DE1816899A1 - Yellow color coupler - Google Patents

Description

Λ "G FA-GEVAERT AG LEVERKUSEN

Yellow color coupler

Priority: Great Britain, January 5, 1968 Nr = 854/68

This invention relates to the production of color photographic images, the yellow color couplers used therein and the photographic materials containing such color couplers.

It is known to produce a photographic color image in a photosensitive silver halide emulsion layer the exposed silver halide is developed into a silver image by means of a primary aromatic amino compound in the presence of a color coupler, which coincides with the oxidized developer substance on the one with the silver image Places to form a dye reacts "

In subtractive three-color photography becomes a photographic one color light-sensitive material which is red-sensitized, green-sensitized and blue-sensitive Silver halide emulsion layer contains, in which the color development through the use of suitable color couplers a blue-green, a purple or a yellow dye image to be generated »

Fundamental difficulties encountered in color photography relate to light fastness and heat resistance and the moisture resistance of those representing the image Dyes. Although color photography has been growing ever since its use of color couplers for the production of color images has been thoroughly perfected, efforts are still being made to produce dyes with better stability to find.

909831/1533

A-G 456

There have now become new benzoylacetamide type photographic color couplers found the yellow dyes on coupling with the oxidized aromatic primary amino developing agent and correspond to the following general formula : ■

0-D

I ί
r ^ v, -COCHCONH-C *

_R - j - Π Ii?

in which:

X is a hydrogen atom or a group which is split off during color development, e.g. a halogen atom, a -SR group in which R is an alkyl group, a substituted ^w alkyl group; an aryl group, or a substituted aryl group,

D a group which makes the molecule diffusion-proof, see B. one acyclic aliphatic hydrocarbon group with 5 to 20 carbon atoms,

F- a hydrogen atom, an alk / I group such as a methyl group, an alkoxy group such as a metr.oxy or decyloxy group, a halogen atom such as a chlorine atom, a dialkyiamino group such as a dimethylamino group or a sulfamoyl group such as a diethylsulfamoyl group, and

Z the atoms necessary to close a ring of the thiazole. Series like thiazole, 4 ~ methyl thiazole, 4-tert ..- butyl thiazole, 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-ethoxycarbonylthiazole, 5-carboxythiazole, 4,5-diethoxycarbonylthiazole, 4-phenyl-5-ethoxycarbonylthiazole, 4-phenyl-5-carboxymethylthiazole, 2-amino-4- {«-, ethoxycarbonylpentyD-thiazole, 4-carboxy-5-phenyl thiazole, 4- (o-. Carboxyphenyl) thiazole, 4,5,6,7-Tetrahydrobenztfeiazole, 4, 5, 6, 7,8, 9-Hexahydrocyclooc ta thiazole, 4H-Indeno (2, 1-d) ■ - ,, thiazole, 6-methoxybenzthiazole, 5, -7-DiTnethoxyGarbo.ri.ylben ^ -? _. thiazole, Thiazolo (5, 4-b) pyridine, 4, 5-diphenyl thir.zol,

809831/1533

BATH ORIGINAL

4 - / ^ - naphthylthiazole, 4- (2 '-thienyl) -thiazole, 4-benzyl-S-phenylttiiazole, 4-ethoxycarbonylmethyl-5-ai; hoxycarbonylthiazole, 4- (m-Dimethylsulfamoylphenyl) - thiazole, etc. where Z is the atoms necessary to close a Thiazole ring means an alkyl-substituted, aryl-substituted or aralkyl-substituted thiazole ring, their alkyl, aryl or aralkyl groups are further substituted may be a thiazole ring which is substituted by an optionally substituted heterocycle, one Thiazole ring with a dialkylamino, sulfamoyl, substituted sulfamoyl, alkoxycarbonyl, fluorosulfonyl or water-solubilizing group such as a SuIfo- or Carboxyl group can be substituted in acid or salt form, and a thiazole ring with fused aliphatic, aromatic or heterocyclic ring systems, which can also be further substituted.

The Yellow Kuepers are very heat and moisture resistant, and have the yellow azomethine dye images produced therewith not only favorable spectral properties and excellent lightfastness, but also an extraordinary one high resistance may be more significant 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 quite puzzling because it is common knowledge among other things through the "publications of the scientific t-hotol'aboratorien Wolfen "Volume X (1965) p.299, S.Hirzel Verlag, Leipzig, GDR, and from the American patent specification 2,728,658 that an ortho substitution, especially one o-alkoxy substitution on the benzoyl part of the benzoylacetarylide color coupler, reduces the coupling ability of the coupler and reduces the coloring power of the dye obtained. It it turns out that in the case of the invention 2-Benzoylacetamidothiazole color coupler an ortho substitution

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does not reduce the coupling ability of the coupler molecule.

The preparation of the yellow color couplers according to the above general The formula can be represented by the following reaction scheme:

N / A

CH COCHCOOR

^R i

COCH,

-D

-CO-CH-COOR
0-D

riaOCH.

CH OH

\\ - CO-CH ₂ -COOR 0-D

-COCH ₂ COOR +

0-D
in the

! ' Il

N S-

R,

R.

-COCH ₂ CONH-J, -0-DI

R _-1 , R _? , R- and D have the same meaning as above, and R represents a lower alkyl group such as methyl and ethyl group.

Benzoylacetamide color couplers falling under the above general Formula I are u "3", the compounds with the following Formulas:

HC C-NHCOCH ₀ CO-.

Il Il 2

A -xN._r Μ C -H 0-1

Ης C-NHCOCH ₂ CO-

HC-N

^ C

HC ^ C-Il Π

HOOC-C .N

WHCOCH-CO-2

909831/153

5, S _p

C ₀ H ₁ -OOC-C ₁ C-NHCOCH, 2 5 || ||

HC N CH.

-C C-NHCOCH ₀ CO- ² II II

C ₀ H ₁ -OOC-C C -C -NHCOCH, ■ 2 5 |, µ

HC C-NHCOCH ₂ CO-

SO ₃ Na

9ο HC C-NHCOCH ₀ CO-

| T Il 2

<p

-C

S.
^^ C

j. HC ^ C-MHCOCH ₀ CO-

COOH

HC

C-UHCOCH ₂ CO l! C ₁₆ H ₃₃ O

CH

-SO ₂ MC CH ₃

HC C-N "HC0CH_C0- | i 2

13. (CH) NSO

NSO
j HC

HC C ₁ -NHCOCH ₀ CO

π 11 -

-Cl

CH ₃ O-,

: -nhcoch ₀ ' ²

9 09831/1533

C-MHCOCH ₀ CO-M ²

^C 16 ^H 33

to

HC CI ¹ HCOCHCO-II H

-CN C. _r H - 0-

16 33

HC C-NHCOCH ₀ CO-O
H Ii 2 j

NHCOCH-CO-,

^NC l0 ^H 21 ° -k ^ - ° ^C i0 ^H 21 The following production examples explain the invention »

Establishing \ _ : connection 1

α) o-Dodecyloxybenzoyl acetic acid methyl ester

153 g (0.5 mol) of o-dodecyloxybenzoic acid, prepared as described in J "Am" ChenuSoc "<oA_ (1942) 1961, and 109 ml of thionyl chloride are refluxed for 3 hours. The excess thionyl chloride is evaporated and it remains light brown oily residue back »·

The oily residue is stirred into a suspension of 152 g (1 mol) of the sodium salt of ethyl acetate added in 250 ml of dichloromethane »Stirring is continued for 3 hours, whereupon the reaction mixture with 500 ml of dilute hydrochloric acid is treated = The Dichloromethane layer is mixed with water until it is acid free washed, dried over magnesium sulfate and concentrated »The oily residue is 3 hours in a vacuum of 2-5 mm Hq kept at 100 ° C to the ethyl acetate to remove..

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The oil is stirred into a solution of 30 g of sodium methylate added 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.Äm.Chem.Soc. SJ (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 mol) of 2-amino-4-phenylthiazole and 0.2 g of sodium acetate and xylene is heated to 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, and 200 ml of hexane are added to the oily residue. The mixture is then left to cool while stirring The precipitate formed is recrystallized from acetonitrile., Melting point: 68-69 ° C.

Manufacture 2 : Connection 4

a) o-Hexadecyloxybenzoyl acetic acid methyl ester

This compound is made in an analogous manner to that of the preparation example la) synthesized, but starting from 0.5 mol of o-hexadecyloxybenzoic acid, the series according to the method of Stanton and coworkers, J. Am.Chem.SoCo (54_ (1942) 1961. Melting point: 53-54 ° C.

b) 2-Amino-4-carbäthoxy_thiazol is prepared as described in J.Am.Chem.Soc. £ 6 (1946) 268.

c) 2- (o-HexadecYlox ^ benzo ^ lacet ^ lamino) -4-carbäthox ^ thiazole is prepared in a manner analogous to that described in preparation example Ic), but using 0.1 mol

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o-Hexadecyloxybenzoyl acetic acid methyl ester and 0.1 mol 2-Amino-4-carbathoxythiazole goes out. A light yellow viscous oil is obtained.

d) 2- (o-Hexadecyloxybenzoylacety_lamino) -4-carboxy thiazole

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 ^° C.

Preparation 3 : Compound 8

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

This compound is prepared in an analogous manner to the compound described in Preparation Example 1, except that 0.1 mol of methyl o-hexadecyloxybenzoyl acetic acid (see Preparation Example 2a) and 0.1 mol of 2-amino-4- (m-fluorosulfonylphenyl) thiazole are prepared as described below. A white crystalline product is obtained. Melting point: 108 ⁰ C.

b) 2- (o-Hexadecyloxybenzoylacety_lamino) -4-ϋτι-sulf ogheny ^ l) ^ thiazole

0.1 mol of the above fluorosulphonyl compound is in 400 ml Acetone heated until the reflux temperature is reached. 60 ml of 5% aqueous sodium hydroxide are slowly added with stirring to, whereupon the mixture 30 min. Under reflux cooling is heated. This mixture is then acidified with an excess of sulfuric acid so that the free Sulfonic acid precipitates.

; ^ ll_u_ng des 2- amine o-4 - (mf luor sulpho ny 1 phenyl) -thiazoles a) m-fluorosulphonylbenzoyl chloride

20.4 g (0.1 mole) of m-fluorosulphonylbenzoic acid by reaction of m-chlorosulphonylbenzoic acid with potassium

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fluoride in aqueous dioxane medium, one leaves with a Excess (0.45 mol) thionyl chloride react. Yield: 21.3 g (96%). Melting point: 116-117 ° C / 2 mmHg.

b) m-fluorosulphonylacetophenone

m-Fluorosulphonylbenzoyl chloride becomes the matched Acetophenone converted, mainly according to the process developed by Long and Troutman for the preparation of p-nitroacetophenone (J. Am. Chem. Soc. 7Jl, 2473 (1949)) process v / ird = that after hydrolysis of diethyl m-fluorosulphonylbenzoylmalonate The product obtained is treated with a saturated sodium hydrogen carbonate solution washed to remove about 5% of the hydrolysis m-fluorosulphonylbenzoic acid »starting of 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 ° C "

c) m-On Fluorsulphonylphenacylbromid 40 A _r g (0.2 mol) of m-Fluorsulfonylacetofenon dissolved in 45 ml of dioxane, is allowed at 40-5O ⁰ C 32 g (0.2 mol) of bromine act by the dilution of the reaction mixture Oily bromoketone precipitated 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 bromoketone is distilled at 170 ° C./2 mm Hg * The oily product slowly solidifies to a crystalline mass. Melting point: 48-5O ° C. Yield: 3.97 g (78.5%).

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

To a solution of 15.2 g (0.2 mol) thiourea in 40 ml A solution of 56.2 g (0.2 mol) is added to boiling ethanol

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m-Fluorosulfonylfenacyl bromide in 45 ml of dioxane increases at such a rate that the heat released during the reaction is sufficient to keep the reaction mixture boiling (40-60 min.). The 2-amino-4- (m-fluorosulfonylphenyD-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 neutralized with sodium hydrogen carbonate, the precipitate formed 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 resistant to diffusion Type, i.e. they contain an organic group in their molecule that is large enough to prevent migration of the coupler molecule from the colloid layer in which it is incorporated to another colloid layer.

For the production of a multilayer color photographic material are the diffusion-resistant color couplers for each color separation image usually in the composition of the differently sensitized silver halide emulsion layers stored. The diffusion-resistant dye couplers but can also be incorporated into the coating compositions "of the non-photosensitive colloid layers which are in a water-permeable relationship with the light-sensitive silver halide emulsion layers, for example in layers which are in direct contact with the light-sensitive layers, or from these light-sensitive layers through water-permeable, non-photosensitive layers are separated.

In the manufacture of the color light-sensitive material can the diffusion-resistant yellow couplers according to the above more generally Formula according to some known technique into the

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The coating composition of the silver halide emulsion layers or of other colloid layers, which are thus more permeable to water To be in a relationship, to be incorporated. For example The water-soluble color couplers, i.e. those which contain one or more water-solubilizing groups, can be used such as a sulfo or carboxyl group Cin acidic or Salt form) from an aqueous solution or the non-water-soluble or insufficiently 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 into the Casting composition can be incorporated into the layer in question. The solution obtained is then optionally dispersed in the presence of a wetting or dispersing agent in a hydrophilic colloid composition which represents all or 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 water-insoluble color couplers, which fluorosulfonyl groups or containing carboxylic ester groups such as ethoxycarbonyl groups can also be converted into the matching sulfonic acids or carboxylic acids, which are sequentially in hydrophilic colloid compositions incorporate in the form of their alkali salts from aqueous solutions let be converted.

The solution of the color coupler does not need to go directly into the Coating composition of the silver halide emulsion layer or another water-permeable layer to be dispersed or dissolved. This solution can be advantageous first in an aqueous non-photosensitive Solution of a hydrophilic. Colloids are dispersed or dissolved, whereupon the mixture obtained after the eventual , Removal of the organic solvents used with this coating composition of the photosensitive Silver halide emulsion layer or the other

909831/153 3

water-permeable layer just before application is mixed. More information about particularly suitable techniques for incorporating color couplers into hydrophilic ones Colloid layers of a photographic material are found in the laid-open Dutch patent applications 6516423, 6516424, 6600098, 6600099, 6600628, in Belgian patent specification 705,389, in American patent specification 2 304 940, in British Patent 791 219.

The inventive couplers can be used together with use various types of photographic emulsions. Various silver salts can be used as sensitive salts used such as silver bromide, silver iodide, silver ™ chloride or mixed silver halides such as silver chloride bromide, Silver bromide iodide and silver chlorobromide iodide. The couplers can be used in drop emulsions as described in US Pat. No. 2,698,794 or in mixed grain emulsions as described in US Pat. No. 2,592,243. The color couplers can be used in emulsions in which latent images are mainly on the surface of the silver halide crystal or in emulsions in which latent images are mainly within the silver halide crystal are formed.

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

The light-sensitive silver halide emulsions for the preparation of a photographic one of the present invention Materials can be sensitized both chemically and optically. They can be chemically sensitized by allowing the ripening in the presence of small amounts

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sulfur-containing compounds such as allyl thiocyanate, allyl thiourea, Sodium thiosulfate, etc. performs. the Emulsions can also be produced with the aid of reducing agents e.g. those in French patent specification 1,146,955 and in tin compounds described in Belgian patent 56-8 687, the aminoaminomethanesulfinic acid compounds described in British Patent 769,823 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 can also contain compounds that sensitize the emulsions by accelerating development, e.g., compounds of the polyoxyalkylene type such as alkylene oxide condensation products as described, inter alia, in U.S. Patents 2,531,832 and 2,533,990, in British Patents 920,637, 940 051, 945 340 and 991 608, and in Belgian patent specification 648 710, and onium derivatives of amino-N-oxides as described in laid-open publication Dutch patent application 6612269.

The emulsion can also contain stabilizers, for example heterocyclic nitrogen-containing thioxo compounds such as benzthiazoline-2-thione and l-phenyl-2-tetrazoline-5-thione and "oxytriazolopyrimidine-type compounds". They can also be stabilized with mercury compounds such as those described in US Pat Belgian patents 524 121 and 677 337, the open ^ - laid down Dutch patent application 6715932 and in American patent specification 3,179,520.

The photosensitive emulsions can also be any other Types of ingredients included such as plasticizers, hardeners, wetting agents, etc.

909831/1533

The diffusion-resistant yellow couplers described in this invention are usually incorporated into the blue-sensitive silver halide emulsion layer. After a The usual method is this silver halide emulsion layer as the upper coupler-containing layer of a color photographic Multilayer material arranged »Such a multilayer material usually contains in the specified Sequence a red-sensitized one containing blue-green coupler Silver halide emulsion layer, a magenta coupler-containing one green-sensitive silver halide emulsion layer and a blue-sensitive one containing yellow coupler Silver halide emulsion layer. Usually between the blue-sensitive silver halide emulsion layer and the green-sensitized silver halide emulsion layer has a yellow filter layer arranged generally in Gelatin contains dispersed colloidal silver »

The emulsions can be applied to any photographic Base to be potted = Typical bases are films made of cellulose ester, polyvinyl acetate, polystyrene, Polyethylene terephthalate, and similar resinous material, as well as paper and glass =

For the production of photographic color images according to the invention, an exposed silver halide emulsion layer with an aromatic primary amino developing agent is developed in the presence of a color coupler according to the invention 'Nylenediamine and its derivatives, for example Γ', Ν-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, Ν, Ν-dialkyl-N ¹ -sulfomethyl-p-phenylenediamines, and N, N-dialkyl N ¹ -carboxymethyl-p-phenylenediamine.

909831/1533

The following examples explain the invention

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, add 0.006 mol of color coupler No. 3 of the above list to "After neutralization and addition 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 at a rate of 150 g per m2. The emulsion layer is then dried and coated with a protective gelatin layer.

After drying, the material is exposed for 1/20 sec. Through a continuous wedge with a constant 0.30, and developed for min. At 20 ^° C. in a developing bath of the following composition:

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

Sodium hexametaphosphate. 4g

anhydrous sodium sulfite 2 g

anhydrous potassium carbonate .75 g potassium bromide 2.5 g

Water up to 1 1

The developed material is 2 min. At 18-2O ° C in one Treated intermediate bath consisting of a 3% aqueous Solution consists of sodium sulfate. Then the material Rinsed with water for 15 minutes and treated in a bleach bath with the following composition:

borax

anhydrous potassium bromide

anhydrous sodium hydrogen sulfate potassium cyanoferrate (III)

Water up to ₉₀ 9831/1533

20th G 15th G 4.2 G 100 G 1 1

After bleaching, the material is rinsed with water for 5 min and in a 20% aqueous solution of sodium thiosulfate fixed »After a final 15 minute rinse, the material is dried» A yellow wedge image is obtained with an absorption maximum at 452 nrtu

Examples 2-4

In three similar silver bromide iodide emulsions as described in Example 1, the color coupler No. 3 is through 0.006 mol of color coupler Mr. 4, 5 or 7 replaced. After neutralizing and adding the usual ingredients the emulsions are cast, exposed through a continuous gray wedge and as described in Example 1 processed «.

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 50 cm3 of distilled water are added. The emulsion is acidified with 72 ml of 0.016 η 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 coupler No. 8 of this same list, dissolved in 15 ml of ethanol, 5 ml of 2 η sodium hydroxide solution and 30 ml of water are 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 m2 of film base, which is provided with an antihalation layer, and the material is then dried. After exposure by a. Gray wedge, the material is developed for 8 minutes at 20 ^° C. in a color developer with the following composition:

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181 6899 900 ml 1 G 4th G 2 , 7 g 25th G 2 , 2 g 0 , 55 g 1 1

water

Sodium hexametaphosphate

anhydrous sodium sulfite

N, N-diethyl-p-phenylenediamine chlorohydrate anhydrous sodium carbonate

Potassium bromide

Sodium bicarbonate

Water up to

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

Water 800 ml

anhydrous sodium thiosulfate 200 g

Sodium hydrogen sulfite 12 g

Glacial acetic acid 12 ml

Borax 20 g

Potassium alum - 15 g

Water up to 11

The material is then rinsed for 3 minutes, whereupon it is 4 minutes in treated with a bleach bath of the following composition: water 900 ml

Potassium cyanoferrate (III) 75 g

. Potassium bromide - 15 g

Glacial acetic acid 10 ml

Sodium acetate 5 g

Potassium alum 15 g

Water up to 11

After bleaching, the material is rinsed with water for 2 minutes, whereupon it is fixed in the above fixer bath for 4 minutes The material is dried in a final rinse. A light, transparent yellow wedge image is obtained an absorption maximum at 439 nm "

9 0 9 8 31/15 3 3

The yellow couplers according to the invention generate during color development with aromatic primary amines such as p-phenylenediamine yellow dyes, which are characterized by their favorable light absorption in the blue region of the spectrum and characterized by their slight absorption in the other areas, moreover, they have in color development resulting dyes have good heat resistance, moisture resistance and lightfastness, and have high reactivity during development, that is, they result in color images with high color density »

In order to compare the favorable properties of the 2- (o-alkoxybenzoylacetamido) ~ thiazole color couplers according to the invention with those of the corresponding 2- (p- ^ lkoxybenzoylacetamido) -thiazole color couplers, experiments were carried out. Phenylenediamine sulphate determines the sensitometric characteristics of silver bromide iodide gelatine emulsions (2.3 mol% iodide) which contain 73.4 g gelatine per kg, an amount of silver halide equivalent to 47 g silver nitrate and a color coupler A of the following formula:

HC C-NHCOCH ₀ CO-

»Τ ²

C C -NHCOCH ₀

if »τ ²

SO ₃ Ma
or a color coupler B of the formula according to the invention

HC C-NHCOCH ₀ CO-

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 of 2 η sodium hydroxide were incorporated.

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BATH ORIGINAL

The sensitometric results are in the following table listed:

Color Relative gradation maximum Absorption coupler Sensation Density maximum in nm opportunity in % A. 100 1.37 • 2.50 460 B. 162 1.41 2.53 445

From the maximum density values it can be seen that the Coupling ability of 2- (o-Alkoxybenoylacetamido) -thiazole ~ Color coupler v / id is not expected to be lower than that of the corresponding p-alkoxy derivatives * In addition, it is the sensitivity achieved is significantly higher than that obtained with the corresponding p-alkoxy color couplers »

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

The results obtained are shown in the following table.

Color
coupler Percentage decrease in density in the fol
low density values D = 1.0 D = 1.5 D = 2.0 A.
B. D = 0.5 -74 %
-10% -75%
- 9% -77%
-11% -66 %
-12%

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BAD ORIQfNAL

Claims (1)

Claims 1. A color coupler which has the ability to react with an oxidized aromatic primary amino developing agent to form a yellow azomethine dye ^2U , which corresponds to the following formula: 0-D i f ■> -CO-CH-CO-NH-C Il .11 ^z in which: X is a hydrogen atom or a group in the Color development can be split off, D is a group making the molecule diffusion-proofing I.
5 to 20 carbon atoms, R ^ a hydrogen or a halogen atom, an alkyl, Alkoxy, dialkylamino or sulfamoyl group, and Z the atoms necessary to close a thiazole ring. 2. Color coupler according to claim 1, characterized in that Z contains the atoms necessary to close a thiazole ring, a substituted thiazole ring, one with an aliphatic, aromatic or heterocyclic ring represents fused thiazole ring or such a substituted thiazole ring system. 3. Color coupler according to claim 1, characterized in that Z has the necessary atoms -to close a thiazole ring, one substituted with alkyl or substituted alkyl Thiazole ring, a thiazole ring substituted with aryl or substituted aryl, one with aralkyl or substituted aralkyl substituted thiazole ring, a thiazole ring substituted by a heterocycle or a substituted heterocycle, a thiazole ring, the one with a dialkylamino, sulfamoyl, 909831/1533 substituted SuIfamoyt ^ AUcoxycarbonyl, fluorosulfonyl, Sulfo or carboxyl group is substituted, the two latter groups can be present in acid or salt form. 4 * Photographic material containing at least one color coupler according to any of the preceding claims contains » ο Multilayer color photographic material that is packaged in one the photosensitive silver halide emulsion layers or in a non-photosensitive water-permeable colloid layer in water-permeable relationship with a light-sensitive silver halide emulsion layer at least a color coupler according to one of claims .1 to 3 contains .. 6 "Multilayer color photographic material containing three silver halide emulsion layers which are various are optically sensitized, the blue-sensitive Silver halide emulsion layer or an adjacent non-photosensitive water-permeable colloid layer contains at least one color coupler according to one of claims 1 to 3 « 7. Process for the production of a photographic color image by developing a photographic, imagewise exposed silver halide-containing material with the aid of a developer substance, which by reduction of the exposed silver halide is converted to its oxidized form and, as such, is yellow Azomethine dye by reaction with at least one A color coupler according to any one of claims 1 to 3, wherein the color coupler is in a blue-sensitive one Silver halide emulsion layer or in another colloid layer of this photographic material in water-permeable relationship with the former layer- 909831/153 3