the formula represents wherein X is a halogen atom, an alkoxy group, an aryloxy group or a tertiary amino group -ι ρ rz . ■ represents Y, Y and Y, which are the same or different can be, each hydrogen atoms, halogen atoms, Alkyl, alkenyl, alkoxy, aryl, aryloxy, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, carboxyl, Alkoxycarbonyl, carbamyl, sulfo-, sulfamyl, acylamino, T -reido, sulfonamido, amino, nitro or cyano groups mean, Y and Y, which can be the same or different, each hydrogen atoms, alkyl or 5 6 7 are alkoxy groups, Y, Y and Y, which can be the same or different, are each hydrogen atoms, Alkyl, alkoxy, aryloxy, amino, alkylamino "or acylainino groups mean, and Z together with the group i - O = C C = O I! 309827/1087 necessary in the general formula aur form a 4 "5- or 6-membered ring Hicht metal atoms represents. 28 · A method for producing color images, characterized in that a photographic silver halide emulsion with an aqueous alkaline solution containing an aromatic primary amine as a developing agent in the presence of a yellow color-forming coupler of the following general formula will
treats / wherein X is a halogen atom, an alkoxy group, an aryloxy group or a tertiary amino group 1 2 "5 represents Y, Y and Y, which are the same or different can be, each hydrogen atoms, halogen atoms, Alkyl, alkenyl, alkoxy, aryl, aryloxy, alkylcarbonyl, Arylcarbonyl, alkylsulfonyl, arylsulfonyl, carboxyl, Alkoxycarbonyl-, carbamyl-, sulfo-, sulfamyl-, acylamino-, Ureido, sulfonamido, amino, nitro or cyano groups A ft mean, Y and Y, which may be the same or different, each represent hydrogen atoms, alkyl or alkoxy groups, Y ^3, Y and Y may be the same or different which ·, are each hydrogen, alkyl, alkoxy, aryloxy, amino -, alkylamino or 309827/1087 1SS - Yes* - Acylamino groups mean and 2L together with the group of the general formula for the formation of a 4-, 5- or 6-membered ring necessary non-metal atoms represents · · 29. A photographic photosensitive element according to claim 16, characterized in that R is Group of formula ρ
and R represents a group of the formula represents, wherein X represents a halogen atom, an alkoxy group, an aryloxy group or a tertiary amino group - _: 1 2 "5 represents, Y ₁ Y and Y, polygons can be the same or different, in each case hydrogen atoms, halogen atoms, alkyl, alkenyl, alkoxy, aryl, aryloxy, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, carboxyl, Alkoxycarbonyl, carbamyl, suIfo, suIfamyl, acylamino, ureido, sulfonamido, amino, nitro or cyano groups mean Y 1 and Y, which can be the same or different, in each case hate atoms, alkyl or 5 6 7 are alkoxy groups, Y, Y and Y, which can be the same or different, are each hydrogen atoms, Alkyl, alkoxy, aryloxy, amino, alkylamino or 309827/1087 1S6 Aoylamino groups mean, and Z together with the Group · O = C. C = O I. j of the general formula for the formation of βineβ 5- or 6-membered Ringes necessary non-metal atoms means 30 · Process for producing color images, thereby characterized in that a photographic silver halide emulsion with an aqueous solution which has a containing aromatic primary amine as a developing agent, in the presence of a yellow color-forming coupler the following general formula COCHCONH N O = C C = O ζ - is treated, wherein X represents a halogen atom, an alkoxy group, an aryloxy group or a tertiary amino group, Y, Y and Y ^J , which may be the same or different, each hydrogen atoms, halogen atoms, alkyl, alkenyl, alkoxy, aryl -, aryloxy, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, carboxyl, alkoxycarbonyl, carbamyl, sulfo, sulfamyl, acylamino, ureido, sulfonamido, amino, nitro or cyano groups mean, Y * and Y ⁸ , which can be identical or different, are each hydrogen atoms, alkyl or • 5 6 7 Alkoxy groups mean Y ^? , Y and Y ', which can be the same or different, each hydrogen atoms, alkyl, alkoxy, aryloxy, amino, alkylamino or 309827/1087 Acylamino groups mean, and Z together with the Group | O = G C = O of the general formula for the formation of a 5- or 6-membered Ringes necessary non-metal atoms "means. 31 · The method for the preparation of v <-öiacylamino- _ (aromatischO-acetamides, characterized in that a compound (aromatic acyl) -acetamidi, wherein the p (position is halogenated with an imide compound in the presence of a basic material and an organic Reacts amide or oxide solvent. 3 0 3 8 2 7 10 8 7 Blank page