DE1547672A1 - Color photographic material - Google Patents

Description

Eastman Kodak Company, 3 * 13-State Street, Rochester, New York State, United States of America

Color photographic material

The invention relates to a color photographic material having at least one layer arranged on a support and containing a color coupler which is formed by coupling with the oxidation product an aromatic amine developing agent to form a yellow dye capable and which requires 2 moles of silver halide to form 1 mole of dye »

The production of color photographic images by coupling the oxidation product of one from one aromatic amine existing developer compound with so-called color couplers is known.

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green, purple and yellow dyes in the red, green and blue-sensitive squiggles. The color couplers which form blue-green dyes normally consist of phenols or naphthols. The couplers which form magenta dyes are usually composed of pyrazolones or cyanoacetyl compounds, and the couplers which form yellow dyes normally consist of open-chain compounds with a methylene group and two adjacent carbonyl groups.

Most of the color couplers used to date are so-called 4-equivalent couplers, i.e. they require 4 moles of silver halide to form 1 mole of dye.

Recently, so-called 2-equivalent couplers have also become known, i.e. couplers which lead to the formation of one mole of dye only 2 moles of silver halide need »Such color couplers are described, for example, in French patent specification 991 453 and described in British Patent Specification 805,505.

The so-called 2-equivalent ^{couplers have the significant advantage over the so-called 1} -equivalent couplers that they require only half of the silver halide for development that the 4-equivalent couplers need for development.

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The previously known 2-equivalent couplers have the disadvantage that they tend to fog and / or are not particularly reactive.

The present invention was therefore based on the object of such To develop 2-equivalent couplers which form yellow dyes without the tendency to color fogging and which have a high reactivity.

The new color couplers should also be developable without the need for particularly high pH values or high developing temperatures for development required are. The new color couplers should also be used when they are in silver halide emulsion layers are housed show good reactivity even if they are in the emulsion layers without high-boiling couplers solvents are housed.

The invention was based on the finding that so-called 2-equivalent couplers which form yellow dyes and which have an active methine group bonded to 2 carboxyl groups, one of which is part of an acyl group and the other part of an amide group, are then obtained when the active methine group has only one hydrogen atom and is substituted by a RjiSOuO group, where R ^ represents an organic group.

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The invention thus relates to a color photographic material with at least one layer which is arranged on a carrier and contains a color coupler, characterized in that the Layer contains a coupler of the following formula:

-R

C =

1.

O
- OSO,

R-

where mean:

R is an alkyl, terpenyl, aryl or heterocyclic groupj R ₁ and Rp are hydrogen atoms, alkyl, aryl or heterocyclic

Groups;

1 or 2 and

if η = 1, an alkyl or aryl group or if η = 2, an alkylene or arylene group *

It has been found that color couplers of the structure described can be used with success * wherever previously possible. be dye-forming couplers which react with the oxidation product / aromatic amine developing agent able to react were used. D4.it means with others Words that the new couplers in all known color schemes

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can be used in the systems, i.e. in image-forming Layers, either alone or together with image-forming compounds, such as silver halide or else Zinc oxide, cadmium sulfide, cadmium selenide, zinc sulfide, nickel sulfide and the like

The color couplers can also be used in layers with and without a binder.

If R has the meaning of an alkyl group, this preferably has from 1 to 22 carbon atoms. In individual cases, R can be, for example, an alkyl group, such as a methyl; 3-pentadecyl phenoxymethyl; Ethyl-; Phenylethyl; n-propyl-; Isopropyl; a- (2, ii-Dl-t-amylphenoxy) -propyl-; 6-sulfobutyl-; sec-butyl-; tert-butyl-; Docosyl-; Chloromethyl-; Trifluoromethyl-; 2-hydroxy · methyl-; ß-carboxyethyl; 2- (2,4,6-trichlorophenyl) ethyl-; 2-aminoethyl-; α, α-diraethylbutyl-; a-methoxy-o-methyloctyl-; o-propylo-octyldocosyl-; α, ο-dibutyl-docosyl-; ο _> a-di-decylundecyl-; a, a-di-t.-butyldodecyl-; M o, α-di-sec-butylpentadecyl group and the like;

a terpeny group, e.g. a 7,7-dimethylnorborny1 or 2 » Alkyl-T.T-dimethylnorbornyl group in which the alkyl group Has 1 to 18 carbon atoms, such as x.B. a methyl; Butyl; Octadecy! Group and the like, such as a 2-methyl-7,7-diaethylnor-

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bornyl or 2-0ctadecy1-7,7-dimethylnorbornyl group or a 2-ary1-7,7-dimethylnorbornyl group such as a 2-phenyl-7,7-dimethylnorbornyl or 2-tolyl-7,7-dimethylnorbornyl group;

an aryl group such as phenyl; 3- (2-carboxybenzamido) phenyl-; 3- (β-sulfopropionamido) -phenyl ·; α-naphthyl-; β-naphthyl-; 2, '1,6-trichlorophenyl-; 4-xthoxyphenyl-; H-Bro »ophenyl-; 4-fluorophenyl-; 3 - & - (2, M-di-t.-a »yl-phenoxy) butyramido] -phenyl-; 3-Q- (2,4-Dl-t * -8ynylphenoxy) butyramido} phenyl group and the like.

a heterocyclic group such as benzofuranyl; furanyl-; Thiazolyl *; Benzothiazolyl-; Naphthothlazolyl-; Oxazolyl-; Benzoxazolyl-; Imidazolyl-; Benzimidazolyl-; Quinolinyl group and the like, which may optionally be substituted.

R ₁ and R ₂ can have the same or different meanings and consist, for example, of: hydrogen atoms or optionally substituted alkyl groups with preferably 1 to 22 carbon atoms, for example methyl; Carbethoxymethyl; Dodecyl-; Docosyl-; 2-sulfoethyl; 2-chlorobutyl-; 2-hydroxyethyl; 2-phenylethyl groups and the like or ary groups, for example phenyl; 2-methoxy phenyl-; 4-net hy! Phenyl-; ¹ * - [p- (2, ¹ '-di-t-amylphenoxy) butyric * amido] phenyl-; M-sulfamylphenyl-4- [5- (3-chlorosulfonylbenzamido) -2- (2,4-di-t-any! Phenoxy) benzanido) phenyl-; 2,4,6-trichlorophene

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nyl-5 3,5-dibromophenyl-; 3,5-dicarbomethoxyphenyl-; 3 »5-dicarboxyphenyl-; Naphthyl or 3-ethylnaphthyl groups or heterocyclic groups such as thiazolyl groups such as ^, S-Dlcarbäthoxy ^ -thiazolyl-; 5-carbethoxy-2-thiazolyl ~ or thiazolyl groups, benzothiazolyl groups, naphthothiazo-IyI-; Oxazolyl-; Benzoxazolyl-; Naphthoxazolyl-; Imidazolyl-; Benzimidazolyl-; Naphthimidazolyl-; Pyridyl-; Quinolyl groups and the like.

If η = 1, R ~ can be an optionally substituted » te alkyl group bit preferably 1 to 22 carbon atoms, for example a methyl; Ethyl-; Octadecyl-; 2-carboxyethyl; 4-sulfobutyl-; 5-hydroxypentyl-; 2-chloroethyl; SS t-butyl-; 3-carbethoxypropyl or 4-methoxybutyl group or an optionally substituted aryl group such as a phenyl group; 3-arainophenyl-; 4-methylphenyl-; 3-carboxyphenyl-; Ί-sulfophenyl-; 3-hydroxyphenyl-; ή-cyanophenyl-; 3-nitrophenyl-; 2-chlorophenyl-; i | -Xthoxyphenyl-; B-octadecylcarbamylphenyl-; ^ -Butyramiidophenyl-; 3-docoeylphenyl-; 1-naphthyl group and the like.

R ^ can, if η = 2, be a divalent organic group, such as an alkylene group having 1 to 22 carbon atoms, such as an ethylene; Propylene; 2-carboxypropylene or 3-hydroxybutylene group or an arylene group such as m-phenylene; 5-carbomethoxy-m-phenylene-; $ -Octadecyloxy-m-phenylene-; 5-carbomethoxy-m-phenylene or 5-octadecyloxy-m-phenylene group.

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Typical color couplers which form a yellow dye according to the invention are, for example:

1. α-Methylsulfonyloxy-α-pivalyl-2-chloro-5-Q- (2,4-di-t-amylphenoxy) butyramido] acetanilide the formula:

IJ-, CCOCHCONH JJ ι

: ch _p ) -o

SO ₉ ^{2 3}

2. a-Pivalyl-a- (p-tolylsulfonyloxy) -2-chloro-5- [j- (2, l | -di-tamylphenoxy) butyramidq] acetanilide;

3. α-Methylsulfonyloxy-o-pivalyl-2-chloro-4- (N-methyl-N-octadecylsulfamydacetanilide;

II, o-methylsulfonyloxy-o-pivalyl-II-iN-methyl-N-octadecylsulfamy-dacetanilide;

5. α-Methylsulfonyloxy-α-pivalyl-2,5-dichloro-M- (N-methyl-N-octadecylsulfamy-dacetanilide;

6. o- {3- [o- (2 »^ - di-t. * - amylphenoxy) butyramidq] benzoyl} -o-methyl sulfonyloxy-2-raethoxyacetanilide;

7. a- (i | -0ctadecyloxyphenylsulfonyloxy) -e-pivalyl-1-sulfamylacetanilide the formula:

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(CH ₀ ) -CCOCHCONH Jj ι 0

S0

SO ₂ NH ₂

8. o-O-NitrophenylsulfonyloxyJ-o-pivalyl-StS-di-carboxyacet · anilide (intermediate for coupler 10);

9. α- (3-Aminophenylsulfonyloxy) -o-pivaly1-3 »5-di-carboxyaeet · anilide (intermediate for coupler 10) j

10. o- {3- [ö- (3-pentadecylphenoxy) acetamido} phenylsulfonyloxy} · a-pivalyl-SjS-dicarboxyacetanilid of the formula:

COOH

(CH ^) ₀ CCOCHCONh Jj »0

SO ₂ ^ COOH

NHCOCH ₂ O

^C 5 ^H 31

11. a- (2-Methoxybenzoyl) -e-propylsulfonyloxy- ⁱ l-J32 "" (2 _> 4-di-t-amylphenoxy) -5- (3-sulfobenzaraido) benzamide ©] acetanilide, sodium salt; ■

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12. o- (| -Carboxybutylsulfonyloxy) -α- {3- [α- (2,4-di-t.-amylphen-

oxy) butyramido] benzoyl} -2-methoxyacetanilide;

13. o- (6-Carbomethoxybutylsulfonyloxy) -a- {3- [o- (2, ¹ l-di-t-amyl · phenoxy) butyramido] benzoyl} -2-methoxyacetanilidj

111. a-Octadecylsulfonyloxy-a-pivalyl-N.N-bisicarbethoxymethyl) acetamide;

15. o-Benzoyl-o-docosylsulfonyIQXy-N- ( ¹ I, S-dicarbethoxy-a-thiazolyl) acetamide of the formula:

S C-COOC ₀ Hc-

, / H 2 5

CtH ₁ -COCHCONHC

0 ^^ n C-C00C _o H _c

ι 2 5

SO ₀

16. o-Furoyl-o-CY-hydroxypropylsulfonyloxyJ - ^ - Jj-O-pentadecyl phenoxy) butyramldojacetanilide of the formula:

HC CH

C-COCHCONH Ü ^ V-NHCO (CHg) ₃ O - ff

\ / ο N = / N =

SO ₂
(

17. o- (7 »7-Dimethylnorbornyl-1-carbonyl) -a- (8-ethoxyoctylsulfo · nyloxy) -3-palraitaraidoacetanilid}

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18. *, a ^l -EthylenediBulfonyloxybis {o-benzoyl - ^ - [o- (2, il-di-t. Amy! Phenoxy) acetamido] acetanilld} of the formula

C ₆ H ₅ COCHCONH - ('M-NHCOCH ₂ O

19 · α- (4-Nitrophenylsulfonyloxy) -a-pvalyl-3- | j- (2,4-di-t-amylphenoxybutyramido] acetanilld;

20, a - ('l-Aminophenyleulfonyloxy) -a-pivalyl-3- [j- (2, Ί-di-t.-araylphenoxy) butyramidq ~} acetanilidj

21. e-Q-t8-Acetamido-3,6-di8ulfo-l-hydroxy-2-naphthylazo) phe-

nylsulfonyloxjTl-a-pivalyl-3-Gf-i ² " ^{1 (} - ^di '*' ^fc " - ^ani y ¹ P ^nenox y) ^bu tyramidq] acetanilide.

The new couplers are non-diffusing and can be arranged in a particularly advantageous manner in photographic emulsion layers. Couplers No. 11 and No. 12 are for example those couplers which, like the known Fischer-type couplers, can be incorporated into photographic emulsion layers. The remaining couplers, i.e., Couplers 1 to 6 and 13 to 20 can be incorporated into emulsion layers by, for example, the methods incorporate those described in U.S. Patents 2,304,939 and 2,322 that is, processes in which the couplers are dissolved in high-boiling organic solvents. The couplers can also be used, for example, according to the

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Patents 2,801,170, 2,801,171 and 2,9 ^ 9,360 Method Incorporate into emulsion layers, with low-boiling Solvents or water-soluble solvents can be used instead of high-boiling solvents.

The couplers used according to the invention have compared to so-called 4-equivalent couplers have the advantage that when they are used thinner photographic layers can be produced because only half of the silver halide is required.

Another great advantage of the couplers used according to the invention is that, in many cases, because of their extremely high reactivity without a high boiling coupler solvent can be used. Thin image-forming layers are particularly desirable because they are smaller Cause light scattering and because they result in sharper images let generate.

Coupler No. 8 forms a diffusible dye after color development and can advantageously be used in the frame an image transfer process or in emulsion layers as a competing coupler together with an image forming coupler *

Coupler No. 7 has a sulfamyl group in non-coupling Position that ionizes and a diffusing dye

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in color development at a pH above 11 and one Form non-diffusing dye at pH below 11.

Color coupler No. 21 has a preformed dye attached to the phenylsulfonyloxy group. This dye will when the coupler molecule is coupled with the oxidation product of a color developer, it is eliminated and diffused out of the layer out. This coupler can therefore be used to color correct the undesirable green absorption of yellow image-forming dyes, i.e., those formed by the coupler itself as well as other yellow dye-forming couplers. Such a coupler can preferably be used in combination with another, a yellow dye-forming coupler of the same layer can be used.

For the development of the new color couplers, the known, from primary aromatic amines, such as the phenylenediamines, e.g. Diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2-araino-5-diethylaminotoluQlhydrochlorid, 2-amino-5- (N-ethyl-N-lauryl) -toluene, N-Xethyl- £ - methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-Ä-methanesulfonamidoethyl-4-aminoaniline, 4-N-ethyl-N-ß-hydroxyethylaminoaniline and the like. The p-aminophenols and their substitution products are also suitable for color development, in which the amlno group is unsubstituted "

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A wide variety of compounds can be added to the developer solutions, for example an alkali metal sulfite, a car « carbonate, a bisulfite, a bromide, an iodine and the like, as well as thickeners such as those used for the production of viscous developers

The new color couplers are particularly suitable for the production of color photographic material with silver halide emulsion layers of the developable type * The emulsion layers can be used as silver halide, silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide and the like. contain*

Hydrophilic colloids suitable for producing such silver halide emulsion layers are, for example, gelatin, colloidal albumin, cellulose derivatives or synthetic resins, such as for example polyvinyl compounds. Examples of synthetic binders that may be mentioned are polyvinyl alcohol or hydrolyzed polyvinyl acetates, as described in US Pat. No. 2,286,215, partially hydrolyzed cellulose esters, such as cellulose acetates, which have an acetyl group content of up to

w 19 to 26 % have been hydrolyzed, for example, in the US Pat. No. 2,327,8o8, water-soluble ethanolamine cellulose acetates, as described, for example, in US Pat. No. 2,322,085, polyacrylamides with a combined acrylamide group content of 30 to 60 % and a specific viscosyl

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did from 0.25 to 1.5 or imidized polyacrylamides with the the same acrylamide group content and viscosities, as described, for example, in US Pat. No. 2,541.W, 0 zein, as described, for example, in US Pat. No. 2,563,791, VinylaUtoholpolymerlsate with urethane carboxylic acid groups, such as for example in US Pat. No. 2,768,154 or Vinyl alcohol polymers with cyanoacetyl groups, such as, for example, the vinyl alcohol / vinyl cyanoacetate copolymers, as described in US Pat. No. 2,8o8,331 or polymeric binders such as can be obtained, for example, by polymerizing a protein or a saturated acrylated protein with a monomer having a vinyl group, such as they are described, for example, in US Pat. No. 2,852,382

The emulsion layers of the photographic material of the invention the usual additives which are used for the production of photographic emulsion layers can be incorporated «See above For example, the emulsion layers may have been chemically sensitized by the usual methods. The emulsions used to produce the Eaul8ionsschichten can des further digested with naturally active gelatine, for example or sulfur-containing compounds can be incorporated into them «The emulsions can also be mixed with salts of the Precious metals such as ruthenium, rhodium, palladium, Iridium and platinum are treated. For example,

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ORIGINAL INSPECTED

Ammonium chloropalladate, potassium chloroplatinate and natriurachloropalladlt. The emulsions can also be chemically sensitized by adding gold salts or with the aid of gold salts be stabilized. Furthermore, the emulsions can be optically sensitized with dyes such as, for example, cyanine and merocyanine dyes. After all, they can Emulsions also contain compounds which increase the sensitivity of the layers, consisting of quaternary ammonium salts or polyethylene glycol compounds.

The emulsions described can be applied to a wide variety of known supports which are known for the production of color photographic material. Examples include cellulose acetate films, cellulose acetate films, polyvinyl acetate tal films, polystyrene films, polyethylene terephthalate films, poly

ethylene foils, polypropylene foils and the like, as well as on paper and

According to a special embodiment, the color photographic material of the invention consists of a support on which at least three differently sensitized emulsion layers have been applied. Preferably, the layer closest to the carrier consists of a red-sensitive layer, on which the green * sensitive layer and then a blue-sensitive layer is applied

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ORIGINAL INSPECTED

Layer and the green-sensitive layer a Carey Lea filter layer be arranged. The three differently sensed layers can, however, also be arranged in a different order be. However, if a Carey Lea filter sheet is used, it should not be placed over the blue-sensitive sheet. Preferably the photosensitive layers are on one Side of the carrier arranged. The blue-sensitive layer contains one of the described new, a yellow dye forming color couplers.

Using the color photographic material of the invention As part of a dye transfer process, the light-sensitive Layer during development with a special receiving layer brought into contact. The receiving layer can, however, also be an integral part of the color photographic material «The receiving layer can be any of the described Be produced carrier materials. The receiving layer has a hydrophilic colloid layer with a cationic mordants, as described, for example, in US Pat. No. 2,882,156. Other suitable mordants are, for example, those described in US Pat 2,484,430 or cetyltrimethylammonylumferomide and the like

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- Io -

The following examples are intended to illustrate the invention in more detail

example 1

Color couplers 3, 4 and using di-n-butyl phthalate as the coupler solvent were added to different proportions of the same camera-sensitive gelatin silver bromoiodide emulsion. The emulsions were coated on a conventional photographic film base. The layers obtained
contained 10 parts by weight of gelatin, 5 parts by weight of silver halide, 2 parts by weight of coupler and one part by weight of coupler solvent.

Strips of the resulting films were exposed for 25ths of a second in an Eastman IB intensity scale sensitometer and then developed according to the following process:

Time ^ stages of development

Immerse in water for 30 seconds

Develop 10 minutes

Interrupt for 5 minutes

5 minutes bleach with ferricyanide

Wash for 5 minutes

Freeze for 5 minutes

Wash for 10 minutes

Treat with wetting agent for 30 seconds.

The following developer solutions were used for development:

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Developer 1 Sodium sulfite (anhydrous)

2-amino-5-diethylaminotoluene HCl

Sodium carbonate, monohydrate Potassium bromide Topped up with water

pH s 10.86

Developer 2

Benzyl alcohol Sodium sulfite (anhydrous)

N-ethyl-ß-methane sulfonamidoftthyl-4-aminoanil sulfate

Sodium carbonate, monohydrate Sodium bromide Sodium hydroxide (20% solution) Sodium hexametaphosphate Topped up with water

2 g

2 g g 2 g 1 liter

M, 00 ml 2.00 G 5.00 G 50.00 G 0.86 G 4.00 ml 0.50 G 1 liter

Of the yellow dye images obtained, a The spectrophotometer determines the λ max values and the D max values are determined using a densitometer. The results obtained are reproduced in the following table I:

Table I. D max Coupler no. Developer No. 2.78
2.58 1 1
2 2.65
2.25 H 1
2 2.92
2.76 5 2

λ max

ORIGINAL INSPECTED

Example 2

The procedure described in Example 1 was used Couplers 3, 4 and 5 are repeated except that the emulsion layers are prepared without using a high-boiling solvent coupler solvent became. Instead of di-n-butyl phthalate, this time there was ethyl acetate used. After the couplers had dispersed in the emulsion, the emulsion was quenched and the ethyl acetate was washed the quenched gelatin removed with cold water. The photographic material obtained was then used in Example 1 exposed, developed and tested. The measurement results obtained are shown in Table II below:

Table II D-max λ-maj KuDDler No. Developer No. _r 2.84
2.80 459
454 3 1
2 2.67
1.30 450
446 4th 1
2 2.82
2.66 464
459 5 IUM

A comparison of the ^D _max ^{values obtained with the} corresponding values of Example 1 shows that the reactivity of the couplers remained essentially unchanged, although the couplers were dispersed in the emulsion layer without the use of a high-boiling solvent.

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ORIGINAL

Example 3

A film was produced according to the procedure described in Example 1, but using Coupler 1. The layer containing the coupler was then exposed as described in Example 1 and developed using developer 1 described in Example 1. The ^D _max "value of the dye image was 3, I ¹ *.

Example 4

Films were produced using the color couplers 7 and 8 according to the procedure described in Example 1. After exposure the films were brought into contact with a receiving layer containing a pickling agent at 23 »9 ° C. for 5 minutes, which had previously been immersed in a developer solution of the following composition:

Sodium carbonate, monohydrate ascorbic acid potassium bromide Sodium sulfite (anhydrous)

4-amino-N-ethyl-N-ß-hydroxyethylaniline sulfate

Topped up with water

The pH of the developer solution was adjusted to 12.5 using a 20% sodium hydroxide solution.

BATH ORIGINAL

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22 g G 0.21 G 0.8 G 2.0 G 11.0 liter 1

After processing, the films became of the receiving layers peeled off, leaving behind transferred yellow dye images *

Equally favorable effects are obtained when the new color couplers which provide yellow images are used in a layer of a multilayer color photographic material of the invention, i.e. in a color photographic material which contains pyrazolone couplers or cyanoacetylcoumarone couplers or indazolone couplers which provide purple color images in one layer and which further contains blue-green dye-forming couplers, such as naphthols and phenols, in a further layer.

The new color couplers are easy to use, starting from a Coupler of the following formula:

0 0

η η

R. C - CH - CN

Br

produce, wherein R, R ₁ and R _{2 have} the meaning already given. The new couplers are prepared by reacting a compound of the formula given with the silver salt of a sulfonic acid. The sulfonic acid has the formula [AgOSO ^) _n R in which Ro ^{and n have} the meanings already given. The compounds of the formula given containing ei o-Bromatora las-

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BATH

sen, for example, according to the US patent 2 728 658 process described in the way it is described for the preparation of a yellow color coupler containing an α-chloro atom "

For example, coupler # 4 can be made as follows:

A mixture consisting of 26 g of a-bromo-a-pivalyl-4- (N-methyl-N-octadecylsulfamyUacetanilide and 9 g of the silver salt of methyl sulfonic acid in 400 ml of acetonitrile was made Boiled for 24 hours on the reflux condenser, whereupon the

fallen silver bromide was filtered off. The filtrate was then concentrated in vacuo, whereupon the residue was dissolved in 500 ml of ethyl acetate. The solution was filtered again to remove a small amount of insoluble compounds. The filtrate was then washed with water and twice with 250 ml of a 1% sodium bromide solution and finally dried over sodium sulfate. The dried solution was then separated from the sodium sulfate and concentrated in vacuo. The solid residue was recrystallized twice from 300 ml of acetonitrile. 23 g of the coupler with a melting point of 94 to 96 ^° C. were obtained.

Couplers 1 to 8 and 11 to 19 were prepared in a corresponding manner using the formula given in the following table. gang compounds and sulfonic acid silver salts produced:

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Table III Coupler No * starting compound

a-Brorao-a-pivalyl-2-chloro-5-Jj- (2,4- «di-t-amylphenoxy) · butyraraidq] acetanilide

Sulfonic acid silver salt Methyl sulfonic acid

p-toluenesulfonic acid

o-Bromo-a-pivalyl-2-chloro-MN-methyl-N-octadecylsulfamyl) acetanilide

o-Bromo-a-pivalyl-4- (N-methy1-N-octadecylsulfamy1) acetanilide

Methyl sulfonic acid Methyl sulfonic acid

11

α-Bromo-α-pivalyl-2,5-dichloro - ^ - (N-methy1-N-octadecy1-sulfamy1) -acetanilide

Methyl sulfonic acid

e-Broeo-a- {3 - & - (2 _# * l-di-t.-aaylphenoxyjbutyranidojbenroyl} -2-methoxyacetanilide methyliulfonic acid

o-Broao-o-piiralyX-il-sulfaayl-M-octadecyloxybeneoli acetanilide sulfonic acid

3-nitrobenzenesafonic acid

oxyacetanilide

α-Broao-α- (2-net hoxybenzoyl) - * -G »- (2, l | -di-t-amylphenoxy) -5- (3-sulfobenzaeido) bentamido] -acetanilide, sodium metalx

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Propyl-1-sulfonic acid

a-bromo-α-ί 3- (jä- (2,4-di-tamylphenoxy) butyramidq] benzoy1} -2-methoxyacetanilld

δ-carboxybutyl-l-sulfonic acid

6-carboxyraethoxybutyl-1-sulfonic acid

α-Bromo-o-pivalyl-NjN-bis- (carbethoxymethyl) acetanilide

Octadecyl-l-sulfonic acid

a-Benzyl-a-bromo-N- (4,5-di-

carbethoxy-2-thiazolyl) acet-

anilide

Docosyl-1-sulfonic acid

α-Bromo-α-furoyl-il- [j- (3-pen-γ-hydroxypropyl-l-sultadecylphenoxy) butyramido] acetanoic acid

anilide

a-Brorao-o- (7 »7-dimethylnorbornyl-

1-carbonyl) -3-palmitamido- 8-ethoxyoctyl-l-sul-

acetanilide fonic acid

2 moles of a-benzoyl-a-brorao-Ί- [a- (2,4-di-t-amylphenoxy) acetamido] acetanilide

Ethyl-i, 2-disulfonic acid, disilver salt

o-Bromo-a-pivalyl-3- | j- (2,4- 4-nitrobenzenesulfonedi-t-amylphenoxy) butyramid§- acid

acetanilide

Compound No. 9 was prepared by reducing Compound No. 8 _{S by} being precipitated on charcoal as a catalyst

ORIGINAL INSPECTED Q 9 8 8 6/1 7 1

Palladium was used. '

Compound No. * 10 was prepared by acylation of the Compound No. 9 using α- (3-pentadeeylphenoxy) acetyl chloride in acetic acid, which contained sodium acetate as a condensing agent.

Compound No. 20 was prepared by catalytic reduction of Compound No. 19 using charcoal-deposited palladium as a catalyst.

Compound No. 21 was prepared by diazotizing the Compound no. 20 and subsequent coupling of the diazo salt obtained with acetyl-H-acid, disodium salt.

Those according to the invention differ from known 2-equivalent couplers therefore used 2-equivalent couplers according to their constitution in that they have a sulfonyloxy group in the coupling position of the coupler molecule. The couplers used according to the invention are notable for the fact that they do not contain any Form color haze and have excellent coupling activity. They can be easily dispersed in emulsions.

The new couplers can be used in particular in emulsion layers alone or together with other 4-equivalent couplers or 2-eq valent couplers, competing couplers and the like.

ORIGINAL INSPECTED

909886/1710

Claims (6)

Claims 1 · Color photography cheesy material with at least one on one Supported layer, which contains a color coupler »by coupling with the oxidation product one of a aromatic amine existing developer compound is able to form a yellow dye and that of the formation of 1 mol Dye requires 2 moles of silver halide, characterized in that the layer contains a coupler of the following formula: N - "1 C * O k ι c » O I. R. ^ η where mean: R is an alkyl, terpenyl, aryl or heterocyclic Group; R ₁ and R ₂ hydrogen atoms »alkyl, aryl or heterocyclic Groups} η 1 or 2 and R if η * 1 is an alkyl or ary! Group or if η * 2 is »an alkylene or arylene group. ORIGINAL INSS 809886 / 171Q 2. Farbphotographieehes material according to claim 1, characterized in that it is used as coupler / a-methylsulfonyloxy-a-pivalyl-2 " contains chloro-l * - (N-ynethyl-N-octadecylsulfamyl) acetanilide. 3. Color photographic material according to claim 1, characterized in that it contains δ-methylsulfonyloxy-α-pivalyl-4- (N-methyl-N-octadecylsulfamy-acetanilide) as a coupler. 4. Color photographic material according to claim 1, characterized in that it contains a-methylsulfonyloxy-a-pivalyl-2,5-dichloro-ii- (N-methyl-N-octadecylsulfamyl) acetanilide as a coupler. 5. Color photographic material according to claim 1, characterized in that it contains a- (3- [a- (3-pentadecylphenoxy) acetamido] phenylsulfonyloxy} -a-pivalyl-3,5-dicarboxyacetanilide as a coupler. 6. Color photographic material according to claim 1, characterized in that it contains as coupler α, α'-ethylenedisulfonyloxybis (abenzoyl-1- [δ- (2,4-di-t.-amy! Phenoxy) acetamido] acetanilide). 7 «Color photographic material according to claims 1 to 6, characterized characterized in that the coupler is housed in a silver halide emulsion layer. 909886/171 0