DE1816899B2 - Yellow coupler - Google Patents

Description

2. Use of the yellow coupler according to claim for the production of a color photographic Material having three silver halide emulsion layers, the yellow coupler in a blue-sensitive silver halide emulsion layer or is contained in an adjacent, non-light-sensitive, water-permeable colloid layer.

3. Use of the yellow coupler according to claim for the production of a photographic color image

15th

20th

25th by developing a photographic image-wise exposed silver halide containing Material with the help of a developer that is obtained by reducing the exposed silver halide in their oxidized form is converted, and as such a yellow azomethine dye by A reaction with a color coupler according to claim 1, wherein the color coupler is in or in a blue-sensitive silver halide emulsion layer another colloid layer of this photographic material in water-permeable relationship with the former layer

This invention relates to the subject matter characterized by the claims.

It is known that the exposed silver halide is used to produce a photographic color image in a photosensitive silver halide emulsion layer. genid developed into a silver image by means of a primary aromatic amino compound in the Presence of a color coupler, the developer substance oxidized with animal at the points corresponding to the silver image to form a dye reacted

In subtractive three-color photography, it becomes a color photographic light-sensitive material used, which has a red-sensitized, a green-sensitized and a blue-sensitive silver halide Contains emulsion layer in which a blue-green, a purple or a yellow dye image are produced during color development through the use of suitable color couplers. Principal difficulties to which one in the color photographic concern the lightfastness Heat resistance and moisture resistance of the dyes representing the image. Although color photography has evolved since the use of color couplers for the generation of color images in depth perfection one is still trying. Dyes with to find better stability.

For example, those described in German patents 12 13 739 and 10 38 916 have Thiazole coupler is an excellent coupling activity on and deliver those in the first mentioned Compound already moisture and heat stable dyes in photographic materials in their photographic processing; however, these connections too are still in terms of their ability To deliver pure yellow dyes of sufficient stability needs improvement.

The yellow couplers according to the invention are very heat- and moisture-resistant, and those produced therewith

yellow azomethine dye images not only have favorable spectral properties and excellent Lightfastness, but also an extremely high level of resistance under certain circumstances can be considerable Moisture and heat similar to those of the corresponding color couplers of the 2- (p-alkoxybenzoylacetamido) -thiazoI-type are superior. In addition, these yellow couplers have high coupling ability, that is, they give dye images with high Color density regardless of the presence of the replaceable groups. This is pretty surprising because of it is generally known, among other things through the »Publications of the scientific photo laboratories Wolfen «Volume X (1965) p. 299, S. Hirzel Verlag, Leipzig,

ok

coci

Na CH3COCHCOOR

0-D

GDR, and from the American patent specification 27 28 658 that an ortho substitution, in particular an o-alkoxy substitution on the benzoyl part of the Benzoylacetarylide color coupler, which reduces the coupling ability of the coupler and the coloring power of the obtained It turns out that in the case of the 2-benzoylacetamidothiazole color couplers according to the invention ortho substitution does not reduce the coupling ability of the coupler molecule

The preparation of the yellow color couplers according to the above general formula can be carried out as follows Represent reaction scheme:

Ri COCH ₃

-> \ / - CO— CH- COOR

CO-CH ₂ -COOR

O —D

COCH ₂ COOR + H ₂ N-

O-D

-COCH ₂ CONH-

O —D

in which R ₁ , Z and D have the same meaning as above and R denotes a lower alkyl group such as a methyl and ethyl group.

Benzoylacetamide color couplers falling under the above general formula I include the Compounds with the following formulas:

C-NHCOCH ₂ CO

Il

^N C ₁₂ -H ₂₅ O

C ₁₆ H ₃₃ O

/ \ C C-NHCOCH ₂ CO

CH

C ₁₆ H ₃₃ O

CH HOOC —C -

C-NHCOCH ₂ CO " ^N C ₁₆ H ₃₃ O

C ₂ H ₅ OOC-CH C-

Il Il

CH N

S \

-NHCOCH ₂ CO- / \ C ₁₆ H ₃₃ O

HOOC-CH ₂ -C C -NHCOCH ₂ CO

/ \ C ₂ H ₅ OOC-C C-

C ₁₆ H ₃₃ O

-NHCOCFi ₂ CO- ^ C ₁₆ H ₃₃ O

CH C-

S ^^ CN

C ₁₆ H ₃₃ O

SO ₃ Na

CH \ c—
Μ NHCOCH ₂ CO Il
N C] ₂ H ₂₅ K ^. - O

SO ₃ Na

CH C-NHCOCH ₂ CO

Y
COOH

CH ₂ S

\ CH ₂ V C-

CH ₂

C ₁₆ H ₃₃ O

-NHCOCH ₂ CO-1 ^ Jp

/ K / C ₁₆ H ₃₃ O

CH ₂

CH C-

C ₁₆ H ₃₃ O

CH C-NHCOCH ₂ CO-

C ₁₆ H ₃₃ O

CH ₃ O

C-NHCOCH ₂ CO-T

Il

CH C -NHCOCHCO

C ₁₆ H ₃₃ O

CH C-NHCOCH ₂ CO

CH C-NHCOCH ₂ CO

The following preparation examples illustrate the invention.

Production 1: connection 1

a) o-Dodecyloxybenzoyl acetic acid methyl ester

CH ₃

CH ₃

45

153 g (0.5 mol) of o-dodecyloxybenzoic acid as described in J. Am. Chem. Soc. 64 (1942) 1961, and 109 ml of thionyl chloride Heated under reflux for 3 hours. The excess thionyl chloride is evaporated and a light brown oily residue remains.

The oily residue is added with stirring to a suspension of 152 g (1 mol) of the sodium salt of ethyl acetate in 250 ml of dichloromethane. Stirring is continued for 3 hours and the reaction mixture is treated with 500 ml of dilute hydrochloric acid. The dichloromethane layer is washed with water until free from acid, getrock- t> o net over magnesium sulphate and evaporated The oily residue was kept for 3 hours in a vacuum of 2-5 mm Hg at 100 ⁰ C, to remove the Acetylessigsäureäthylester.
The oil is added with stirring to a solution of 30 g of sodium methylate in 350 ml of methanol. After standing for 24 hours, the solution is acidified and extracted with dichloroethane. The OC ₁₀ H

IO "21

Solution in dichloromethane is washed, dried and concentrated. One receives a light yellow oil.

b) 2-amino-4-phenylthiazole

is prepared as described by Dodson and King in J. Am. Chem. Soc. 67 (1945) 2242.

c) 2- (o-Dodecyloxybenzoylacetylamino) -4-phenylthiazole

A mixture of 36.2 g (0.1 mol) of o-dodecyloxybenzoyl acetic acid methyl ester, 17.6 g (0.1 mole) 2-amino-4-phenylthiazole and 0.2 g sodium acetate and xylene is heated until the reflux temperature is reached. A mixture becomes over 1 hour distilled off from xylene and formed methanol. The remaining xylene is distilled off under reduced pressure distilled off, and 200 ml of hexane is added to the oily residue Cool the mixture while stirring. The precipitate formed is recrystallized from acetonitrile Melting point: 68-69 ° C

Production 2: connection 4
a) o-Hexadecyloxybenzoyl acetic acid methyl ester

This compound is synthesized in a manner analogous to that of preparation example la) wherein but one of OJ moles of o-hexadecyloxybenzoic acid goes out in sequence according to

Method of Stanton and coworkers, J. Am. Chem. Soc. 64 (1942) 1961. Melting point: 53-54 ° C.

b) 2-amino-4-carbethoxythiazole

is prepared as described in J. Am. Chem. Soc. 68 (1946) 268.

c) 2- (o-Hexadecyloxybenzoylacetylamino) -4-carbethoxythiazole

is prepared in a manner analogous to that described in preparation example Ic), but one of 0.1 mole of methyl o-hexadecyloxybenzoyl acetate and 0.1 mol of 2-amino-4-carbäthoxythiazole goes out. A light-emitting viscous oil is obtained.

d) 2- (o-Hexadecyloxybenzoylacetylamino) -4-carboxythiazole

0.1 mol of the oil obtained according to preparation example 2c), 250 ml of ethanol and 100 ml of 2 η aqueous Sodium hydroxide is refluxed for 1 hour. The mixture is diluted with Acidified sulfuric acid, and the white to light yellow precipitate formed from isopropanol recrystallized. Melting point: 110 ° C.

Production 3: connection 8

a) 2- (o-Hexadecyloxybenzoylacetylamino) -4- (m-fluorosulfonylphenyl) thiazole

This compound is prepared in a manner analogous to that described in the preparation example 1, but 0.1 mol of methyl o-hexadecyloxybenzoyl acetate (see preparation example 2a) and 0.1 mol of 2-amino-4- (mfluorosulfonylphenyl) -thiazo! produced as described below, starting out A white crystalline product is obtained. Melting point: 108 ° C.

b) 2- (o-Hexadecyloxybenzoylacetylamino) -4- (m-sulfophenylj-thiazole

0.1 mol of the above fluorosulfonyl compound is heated in 400 ml of acetone until the reflux temperature is reached. 60 ml of 5 η aqueous sodium hydroxide are slowly added with stirring, whereupon the mixture is refluxed for 30 min. This mixture is then with acidified with an excess of sulfuric acid, so that the free sulfonic acid precipitates

Manufacture of the
2-amino-4- (m-fluorosulfonylphenyr) thiazoles

a) m-Fluorosulfonylbenzoyl chloride

20.4 g (0.1 mol) of m-fluorosulfonylbenzoic acid, prepared by reacting m-chlorosulfonylbenzoic acid with potassium fluoride in an aqueous dioxane medium, are allowed to react with an excess (0.45 mol) of thionyl chloride. Yield: 213g (96%) - Melting point: 116-117 ^o C / 2mm Hg-

b) m-fluorosulfonylacetophenone

m-Fluorosulfonylbenzoyl chloride is converted to the matching acetophenone, whereby

principally according to the process developed by Long and Troutman for the preparation of the p-nitroacetophenone (J. Am. Chem. Soc. 71, 2473 [1949]). That after the hydrolysis of diethyl m-fluorosulfonylbenzoylmalonate The product obtained is treated with a saturated sodium hydrogen carbonate solution washed by about 5% of the hydrolysis m-fluorosulfonylbenzoic acid to remove. Obtained starting from 52.5 g (0.24 mol) of m-fluorosulfonylbenzoyl chloride after recrystallization from approximately 350 ml of methanol, 36.8 g (76%) of m-fluorosulfonylacetophenone are obtained. Melting point: 92 ° C.

c) m-fluorosulfonylphenacyl bromide

To 40.4 g (0.2 mol) of m-fluorosulfonylacctophenone, dissolved in 45 ml of dioxane, 32 g (0.2 mol) of bromine are allowed to act at 40-50 ° C. That through the Dilution of the reaction mixture with water, precipitated oily bromoketone is collected, whereupon the aqueous phase is extracted with methylene chloride. The oil and the methylene chloride solution are combined, washed with aqueous sodium hydrogen carbonate solution and dried over magnesium sulfate. After removing the solvent, the bromoketone is added distilled at 170 ° C / 2 mm Hg. The oily product slowly solidifies to a crystalline one Dimensions. Melting point: 48-50 ° C. Yield: 3.97 g (78.5%).

d) 2-Amino-4- (m-fluorosulfonylphenyl) thiazole

A solution is added to a solution of 15.2 g (0.2 mol) of thiourea in 40 ml of boiling ethanol

S5 of 56.2 g (0.2 mole) of m-fluorosulfonylphenacyl bromide in 45 ml of dioxane at such a rate that the released in the reaction Heat is sufficient to keep the reaction mixture boiling (40-60 min.). The 2-amino-4- (mfluorosulfonylphenyl) thiazole bromohydrate, obtained by cooling the reaction mixture to room temperature is at 80-90 ° C in about 120 ml of water containing about 15% ethylene glycol monomethyl ether contains dissolved and neutralized with sodium hydrogen carbonate. The precipitate formed is collected with water washed and dried at 90 ° C. Yield: 29 g (62%). Melting point: 154-156 ° C

The yellow couplers of the present invention are of the non-diffusible type; H. they contain in their molecule an organic group that is large enough to prevent the coupler molecule from migrating out of the colloid layer, in which it is incorporated, to prevent another colloid layer.

For the production of a color photographic multilayer material, the diffusion-resistant Color couplers for each color separation image usually in the composition of the differently sensitized . Silver halide emulsion layers incorporated. However, the diffusion-resistant color couplers can also in the casting compositions of the non-photosensitive Colloid layers are incorporated, which are in a water-permeable relationship with the light-sensitive . Silver halide emulsion layers, for example in layers that coincide with the photosensitive Layers are in direct contact, or from

these light-sensitive layers separated by water-permeable, non-light-sensitive layers are.

In the production of the color photosensitive material, the diffusion-resistant yellow couplers can be used after of the above general formula according to any known technique into the casting composition of Silver halide emulsion layers or others Colloid layers, which are thus in a water-permeable relationship, are incorporated. For example the water-soluble color couplers, i. H. those that have one or more water-solubilizing agents Contain groups such as a sulfo or carboxyl group (in acid or salt form) from an aqueous one Solution or the insoluble or insufficiently water-soluble color couplers from a solution in the suitable water-miscible or non-water-miscible high boiling point or low boiling point organic solvents or mixtures thereof in the coating composition of the layer in question be incorporated. The solution obtained is then optionally in the presence of a network or Dispersant dispersed in a hydrophilic colloid composition, the whole or just one Is part of the binder of the colloid layer. In addition, the hydrophilic colloid composition may naturally contain some other type of ingredient in addition to the colloid. The non-water soluble Color couplers which contain fluorosulfonyl groups or carboxylic acid ester groups such as ethoxycarbonyl groups can also be converted into the corresponding sulfonic acids or sulfonic acids by alkaline hydrolysis. Carboxylic acids, which in turn form hydrophilic colloid compositions in the form of their alkali salts can be incorporated from aqueous solutions, converted.

The solution of the color coupler does not need to be incorporated directly into the coating composition of the silver halide emulsion layer or another water-permeable layer to be dispersed or dissolved. These Solution can advantageously first be in an aqueous, non-photosensitive solution of a hydrophilic colloid dispersed or dissolved, whereupon the mixture obtained after the eventual removal of the used organic solvent with this coating composition of the photosensitive silver halide emulsion layer or the other water-permeable layer is thoroughly mixed just before application. More about, particularly suitable Techniques for incorporating color couplers into hydrophilic colloid layers of a photographic Materials can be found in laid-open Dutch patent applications 6516 423, 6516 424, 66 00 098.66 00 099.66 00 628, in the Belgian patent 7 05 889, in American patent 23 04 940, in British patent 7 91 219.

The couplers of the present invention can be used in conjunction with various kinds of photographic printing Use emulsions. Various silver salts can be used as sensitive salts such as Silver bromide, silver iodide, silver chloride or mixed Silver halides such as silver chlorobromide, silver bromide iodide and silver chlorobromide iodide. The couplers can be used in drop emulsions as described in US Pat American Patent 26 98 794 or in mixed comemulsions as described in American Patent 2592 243 can be used. The color couplers can be used in emulsions where latent images are mainly on the surface of the silver halide crystal or in emulsions in which latent images are mainly are formed within the silver halide crystal.

The hydrophilic colloid for dispersing the silver halide may be gelatin, colloidal, for example Albumin, zein, casein, a cellulose derivative, a synthetic hydrophilic colloid such as polyvinyl alcohol or Be poly-N-vinylpyrrolidone. If desired, one can use miscible mixtures of two or more use these colloids to disperse the silver halide.

The light-sensitive silver halide emulsion for preparing a photographic material can be both chemically and optically sensitized. You can be chemically sensitized by the Maturation in the presence of small amounts of sulfur-containing compounds such as allyl thiocyanate, allyl thiourea or sodium thiosulphate. The emulsions can also be carried out with the help of reducing agents z. B. those in French patent specification 11 46 955 and in Belgian patent specification 5 68 687 tin compounds described, the iminoaminomethanesulfinic acid compounds described in British patent specification 7 89 823 and small amounts of precious metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium will. They can be optically sensitized using cyanine and merocyanine dyes.

These emulsions may also contain compounds that accelerate the development of the emulsions raise awareness, e.g. B. Polyoxyalkylene type compounds such as alkylene oxide condensation products as described in American patents 25 31832 and 25 33 990, in the British patents 9 20 637, 9 40 051, 945 340 and 9 91608, and in Belgian patent 6 48 710, and onium derivatives of amino-N-oxides such as described in laid-open Dutch patent application 66 12 269.

The emulsion can also contain stabilizers, for example heterocyclic nitrogen-containing thioxo compounds such as benzthiazoline-2-thione and 1-phenyl-2-tetrazoline-5-thione and oxytriazolopyrimidine type compounds. They can also be stabilized with mercury compounds such as those described in Belgian patents 5 24 121 and 6 77 337, laid-open Dutch patent application 67 15 932 and in American patent specification 31 79520.

The light-sensitive emulsions can also contain all other types of ingredients such as plasticizers, Hardeners, wetting agents.

The diffusion-resistant yellow couplers mentioned in this invention are usually converted to blue-sensitive ones Silver halide emulsion layer incorporated This silver halide emulsion layer is incorporated in a conventional method as the upper coupler-containing layer of a multilayer color photographic material Such a multilayer material usually contains in the specified Order a red-sensitized one containing blue-green coupler Silver halide emulsion layer containing a magenta coupler green-sensitive silver halide emulsion layer and a yellow coupler-containing blue-sensitive silver halide emulsion layer Usually is between the blue-sensitive silver halide emulsion layer and the green-sensitized silver

halide emulsion layer a yellow filter layer arranged, which generally contains colloidal silver dispersed in gelatin.

The emulsions can be coated on any photographic substrate. Typical Supports are films made of cellulose ester, polyvinyl acetal, polystyrene, polyethylene terephthalate, and similar resinous material, as well as paper and glass.

To produce photographic color images, an exposed silver halide emulsion layer is developed with an aromatic primary amino developing agent in the presence of a color coupler according to the invention. All color developing agents which have the ability to give azomethine dyes can be used as developing agents. Suitable developer substances are aromatic compounds such as p-phenylenediamine and its derivatives, for example Ν, Ν-dialkyl-p-phenylenediamines such as Ν, Ν-diethyl-p-phenylenediamine, N ₁ N-dialkyl-N'-sulfomethyl-p-phenylenediamines , and N, N-dialkyl-N'-carboxymethyl-p-phenylenediamines.

example 1

To 300 g of a blue-sensitive silver bromide iodide emulsion (2.3 mol% iodide) containing 23 g gelatin and an amount of silver halide equivalent to 20 g silver nitrate, 0.006 mol of color coupler No. 3 of the above list is added. After neutralization and the addition of the usual additives such as stabilizers, wetting agents and hardeners, the necessary amount of distilled water is added to obtain 575 g of emulsion. The emulsion is then applied to a cellulose triacetate carrier in a ratio of 150 g per m ^2. The emulsion layer is then dried and coated with a protective gelatin layer.

After drying, the material V20 sec is exposed through a continuous wedge with constant 0.30 and developed 8 min at 2O ⁰ C in a developing bath of the following composition..:

Ν, Ν-diethyl-p-phenylenediamine- 2.75 g
sulfate

Hydroxylamine sulfate 1.2 g

Sodium hexametaphosphate 4 g

anhydrous sodium sulfite 2 g

anhydrous potassium carbonate 75 g

Potassium bromide 2.5 g

Water up to 1 1

Borax 20 g

anhydrous potassium bromide 15 g

anhydrous sodium hydrogen sulfate 4.2 g

Potassium hexacyanoferrate (III) 100 g
Water up to 11

A yellow wedge image is obtained with an absorption maximum at 452 nm.

Examples 2-4

In three similar SiIb bromide iodide emulsions As described in Example 1, color coupler No. 3 is replaced by 0.006 mol of color coupler No. 4, 5 and 7, respectively replaced. After neutralization and the addition of the usual ingredients, the emulsions become encapsulated, exposed through a continuous gray wedge and processed as described in Example 1.

Yellow wedge images with absorption maxima of 450, 456 and 456 nm are obtained.

Example 5

400 g of a blue-sensitive silver bromide iodide emulsion (5 mol% iodide) containing 30 g gelatin and an amount of silver halide equivalent to 27.5 g silver nitrate are melted and ^{mixed with 50 cm 3 of} distilled water The emulsion is acidified with 72 ml 0.016 η acetic acid, whereupon 5 g of color coupler no. 2 of the above list of inventive color couplers, dissolved in 25 ml of ethanol, 5 ml of 2 η sodium hydroxide and 20 ml of distilled water are added, then 5 g of color coupler no. 8 of this same list, dissolved in 15 ml of ethanol, are added 5 ml 2 η sodium hydroxide solution and 30 ml of water is added after adding the usual additives such as hardeners, wetting agents and stabilizers, the pH of the emulsion is adjusted to 6.4 this emulsion is 10 m ² film support coated is provided with an antihalation layer, whereupon the material is dried. After exposure through a gray wedge, the material is developed for 8 minutes at 20 ° C in a color developer with the following composition:

The material is developed for 2 min at 18-20 ⁰ C in an intermediate bath treats the coated from a 3% aqueous solution of sodium sulfate bestehL Then the material is 15 minutes rinsed with water and treated in a bleaching bath of the following composition..:

After bleaching, the material is rinsed with water for 5 minutes and fixed in a 20% strength aqueous solution of sodium thiosulphate. After a final 15 minute rinse, the material is dried

water 900 ml Sodium hexametaphosphate ig anhydrous sodium sulfite 4g Ν, Ν-diethyl-p-phenylenediamine-chloro- 2.7 g hydrate anhydrous sodium carbonate 25 g Potassium bromide 2.2 g Sodium bicarbonate 0.55 g Water up to 1 I.

The developed material is rinsed for 10-20 seconds, whereupon it is treated for 4 minutes in a fixing bath of the following composition:

water 800 ml anhydrous sodium thiosulfate 200 g Sodium hydrogen sulfite 12g Glacial acetic acid 12 ml borax 20 g Potassium alum 15g Water up to H

The material is then rinsed for 3 minutes, whereupon it 4 min. In a bleaching bath with the following composition:

water

Potassium hexacyanoferrate (III)
Potassium bromide
Glacial acetic acid
Sodium acetate

900 ml

75 g

15 g

10 ml

5g

Potassium alum Water up to

After bleaching, the material is rinsed with water for 2 minutes, whereupon it is 4 billion in the above Fixing bath is fixed. After a final flushing process, the material is dried bright, transparent yellow wedge image with a Absorption maximum at 439 nm.

The yellow couplers of the present invention produce primary aromatic compounds when they are color-developed Amines such as p-phenylenediamine yellow dyes, which due to their favorable light absorption in the blue part of the spectrum and their slight absorption Excellent absorption in the other areas. In addition, they have in color development

the resulting dyes have good heat resistance,

Moisture resistance and durability, and white

have high responsiveness during development, i.e. they give color images with high Color density.

In order to compare the favorable properties of the 2- (o-alkoxybenzoylacetomido) -thiazole color couplers according to the invention with those of the 2- (p-alkoxybenzoylacetamido) -thiazole color couplers, Experiments carried out For this purpose, after development with p-benzene diamine sulfate, the sensitometric characteristics of silver bromide iodide gelatin emulsions (23 mol% iodide) were determined 73.4 g of gelatin per kg, an amount of silver halide equivalent to 47 g of silver nitrate and a color coupler A contain the following formula:

C-NHCOCH ₂ CO

Il

OC ₁₆ H ₃₃

SO ₃ Na

or a color coupler B according to the invention of the formula:

S CH C — NHCOCH ₂ CO- / \

^ "H ₃₃ C ₁₆ O

SO ₃ Na

each from a solution of 0.01 mol of color coupler in 24 ml of distilled water, 12 ml of ethanol and 4.5 ml 2 η sodium hydroxide were incorporated.

The sensitometric results are shown in the following table:

Color Relative Gradation Maximum Absorption

Coupling sensation density maximum

probability in nm

A. 100 1.37 2.50 460 B. 162 1.41 2.53 445

The maximum density values show that, contrary to expectations, the coupling ability of the 2- (o-alkoxybenzoylacetamido) thiazole color couplers is not is lower than that of the corresponding p-alkoxy derivatives. In addition, the achieved sensitivity significantly higher than those obtained with the matching p-alkoxy color couplers.

The moisture resistance and the heat resistance of the in the development by the reaction of the oxidation products of p-phenylene diamine with the above color couplers dyes generated is determined from the Densitätsabnahme a developed wedge imprint after a Abdrück been stored for 24 hours at 60 ⁰ C and 100% relative humidity in the dark was.

The results obtained are shown in the following table.

Color coupler

Percentage decrease in density for the following density values

D-0.5

D- 1.0

0 = 1.5

D = 2.0

A. -66% -74% -75% -77% B. -12% -10% - 9% -11%

To compare the favorable properties of the 2- {o-alkoxybenzoylacetamido) -thiazole color couplers according to the invention with those of the sulfobenzoylacetamido-thiazole color couplers of the German patent To compare 1213 739, experiments were carried out leads.

For this purpose four silver bromide iodide gelatin emulsions (23 mol% iodide) were prepared, with each emulsion 73.4 g of gelatin per kg, an amount of silver halide equivalent to 47 g of silver nitrate and 0.01 mol of one of the color couplers given below.

Emulsion A: Coupler 3 of DE-PS 12 13 739 Emulsion B: Coupler 7 of DE-PS 12 13 739 Emulsion C: Coupler 2 according to the invention Emulsion D: Coupler 8 according to the invention

The emulsions were applied to a cellulose triacetate base in an amount of 150 g per m ² , dried and covered with a protective gelatin layer.

After drying the materials thus produced, a test strip was made from each material

030142/11

'/ μ second through a gradient wedge with a Constant of 03 exposed and 8 minutes at 20 ° C in a developer bath of the following composition long developed:

N, N-diethyl-p-phenylenediamine sulfate 2.75 g Hydroxylamine sulfate 1.2 g

Sodium hexameiaphospha! 4.0 g Anhydrous sodium sulfite 2.0 g Potassium carbonate anhydrous 75.0 g Potassium bromide 23 g

fill up with water to 1 l

The developed materials were placed in an intermediate bath containing 30 g Contains sodium sulphate in one liter of water. Then the materials are for 15 minutes soaked in water and treated in a bleach bath of the following composition:

10

.'0

Borax 20 g

Potassium bromide anhydrous 15 g Sodium bisulfate anhydrous 4.2 g Potassium hydroxacyanoferrate (III) 100.0 g 2 ^r >

fill up with water to 1 1

After bleaching, the materials are soaked with water for 5 minutes; and in an aqueous one Solution of 200 g of sodium thiosulfate per liter fixed. After a 15 minute final bath, the materials were dried

The following table shows the percentage secondary absorption in the green and red spectral range of the yellow color image as well as its percentage decrease in the density of the developed images after the images had been stored in the dark for ^{24 hours at 60 ° C. and 100% relative humidity.}

Tabel

Etnul- Λ max sion % Absorption blue green

Red

mm

% Decrease in density,

measured at density density 0.5 13

ABCD 468
456
450
448

100 100 100 100

22nd
21

4th 6th

-62

-48

-68

-15

-10

Claims (1)

Patent claims: 1. Yellow coupler of the general formula: ο — υ CO-CH-CO-NH-C in which: X is a hydrogen atom or a group which is customary in color couplers and which can be split off during color development, One of the molecules that is common in color couplers diffusion-proofing group with 5 to 20 carbon atoms, Ri is a hydrogen or a halogen atom, a Alkyl, alkoxy, dialkylamino or sulfamoyl group, and Z is the atoms required to complete one of the following thiazole rings: Thiazole, 4-methylthiazole, 4-tert-butylthiazole, 4-benzylthiazole, 4-phenylthiazole, 5-phenylthiazole, 4- (p-methoxyphenyl) thiazole, 4- (p-chlorophenyl) thiazole, 4-phenyl-5-fluorosulfonylthiazole, 4-methyl-5-sulfothiazole, 4- (m-fluorosulfonylphenyl) thiazole, 4- (p-sulfophenyl) thiazole, 4- (m-sulfophenyl) thiazole, 4-ethoxycarbonylthiazole, 5-ethoxycarbonylthiazole, 4-carboxythiazole, 5-carboxythiazole, 4,5-diethoxycarbonylthiazole, 4-phenyl-5-ethoxycarbonylthiazole, 4-phenyl-5-carboxymethylthiazole, 4-carboxy-5-phenylthiazole, 4- (o-carboxyphenyl) thiazole, 4,5,6,7-tetrahydrobenzothiazole, 4,5,6,7,8,9-hexahydrocyclooctathiazole, 4 H-indeno- [2, l-d] thiazole, 6-methoxybenzthiazoI, 5,7-dimethoxycarbonylbenzthiazole, Thiazolo [5,4-b] pyridine, 4,5-diphenylthiazole, 4-J? -Naphthylthiazole, 4- (2-thienyl) thiazole, 4-benzyl-5-phenyl-thiazole, 4-ethoxycarbonyl-methyl-5-ethoxycarbonyl thiazole or 4- (m-Dimethylsulfamoylphenyl) thiazole.