DE1816899C3 - Yellow coupler - Google Patents

Description

2. Use of the yellow coupler according to claim for the production of a color photographic Material with three silver halide emulsion layers, with the yellow coupler in a blue-sensitive Silver halide emulsion layer or in a non-photosensitive layer adjacent to it water-permeable colloid layer is included.

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

15th

20th

25 by developing a photographic, image-wise exposed silver halide-containing material with the aid of a developer which is converted into its oxidized form by reducing the exposed silver halide, and as such forms a yellow azomethine dye by reaction with a color coupler according to claim 1, the color coupler in a blue-sensitive silver halide emulsion layer or in another colloid layer of this photographic material is in water-permeable relationship with the former layer

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

It is known to form a color photographic image in a photosensitive silver halide emulsion layer the exposed silver halide by means of a primary aromatic amino compound developed into a silver image in the presence of a color coupler, which is oxidized with the Developing substance at the points corresponding to the silver image to form a dye reacted.

In subtractive three-color photography, a color photographic light-sensitive material is used which contains a red-sensitized, a green-sensitized and a blue-sensitive silver halide emulsion layer in which a blue-green, a purple or a yellow dye image is formed during color development by the use of suitable color couplers.
Fundamental difficulties encountered in color photography relate to the light fastness, heat resistance and moisture resistance of the dyes representing the image. Although color photography has been thoroughly perfected since the use of color couplers to produce color images, efforts are still being made to find dyes with better stability.

For example, those described in German patents 12 13 739 and 10 38916 have Thiazole couplers are an excellent coupling

bo activity and provide those already more moisture and heat stable in the first-mentioned compound Dyes in photographic materials during their photographic processing; nevertheless are also these compounds still in terms of their ability

b5 pure yellow dyes of sufficient stability to deliver, 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 an excellent one Lightfastness, but also an extremely high level of resistance under certain circumstances can be considerable Moisture and heat similar to that of the corresponding color couplers of the 2- (p-alkoxybenzoylacetamido) -thiazole-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,

N / A
Ch ₃ COCHCOOR

Ri
\ y> - ^C0C1

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, the coupling ability of the coupler and the coloring power of the dye obtained. that in the case of the 2-benzoylacetamidothiazole color couplers according to the invention an ortho substitution does not reduce the coupling ability of the coupler molecule

ίο reduces the production of the yellow color coupler according to the above The general formula can be represented by the following reaction scheme:

Ri COCH ₃

CO-CH-COOR

O —D

CO-CH ₂ -COOR

j> - COCH ₂ COOR + H ₂ N- / £

Ο —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:

CH C - NHCOCH

CH C - NHCCK

^{: HiCO} X)

CH ₂₅ O X)

^{: HiC0} ; 0

C ₁₆ H ₃₃ O

C-NHCOCH ₂ CO C ₁₆ H ₃₃ O

CH ^N C -NHCO CH ₂ CO-1 / \ C ₁₆ H ₃₃ O

C ₂ H ₅ OOC-CH ^N C -NHCOCH ₂ CO- / ^

C ₁₆ H ₃₃ O

HOOC-CH ₂ -C

CH N

C-NHCOCH ₂ CO- ^] |

C ₁₆ H ₃₃ O

C ₂ H ₅ OOC-C C -C -NHCOCH ₂ CO-T

< ^/ ~ ^ -CN _Ci6H33O

CH C-NHCOCH ₂ CO

SO ₃ Na SO ₃ Na

C ₁₆ H ₃₃ O

S.
CH C-NHCOCH ₂ CO

C ₁₂ H ₂₅ -O

CH ^X C-NHCOCH ₂ CO- /

C ₁₆ H ₃₃ O COOH

CH ₂ S

/ \
CH ₂ Y C-NHCOCH ₂ CO

CH ₂

-N

C ₁₆ H ₃₃ O

CH ₂

SO ₂ N (CH ₃ ) J

CH 'C-NHCOCH ₂ CO / ■ V_c N

C ₁₆ H ₃₃ O

(CHj) ₂ NSO ₂

CH C-NHCOCH ₂ CO

C ₁₆ H ₃₃ O

Cl

CH ₃ OT

C-- NHCOCIl-CO- '- ■

C — NHCOCH-CO-

-N

y?

CH C-NHCOCHCO

Il Il

c _{N c} . ,,,, y

C-NHCOCH-CO

Il

^N C ₁ -HvO N

CH,

CH-

C-NHCOCH-CO- / "% AA

C10H21O 0C10H21

The following preparation examples illustrate the invention.

Production 1: connection 1

a) o-Dodecyloxybenzoyl acetic acid methyl ester

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 are refluxed for 3 hours. That Excess thionyl chloride is evaporated off, and a light brown oily residue remains return.

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 it is free from acid, dried over magnesium sulfate and concentrated. The oily residue is 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 solution in dichloromethane is washed, dried and concentrated. A light yellow oil is obtained.

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 methyl o-dodecyloxybenzoyl acetate. 17.6 g (0.1 mol) of 2-amino-4-phenylthiazole and 0.2 g of sodium acetate and xylene is heated until the reflux temperature is reached. A mixture of xylene and methanol formed is distilled off over a period of 1 hour. The remaining xylene is distilled off under reduced pressure and the oily residue becomes 200 ml of hexane were added. The mixture is then allowed to cool while stirring. The educated The precipitate is reprecipitated 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 starts from 0.5 mol of o-hexadecyloxybenzoic acid in sequence according to the

Method of S - ,. πΐυπ u: l: Miiarbeiior.
Chem. Soc. 64 (1942) 1961 nen · ■■ · viii Melting point: 5.3- "·! C

Ά ill til '.

b) 2-Amino-4-carbäihoxythia / oi

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 mole of 2-amino-4-carbäihoxythiazole goes out. A light yellow, 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 2η aqueous sodium hydroxide are refluxed for 1 hour. The mixture is acidified with dilute sulfuric acid and the white to light yellow precipitate formed is recrystallized from isopropanol. Melting point: 110 ⁰ 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 preparation example 1, but 0.1 Mo! o-Hexadecyloxybenzoyl acetic acid methyl ester (see preparation example 2a) and 0.1 mol of 2-amino-4- (mfluorosulfonylphenyl) thiazole prepared as described below, starts out. A white crystalline product is obtained. Melting point: 108 ⁰ C.

b) 2- {o-Oxadccyloxybcnzoy! acctylamino) -4- (m-sulfophenyl) -thiazole

0.1 mol of the above fluorosulfonyl compound is heated in 400 ml of acetone until the reflux temperature is reached. With stirring, 60 ml of 5 η aqueous sodium hydroxide are slowly added. 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-fluorosulfonylphenyl) 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 aqueous dioxane medium, left with an excess (0.45 Mo!) Thionyl chloride react. Yield: 21.3 g (96%). Melting point: 116-117 ° C / 2 mm Ed.

b) m-fluorosulfonylacetophenone

m-Fluorosulfonylbenzoyl chloride is converted to the corresponding acetophenone, the procedure being mainly in accordance with the process developed by Long and Troutman for the preparation of p-nitroacetophenone (J. Am. Chem. Soc. 71, 2473 [1949]). The product obtained after the hydrolysis of diethyl m-fluorosulfonylbenzoylmalonate is washed with a saturated sodium hydrogen carbonate solution in order to remove approximately 5% of the m-fluorosulfonylbenzoic acid obtained during the hydrolysis. Starting from 52.5 g (0.24 mol) of m-fluorosulfonylbenzoyl chloride. obtained after recrystallization from approximately 350 ml of methanol, 36.8 g (76%) of m-fluorosulfonylacetophenone are obtained. Melting point: 92 ⁰ C.

c) m-fluorosulfonylphenacyl bromide

40.4 g (0.2 mol) of m-Fluorsulfonylacetophenon dissolved in 45 ml of dioxane, is allowed to act at 40 -50 C ⁼ 32 g (0.2 mol) of bromine. The oily bromoketone precipitated by dilution of the reaction mixture with water is collected and 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 the solvent has been removed, the bromine ketone is distilled at 170 ° C./2 mm Hg. The oily product slowly solidifies to a crystalline mass. Melting point: 48-50 ⁰ C. Yield: 3.97 g (78,5o / o).

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

To a solution of 15.2 g (0.2 mol) of thiourea in 40 ml of boiling ethanol is added a solution of 56.2 g (0.2 mol) of m-fluorosulfonylphenacyl bromide in 45 ml of dioxane at such a rate that the The heat released during the reaction is sufficient to keep the reaction mixture boiling (40 - 60 min.). The 2-amino-4- (mfluorosulfonylphenyl) thiazole bromohydrate, which was obtained by cooling the reaction mixture to room temperature, is dissolved at 80-90 ° C. in about 120 ml of water containing about 15% ethylene glycol monomethyl ether, and with sodium hydrogen carbonate neutralized. The formed precipitate is collected, washed with water and dried at 90 ⁰ C. Yield: 29 g (62.5%). Melting point: 154-156 ° C.

The yellow couplers according to the invention are of the diffusion-resistant type, ie they contain oirto r * »- i>or> icr * ho f ^ t-norvia Hi *» ornR crAnncr IQt um ρς in their molecule

^M " ^V WIgUHIJVHV V ~ .f * r * ~, --... _c . _{O o} ,

Layer migration of the coupler molecule from the Colloids Vi, in which it is incorporated to prevent according to another colloid layer.

For the production of a color photographic multilayer material, the diffusion-resistant Color couplers for each color separation image usually in do the composition of the differently sensitized Silver halide emulsion layers embedded. However, the diffusion-resistant color couplers can also are incorporated into the casting compositions of the non-photosensitive colloid layers which are disclosed in n5 water-permeable relationship stand 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 of other colloid layers that are thus more permeable to water To be in a relationship, to be incorporated. For example, the water-soluble color couplers, i.e. H. those, which contain one or more water-solubilizing groups such as a sulfo or carboxyl group (in acid or salt form) from an aqueous solution or the water-insoluble or inadequate water-soluble color couplers from a solution in the suitable water-miscible or non-water-miscible high-boiling or low-boiling organic solvents or mixtures thereof in the coating composition can be incorporated into the layer in question. Thereupon the solution obtained optionally in the presence of a wetting or dispersing agent in a hydrophilic colloid composition dispersed, which represents all or only part of the binder of the colloid layer. In addition, the hydrophilic colloid composition may of course be any other than the colloid Kind of ingredients included. The non-water-soluble color couplers, which fluorosulfonyl groups or contain carboxylic ester groups such as ethoxycarbonyl groups can also be replaced by alkaline Hydrolysis into the corresponding sulfonic acids or carboxylic acids, which in turn become hydrophilic Allow colloid compositions to be incorporated in the form of their alkali salts from aqueous solutions, being transformed.

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 ones Techniques for incorporating color couplers into hydrophilic colloid layers of a photographic Materials can be found in laid-open Dutch patent applications 65 16 423. 65 16 424. 66 00 098, 66 00 099.66 CO 628, in 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 grain emulsions as described in the American Patent 25 92 243 can be used. The color couplers can be used in emulsions, in where latent images are mainly formed on the surface of the silver halide crystal, or in Emulsions in which latent images are formed primarily within the silver halide crystal. > The hydrophilic colloid for dispersing the silver halide can e.g. B. gelatin, colloidal Albumin, zein, casein, a cellulose derivative, a synthetic hydrophilic colloid such as polyvinyl alcohol or Be poly-N-vinylpyrrolidone. If desired, can

κι one 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

i: be sensitized both chemically and optically. she can be chemically sensitized by allowing the ripening in the presence of small amounts of sulfur Compounds such as allyl thiocyanate, allyl thiourea or sodium thiosulfate performs. the

2c emulsions can also be used with the help of. Reducing agents e.g. B. in the French patent 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.

jü These emulsions can also be compounds ; nthalten that sensitize the emulsions by accelerating development, e.g. B. Connections of Polyoxyalkylene type such as alkylene oxide condensation products as described in the American Patents 25 31 832 and 25 33 990, in Oritic patents 9 20 637, 9 40 051, 945 340 and 9 91 608, 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 no font 31 79 520.

The light-sensitive emulsions can also contain all other types of ingredients such as plasticizers. Hardener · wetting agent.
The diffusion-resistant yellow couplers mentioned in this invention are usually incorporated into the blue-sensitive superhalide emulsion layer. According to a conventional method, this over halide emulsion layer is used as the upper coupler-containing layer of a color photographic multilayer

bo materials arranged Such a multilayer material usually contains in the specified Order a cyan coupler-containing red-sensitive super halide emulsion layer, a magenta coupler-containing green-sensitive superhalide mul-

b5 sion layer and a blue-sensitive one containing yellow coupler Over halide emulsion layer Usually, between the blue-sensitive silver halide emulsion layer and the green sensitized silver

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

The emulsions can be applied to any photographic Underlay to be potted. Typical substrates are both films made of cellulose ester. Polyvinyl acetate, 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 substances which have the ability to give azomethine dyes can be used as developing substances. Suitable developer substances are aromatic compounds such as p-phenylenediamine and its derivatives, for example NN-dialkyl-p-phenylenediamines such as Ν, Ν-diethyl-p-phenylenediamine, N ₁ N-dialkyl-N'-sulfomethyl-p-phenylenediamine, 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 is exposed 1/20 seconds through a continuous wedge with a constant 0.30, and developed for 8 minutes at 20 ^° 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

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

Examples 2 -A

In three similar silver bromide iodide emulsions as described in Example 1, the color coupler No. 3 replaced by 0.006 mol of color coupler No. 4, 5 and 7, respectively. After the neutralization and the clogging The emulsions of the usual ingredients are poured and exposed through a continuous gray wedge and processed as described in Example 1.

Yellow wedge images with an absorption factor of 450, 456 or 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 50 cm ^J distilled water are added. The emulsion is acidified with 72 ml of 0.016 η F. acetic acid, whereupon 5 g of color coupler No. 2 of the above list of color couplers according to the invention, 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 couplers are added No. 8 of this same list, dissolved in 15 ml of ethanol, 5 ml of 2 π sodium hydroxide solution and 30 ml of water were 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 used to ^{coat 10 m 2 of} film base which is provided with an antihalation layer, after which 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 developed material is treated for 2 min. At 18-20 ° C in an intermediate bath, consisting of a 3 ^u / o aqueous solution of sodium sulfate. The material is then rinsed with water for 15 minutes and treated in a bleach bath with the following composition:

Borax 20 g

anhydrous potassium bromide 15 g
anhydrous sodium hydrogen sulfate 4.2 g

Potassium hexacyanoferrate (III) 100 g
Water up to 11

After bleaching, the material is rinsed with water for 5 minutes and in a 20% aqueous solution fixed by 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 ε Potassium bromide 2.2 g Sodium bicarbonate 0.55 g Water up to 1 1

The developed material is rinsed for 10-20 seconds, followed by 4 minutes in a fixing bath of the following Composition is treated:

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 11th

The material is then rinsed for 3 minutes, followed by 4 minutes in a bleach bath of the following composition is treated:

water

Potassium hexacyanoferrate (III)

Potassium bromide
Glacial acetic acid
Sodium acetate

900 ml

75 g

15g

10 mi

5g

Kahumalaun
Water up to

15g
1 1

After bleaching, the material is used for 2 minutes Rinsed with water, whereupon it is fixed in the above fixing bath for 4 minutes. After a final rinse the material is dried. A light, transparent yellow wedge image is obtained 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

CH

C-NHCOCH _: CO

H ₃₃ C ₁₆ O

resulting dyes have good heat resistance, moisture resistance and lightfastness, and have high responsiveness during development. d. H. they give color images with high Color density.

To the favorable properties of the invention 2- (o-Alkoxybenzoylaeetamido) thiazole color couplers to be compared with those of the 2- (p-alkoxybenzoylacetamido) thiazole color couplers Tests carried out. For this purpose, after development with p-phenylenediamine sulfate, the Sensitometric characteristics of gelatin silver bromide iodide emulsions (2.3 mol% iodide) 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:

OC ₁₆ H ₃₃

SO ₃ Na

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

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 coupler Sensation opportunity in %

Gradation maximum Absorption density maximum

100
162

1.37
1.41

2.50
2.53

460
445 color coupler

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

The moisture resistance and heat resistance of the development through reaction of the oxidation products Dyes produced by p-phenylenediamine sulfate with the above color couplers is obtained from the Decrease in density of a developed wedge impression determined after an impression was taken at b0 ° C for 24 hours and 100% relative humidity had been stored in the dark.

The results obtained in Ulm are as follows Table listed.

Percentage decrease in density for the following density values

D = 0.5

-66%
-12%

D = 1.0

- 74%
-10%

D = 1.5

- 75%

- 9%

D = 2.0

-77% -11%

j '. To the favorable properties of the invention 2- (o-alkoxybenzoylacetamido) thiazole color couplers with those of the sulfobenzoylacetamido To compare thiazole color couplers of German Patent 12 13 739, experiments were carried out

-, ι. leads.

For this purpose, four silver bromide iodide gelatin emulsions were made (2.3 mol% iodide) produced each emulsion per kg 73.4 g gelatin, a zi 47 g of silver nitrate equivalent amount of silver halogens

■ r, and 0.01 mol of one of the colors indicated below coupler.

Emulsion A: Coupler 3 of DE-PS 12 13 739

Emulsion B: Coupler 7 of DE-PS 12 13 739

with 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 in ² dried and covered with a protective gelatin layer.

After drying the materials thus produced, each material became a test tire

130 230/14

Illuminated for about one second through a gradient wedge with a constant of 0.3 and at 20 ° C in a developer bath of the following composition developed for 8 minutes:

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

Hydroxylamine sulfate 1.2 g

Sodium hexametaphosphate 4.0 g

Anhydrous sodium sulfite 2.0 g

Potassium carbonate anhydrous 75.0 g

Potassium bromide 2.5 g

fill up with water to 1 1

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:

Borax 20 g

Potassium bromide anhydrous 15 g

Sodium bisulfate anhydrous 4.2 g

Potassium hexacyanoferrate (III) 100.0 g

fill up with water to 1 l

After bleaching, the materials are soaked in water for 5 minutes and in an aqueous one Fixed solution of 200 g of sodium thiosulfate per liter. 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 the images had been stored in the dark at 60 ° C and 100% relative humidity for 24 hours.

Tabel

Emul- λ max
sion

% Absorption
blue green

Red

% Decrease in density,

measured at density density 0.5 1.5

ABCD 468
456
450
448

100
100
100
100

-62

-48

-68

-15

-10

Claims (1)

Patent claims: 1. Yellow couplers of the general formula: O —D CO-CH-CO-NH-C in which: X is a hydrogen atom or a group which is customary in color couplers and which is involved in color development can be split off, D a group with 5 to 5 which is customary in color couplers and which makes the molecule diffusion-proof 20 carbon atoms,
Ri is a hydrogen or a halogen atom, an 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-tetrahydrobenzthiazole, 4,5,6,7,8,9-hexahydrocyclooctathiazole. 4H-indeno- [2, l-d] thiazole, 6-methoxybenzothiazole, 5,7-dimethoxycarbonylbenzthiazoI, thiazolo [5,4-b] pyridine, 4,5-diphenylthiazole, 4-j9-naphthylthiazole, 4- (2-thienyl) thiazole, 4-benzyl-5-phenyl-thiazole, 4-ethoxycarbonyl-methyl-5-ethoxycaΓbonylthiazole or 4- (m-Dimethylsulfamoylphenyl) thiazole.