DE1547730A1 - Use of color couplers to develop color photographic material - Google Patents

Description

Eastman Kodak Company, 343 State Street, Rochester, State of .New York, United States of America

Use of color couplers to develop color photographic material

The generation of color images on phot ο graphic VJegü is known to be based on the imagewise coupling of the oxidation products of primary, aromatic amines existing developer compounds with so-called color couplers, with indoaniline, indophenol and azomethine dyes are formed. In the case of the dye images formed by the so-called subtractive color formation process these are usually cyan, magenta and yellow dye images, i.e. images of such colors which are complementary to the primary colors red, green and blue. Normalerweis® are so-called, phenolic or naphtholic couplers for the formation of the blue-green dye images, pyrazolone couplers or cyanoacetyl derivatives

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to produce the magenta dye images and acylacetamide couplers used to produce the yellow dye images.

The color couplers can either be used in the developer solutions or in the light-sensitive ones Emulsion layers of the color photographic material are incorporated so that they can be used during the development process can react with the oxidation product of the color developer compound. In dye developer solutions, diffusing Couplers and non-diffusing couplers used in photographic emulsion layers.

The majority of the couplers known to date consist of so-called 4-equivalent couplers, ie the reduction of ² l moles of silver halide is required to form one mole of the dye.

However, so-called 2-equivalent couplers have also become known, i.e. color couplers which lead to the formation of 1 mole of dye only require the reduction of 2 moles of silver halide. However, it has been shown that the previously known so-called 2-equivalent couplers have various disadvantages. For example, it has been shown that the well-known 2-Kqui • Valentine couplers are generally only weakly reactive,

BATH ORIGINAL

tend to form color haze and enter into other undesirable side reactions.

The invention was therefore based on the object of new 2-equiva-. To develop lent color couplers, the disadvantages of the previously not have known 2-equivalent color couplers

The invention was based on the surprising finding that 2-equivalent color couplers of the desired beneficial properties can be obtained if, in 2-equivalent color couplers, the at least one iJ-hydroxy-3-carbamyl-l-naphthyl group, in the 1-position of the naphthyl ring the Hydrogen atom replaced by an aryloxy group.

Accordingly, the invention relates to the use of color couplers which contain at least one II-hydroxy-S-carbamyl-inaphthyl group, in which the hydrogen atom in the! position of the naphthyl ring is replaced by an aryloxy group, for the production of dyes by coupling with the oxidation product of an aromatic amine Developer compound in the development of color photographic material.

It has been found that the color couplers used according to the invention not only have a satisfactory reactivity, but also a greatly reduced tendency towards color fogging in the non-image districts. Her

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The tendency to enter into negative reactions is considerable

the
lower than the / known 2-equivalent color couplers, which is why the pigment yield is particularly high when they are used. By using the new color couplers in the development of color photographic material, blue-green dye images of excellent quality can be obtained.

Color couplers which can be used according to the invention can also be passed through the following formula I:

ΚΟ (η = 1 or 2)

represent where R is Jl-hydroxy-S-carbamyl-1-naphthyl and R represents an aryl or arylene group, i.e. a divalent aromatic organic group.

In the given formula I, R and R can be represented by the most varied Substituönten be substituted. By introducing various substituents into the groups R and R the most diverse properties of the color couplers can be influenced, for example the spectral absorption, the reactivity, the solubility of the color coupler molecule and the like. It has been found that the effectiveness of the new 2-equivalent color couplers from the introduction of special Substituents in the radicals R and R is independent.

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ORIGINAL,

Color couplers which can be used according to the invention can also be used represented by the following formula II:

ID

CON

R ² and

where mean:

η = 1 or 2

3 hydrogen atoms, alkyl, aryl or heterocyclic Radicals or together the atoms required to complete a heterocyclic ring and an aryl radical when η = 1 or an arylene radical when η = 2 1st.

If R ² and R- * are alkyl radicals, then these can be straight-chain or branched and preferably have 1 to 30 carbon atoms. The alkyl radicals can, however, ^j

2 ^and λ i can also be mono- or bicyclic in nature, d # h. R % »&. R ^J can also have the meaning of, for example, cycloalkyl groups, such as, for example, cyclohexyl groups, or of ten penyl groups, for example norbornyl groups. Own R *. and R ³ the meaning of aryl radicals, so these can be atapiel *

00ÖI16 / 1S52

^BA0

t '1 * - -Vl t-

■■> ■■ - ^

-D-

wise consist of phenyl or naphthyl residues. Examples of heterocyclic radicals that may be mentioned are benzimidazolyl and benzothiazolyl radicals. If R and R- ^{5 have} the meanings required to complete a heterocyclic ring

2 λ

borrowed atoms, the ^{ring formed by R and R J} can consist, for example, of a morpholine or pyridine ring. The alkyl, aryl or heterocyclic radicals represented by R and R ^J can be substituted by a wide variety of substituents, for example by halogen atoms or nitro, hydroxyl or carboxyl groups (such that the coupler molecule has ballast groups with at least 12 carbon atoms or one equivalent in one contains non-coupling position) or amino groups substituted by amino groups, aryl groups, for example alkylamino, dialkylamino, anilino or N-alkylanilino groups, carboxy! ester groups, for example carboalkoxy or carboaryloxy groups, amido groups, for example acetamido, butyramido, ethyl sulfonamido -Methylbenzamido, N-propylbenzamido or 4-t-butylbenzamido groups or carbamido groups, for example carbarayl, N-octadecylcarbarayl, Ν, Ν-dihexylcarbamyl, N-methyl-N-phenylcarbamyl or 3-pentadecylphenylcarbamyl groups, Sulphamyl groups (such that the Parbkupplermolekül ballast groups with at least 12 carbon atoms men or one. Contains equivalent in the non-coupling position), for example N-propylsulfamyl or N-tolyleulfamyl groups, alkoxy groups, various ethoxy or ootadecoxy groups, aryl groups

009-16 / 18S2 I.

BAD ORIGINAL ",

· «; t'i

15V / V3Ü

oxy groups, for example phenoxy, tolyloxy or naphthyl oxy groups, sulfo groups, such that the color coupler molecule Balllast groups containing at least 12 carbon atoms or an equivalent in the non-coupling position, substituted Sulfonyl groups, for example methylsulfonyl, octad

Dccyl
cylsulfonylethoxysulfonyl-, KMKoxysulfonyl-, phenylsulfonyl · ·,

Tolylsulfonyl or phenoxysulfonyl groups and the like.

H
If R has the meaning of an aryl radical, if η - 1,

Ä
for example, R can be a phenyl, naphthyl, Py

η
ricyl or quinolyl radical. If R has the meaning of an arylene radical when η = 2, then R can be, for example, a 1,2-phenylene-; 1,3-phenylene-; 1,4-phenylene-; 1,5-naphthylene-; 2,5-pyridylene-; Ethylene bis (l, i | -phenylene) -; 4, Ii-Di-phenylenesulfonrest.and the like.

The aryl and arylene groups represented by R can furthermore be substituted, for example by halogen atoms or nitro, hydroxyl, carboxyl, optionally substituted amino, car oxy le st ^ amido, carbamyl, sulfamyl, Alkoxy, aryloxy, sulfonyl or sulfonyl groups, as described as substituents for the alkyl, aryl and heterocyclic radicals formed ^{by R and R J.}

It
Furthermore, the aryl and Arj?

len groups by phenylazo and substituted phenylazo groups be substituted.

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The excellent properties of the color couplers used according to the invention are based on the aryloxy group in coupling position of the color coupler molecule

The new color couplers used according to the invention leave easily work into emulsion layers without the use of high boiling coupler solvents. Become the When dispersing the color coupler high-boiling color coupler solvents are used, the most varied of ratios can be used can be used from color coupler to solvent without producing color fog and reducing the dye yield. The color couplers used according to the invention can be use with equally favorable effects in photographic emulsion layers, such as color developer solutions.

In the following, some particularly advantageous ones are described according to the invention usable new 2-equivalent color couplers specified:

Coupler 1 - 1-Hydro Xy- ¹ JC 4-methylsulfonylphenoxy) -2-naphth-

amide;
Coupler 2 - l-Hydroxy-i | - {* J ~ [o- (3-pentadecylphenoxy) butyramidq] -phenoxy} -N-octadecyl-3 ', 5'-dicarboxy-2-naphth-anilide of the formula:

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OH

COOH

COOH

NHCOCHO

Coupler 3 - l-hydroxy-4- (4-nitrophenoxy) -N- [] s- (2 _> ¹ -di-t-amylphenoxy) butyl] -2-naphthamide of the formula:

OH

CONH (CH

Coupler * l

Coupler 5 coupler 6

l-Hydroxy-4- (2 ₄ 4-dinitrophenoxy) -N-ethyl-2-naphthamidj

1-hydroxy-4-phenoxy-2'-methoxy-2-nap.hthanilide; l-Hydroxy-4- (lJ-nltrophenoxy) -N- (β-phenylethyl) -2-naphthamide the formula:

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CONHCH ₂ CH ₂ C ₆ H

Coupler 7 - l-Hydroxy-4- (4-acetaidüophenoxy) -N-Q- (2-acet-

amidopheny1) äthy Γ] -2-naphthamide;

penta
Coupler 8 - l-hydroxy-4- (tarxafluorophenoxy) -N- {ß- {4- [a- (2,4- ·

di-t-amylphenoxy) acetamido] phenyl} ethy1} -2-naphth-

amide;
Coupler 9 - l-hydroxy-4- (1-naphthyloxy) -N, N-dioctyl-2-naphth-

amide;
Coupler 10- l-hydroxy-4- (4-pyridyloxy) -4 '- (4-t-butylphenoxy) -

2-naphthanilide; i

Coupler 11-1-hydroxy-4- (4-chlorophenoxy) -2'-tetradecyloxy-2 ^ j

i naphthanilide; ]

Coupler 12- l-Hydroxy-4- Ql- (N-methy1-N-propylsulfamyl) -phen-

oxjT) -N-octadecyl-3 '»5'-dicarboxy-2-naphthanilide; j

Coupler 13-1-Hydroxy-4 - [} 1- (4-hydroxyphenylsulfonyl) phenoxy] 3 ^f - [p- (3-pentadecylphenoxy) butyramidq] -2-naphthanilide; ;

Coupler 14 l-Hydroxy-4- (4-nitro-3-pentadecylphenoxy) -N-octadecyl-4 -sulfo ^{t-2-naphthanilide,} sodium salt; .

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-.11 -

Coupler 15-1-hydroxy-4- (3-nitrophenoxy) -N-octadecyl-3 ', 5'-dicarboxy-2-naphthanilide; , .. ';,

Coupler 16 - l-IIydroxy-4-phenoxy-N- {e- {4- £ 2- (2,4-di-t-amylphene

oxy) -5- (3,5-disulfobenzamido) benzamido] -phenylJ-ethyl} -2-naphthamide _< -Disodium salt-der-Pormeli-_

SP ₃ Na

OH'

CONHCH ₂ CH ₂ γ

NHCO

Coupler 17-1-Hydroxy- ^ - Ql-Cil-BulfophenylazoOphenyloxy] ^-1 } ¹ - (. 4-t-butylphenoxy) -2-naphthaneIlide, sodium salt;

Coupler 18 - 1-Hydroxy-4- (4-sulfophenoxy) -N-octadecyl-2-naphtharnide, sodium salt; -: *

Coupler 19 - l-IIydroxy-4-phenoxy-2-naphthomoΓpholide of the formula j

- CH ρ - CH
CON "0

CH ₂ - CH ₂

0-C ₆ H ₅

Coupler 20 - l-Hydroxy-4- (i | -nItrophenoxy) -N-cyclohexyl-2 naphthatnidj

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copy

Coupler 21-4, ¹ I'-bis 13-hydroxy-3- (N-ethylcarbamyl) -l-naphthyl. ox £ 3diphenyl sulfone of the formula:

CONHC ₀ H ₁

CONHC ₂ H ₅

Coupler 23
Coupler 2 ¹ J

Coupler 22-1, ¹ J-BIs {Jl-hydroxy-3- [N- (2-acetamidophenyl) carb "amyl] -1-naphthyloxy-benzene;

l-Hydroxy-4- (4-sulfophenoxy) -N-methyl-2-naphthanide, Sodium salt;

l-Hydroxy - ^ - C ^ -acetamlclophenoxyJ-H-octadecyl-3 ¹ , 5'-dicarboxy-2-naphthanllld of the formula:

COOH

COOH

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NHCOCH.

Coupler 25 - l-Hydroxy-4- (4-nitrophenoxy) -N-octadecyl-3 ♦ »5 ¹ -disulfo-2-naphthanilide, disodium salt j

Coupler 26-1-hydroxy-4-phenoxy-N- (2-benzimidazolyl) -2-naphthamide; !

Coupler 27 - l-Hydroxy-i | - (4-nitrophenoxy) -N-methyl-N-ethyl- \

2-naphthamide; ^:

Coupler 23 - 1-Hydroxy-1 | -phenoxy-N, N- (dimethyl) -2-naphthamide.

To those for the inventively used color coupler, characteristic aryloxy wide variety of groups and substituents may be attached, for example, preformed Parbstoffgruppen for color correction, for FarbstoffÜber- \ transmission method and the like. On the aryloxy further additional ballast groups can be introduced into the coupler molecule, these ballast groups then being eliminated during the coupling reaction with the oxidation product of the color developing agent.

The specified couplers 1, 4, 5 »6, 7» 19 »20, 23, .26» 27 and 28 represent diffusing couplers which can therefore be used in color developer solutions for developing light-sensitive, photographic materials which do not Color coupler included.

The new color couplers can be used in alkaline color developer solutions sung together with the well-known, customary from primary, aro-

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ORIGINAL INSPECTED *

matic amino compounds can be used, for example together with phenylenediamines, for example diethyl-p-phenylenedlamine hydrochloride; Monomethyl-p-phenylenediamine hydrochloride; Dimethyl-p-phenylenediamine hydrochloride; 2-amino-5-diethylaminotoluene hydrochloride; 2-amino-5- (N-ethyl-N-laurylamino) toluene; N-ethyl-N- (ß-methanesulfonamidoethyl) -3-methyl-4-aminoaniline; H-JN-ethyl-N- (ß-hydroxyethyl) amino} aniline and the like. Or p-aminophenols and their substitution products in which the amino group is unsubstituted is.

The developing solutions can thereby variety of other additives are incorporated in a known manner, such as Alkalimethalleulfite, carbonates bisulfite, bromides, yo: dide and the like, as well as thickeners, such as carboxymethylcellulose, Carboxyäthylcellulose, gelatin and the like..

A developer solution containing a color coupler used according to the invention can, for example, have the following composition :

2-Amino-5-diethylaminotoluene HCl 2.0 g

Sodium sulfite (anhydrous) 2.0 g

Sodium carbonate monohydrate 20.0 g Potassium Bromide I ₁ Og

Coupler 2.0 g

Made up to 1 liter with water.

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'· ■ ORIGINAL

The rest of the examples listed, according to the invention Color couplers used are non-diffusing color couplers which are therefore advantageously photographic Emulsion layers are incorporated.

The couplers 2, 12, 14, 15, 16, 17, 18, 2k and 25 are so-called Fischer-type couplers. The other indicated, non-diffusing couplers, ie the couplers 3, 8, 9, 10, 11, 13 , 21 and 22 can be incorporated into photographic emulsion layers in an advantageous manner by processes such as those given in US Pat. Nos. 2,304,939 and 2,322,027, high-boiling organic solvents being used to dissolve the color couplers. Further processes for incorporating the last-mentioned non-diffusing color couplers into photographic emulsion layers are described, for example, in U.S. Patents 2,801,170j 2,801,171 and 2,919,360, low-boiling or water-soluble organic solvents being used instead of the high-boiling solvents.

The use of the color couplers in the form of color coupler dispersions enables the production of particularly thin emulsion layers. The production of thin emulsion layers is known to be very desirable because these layers become one lower light scattering, which in turn leads to the generation enables sharper images.

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j The coupler 17 contains an aryloxy group in the coupler molecule bound, a preformed dye molecule. This dye molecule is eliminated and diffused upon coupling of the coupler with the oxidation product of a developer compound from the movie. This color coupler can therefore be used as a yellow-colored coupler for color correction purposes, namely for correction unwanted blue absorption of the cyan dye images are used, i.e. for color correction of cyan dye images, generated by this coupler itself or by other cyan couplers. Appropriately, a sol- ; rather color coupler in combination with another skin green dye coupler used in the same emulsion layer.

The new color couplers are particularly suitable for color development photographic hydrophilic silver halide emulsion layers of the developable type, wherein the color couplers in the silver halide emulsion layers themselves or in layers adjoining these silver halide emulsion layers, The developable silver halide emulsion layers silver chloride, Silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide and the like.

The silver halides can thereby in a known manner by, the usual, hydrophilic colloids, which are used for the production of photographic Emulsion layers are used, be dispersed, for example in gelatin, colloidal albumin, cellulose

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loose derivatives or synthetic high polymers, for example Polyvinyl compounds.

The emulsion layers can also be used in a known manner be chemically or optically sensitized.

The new color couplers can also be used in image-forming layers, either alone or with others image-forming compounds that do not consist of silver halide, such as zinc oxide, zinc sulfide, cadmium sulfide, Cadmium selenide, nickel sulfide and the like with either or without binders such as gelatin, polyvinyl alcohol and the like.

The use of the invention has proven to be particularly advantageous color couplers used in multilayer, color photographic Materials have been shown to consist of a carrier and at least three differently sensitized emulsion layers exist. A typical material of this type consists of a carrier and a red-sensitive layer applied thereon, a green-sensitive layer applied to this layer and one on the green-sensitive layer Layer arranged blue-sensitive layer, where appropriate a yellow Carey Lea silver filter layer is arranged between the blue-sensitive and the green-sensitive layer can be * the three * different colored people

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ORIGINAL INSPECTED

Layers can also be arranged in a different order on the carrier. In doing so, however, when using a Carey Lea filter layer, these are not arranged over the blue-sensitive layer. Preferably those are photosensitive Layers arranged on the same side of the support.

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

example 1

Samples of photographic material having a gelatin-silver bromoiodide emulsion layer were exposed for one twenty-fifth of a second in an Eastman IB intensity-scale sensitometer. Subsequently, the samples according to the following methods have been developed to color positive at 2O ⁰ C:

Develop (MQ developer) 5 minutes

KXXXSlütX Interrupt (2-liter vinegar 5 "

acid)

Re-expose (12 seconds with a
100 watt lamp placed at a distance of 30.5 cm) 1 "

Parb Develop 10 "

Fix 5 "

Soak _A 5 "

Bleaching with ferric cyanide 5 "

Soak 5 "

Fix 5 "

Soak · 10 "

ORIGINAL INSPECTED

A fixing bath of the following composition was used for fixing:

Water, 50 ° C 600 cm ^

Sodium thiosulphate 2 ¹ IO g

Sodium sulfite, dehydrated 15.0 g

Acetic acid, 28 Ji-ig 18.0 cm ³

Boric acid, crystalline 7 »5 g

Potassium aluminum sulfate 15.0 g

Made up to 1 liter with water.

A color developer of the following composition was used for color development used:

Benzyl alcohol 4 cm ^

Sodium hexametaphosphate 0.5 g

Sodium sulfite, dehydrated 2.0g

Sodium hydroxide 0.16 g

Color coupler 2.0 g

il-Amino-3-methyl-N-ethyl-N [ß-methan-Bulfonamido) äthyi | aniline, Sesquisulfate hydrate 5 »0 g

Sodium carbonate, monohydrate 50.0 g, sodium bromide 0.2 g

Made up to 1 liter with water

pH adjusted to 10.75.

The couplers 1, 4, 5, 6, 7, 19 and were used

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In all cases, blue-green dye images of excellent quality were obtained.

Example 2

Films with a gelatin-silver bromoiodide emulsion layer were made containing Couplers 3, 8, 9, 10, 11, 13, 21 and 22.

During the production of the films, the couplers were incorporated into the silver halide emulsion in the form of dispersions, whereby di-n-butyl phthalate was used as the coupler solvent. The silver halide emulsion layers contained 10 parts by weight of gelatin, 5 parts by weight of silver, 2 parts by weight Color coupler and 1 part by weight coupler solvent.

Samples of the resulting films were again exposed for 1/25 second in an Eastman IB intensity scale sensitometer and developed in a known manner to give color negatives, using a developer solution of the following composition became:

Sodium sulfite, (anhydrous) 2.0 g

2-Amino-5-diethylaminotoluene HCl 2.0 g

Sodium carbonate, monohydrate 20.0 g

Potassium bromide 2.0 g

Made up to 1.0 liter with water

pH adjusted to 10.86.

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All of the color negatives obtained stood out excellent quality blue-green pigment images. In all cases, the color negatives obtained were excellent Heat resistance and light stability and had extremely low fog values.

The new 2-equivalent color couplers of the invention are suitable especially for use in multilayer color photographic materials as cyan color couplers along with magenta Dye-forming couplers and yellow dye-forming couplers. Yellow dye forming couplers are for example the known ones, a methylene group or a substituted methylene group with two adjacent carbonyl groups color couplers comprising and the magenta dye-forming couplers of 5-pyrazolone type or cyanoacetylcoumarone type.

The color couplers used according to the invention can be produced in a simple manner by reacting an 1-hydroxy- ¹ i-aryloxy-2-naphthoyl chloride with an appropriately substituted amine.

On the other hand, however, it is also possible to convert the coupler ^{into the l-benzyloxy-2-naphthamide by reacting l-hydroxy-i} l-acetoxy-2-naphtoyl chloride with an amine. acetoxy-2-naphthamide, Hy-

009816/1852

ORIGINAL INSPECTED

■:. '· ■ - al · ·

drolysis of this compound into the corresponding 4-hydroxy compound and reaction, the * sodium salt of this compound with fluorobenzene. The 4-benzyloxy-4-aryloxy-2-naphthamide can then be converted into the corresponding l-hydroxy-4-aryloxy-2-naphthamide by hydrogenolysis of the 1-benzyloxy group will.

The production of some of the color couplers which can be used according to the invention will be described in more detail below.

Preparation of Coupler No. 2 (! -Hydroxy- ¹ ! - {4- [a- (3-pentadecy! Phenoxyjbutyramidojphenoxy> -N-octadecyl-3 ', 5'-dicarboxy-2-naphthaniline)

Intermediate compound 1: l-hydroxy-4- (4-nitrophenoxy) -2-naphthoic acid:

To a solution of 20 g of 1,4-dihydroxy-2-naphthoic acid in 150 m] Dimethylformamide were 20 g of an aqueous, 40 # strength Na-

4-

trium hydroxide solution and 14 g / nitrofluorobenzene within 5 minutes added with stirring and a nitrogen atmosphere. The reaction mixture was stirred for a total of 2 hours, after which the mixture was poured into dilute hydrochloric acid became. The resulting solid precipitate, i.e. the desired intermediate, was filtered off and extracted twice Recrystallized methyl alcohol.

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ORIGINAL INSPECTED

Intermediate 2: l-Hydroxy-4- (4-nitrophenoxy) -2-naphthoyl chloride:

A mixture of 3.25 g of intermediate 1 in 10 ml Thionyl chloride was stirred at room temperature for 2 hours, during which time all the acid went into solution and a solid, yellow precipitate separated. This was filtered off and recrystallized from warm, anhydrous acetonitrile.

Intermediate 3: l-Hydroxy-i | - (i | -nitrophenoxy) -N-octadecyJ.-3 ', 5 * -dicarbomethoxy-2-naphthanilide:

3.4 g of N-octadecyl-SiS-dicarbomethoxyaniline were added to a solution of 2.4 g of intermediate 2 in 100 ml of anhydrous dioxane and 1 ml of N, N-dimethylaniline was added. The clear reaction mixture was then left overnight at room temperature stored, whereupon it was poured into 500 ml of cold water. An oil separated out, which was changed with further washing solidified with water. The solid reaction product was filtered off and recrystallized twice from acetonitrile.

Intermediate 4: l-Hydroxy-4- (4-aminophenoxy) -N-octadecyl-3 », 5'-dicarbomethoxy-2-naphthanide:

A solution of 1.6 g of intermediate 3 in 100 ml of absolute lutem ethyl alcohol was made using Raney nickel as a

009816/1852

Catalyst reduced in a Parr hydrogenation apparatus. To. the reduction, the catalyst was filtered off, whereupon the The concentrate was concentrated in vacuo and the solid residue was removed from acetonitrile. The recrystallized compound consisted of the desired intermediate.

Intermediate 5ί l-hydroxy-4- {4- [ä- (3-pentadecylphenoxy) -butyramidq] phenoxy} -N-octadecyl-3 ^f , 5'-dicarbomethoxy-2-naphthanilide:

A solution of 2 g of α- (3-pentadecylphenoxy) butyryl chloride in 25 ml of acetic acid was added with stirring at room temperature to a solution of 3 » ^{1 J g of intermediate 4 and an excess of sodium acetate in 50 ml of acetic acid.} After the reaction mixture was stirred at room temperature for 1 hour, it was heated to 60 ° C. and then allowed to stand at room temperature overnight. The mixture was then poured into 500 ml of cold water, a solid precipitate separating out, which was filtered off and dried. The precipitate consisted of the desired intermediate 5

Coupler No. 2

A solution of 6 g of sodium hydroxide in 100 ml of water was added to a solution of intermediate product 5 in 250 ml of absolute ethyl alcohol over a period of 2 minutes. added vigorous stirring. The mixture was at a tem- . 009816/1852

temperature of 65 ⁰ C for 1 1/2 hours, whereupon it was poured into 1 liter of water containing 25 nil concentrated hydrochloric acid. The color coupler failed. It was filtered off, washed with cold water, dried and recrystallized twice from acetonitrile.

Preparation of coupler 3 (l-hydroxy-4- (4-nitrophenoxy) -N-

R - (2,4-di-t-amylphenoxy) butyl] -2-naphthamide)) \

To a solution of 17 g of 5- (2 _i ⁱ l-di-t-amylphenoxy) butylamine and 6 ml of dimethylaniline in 200 ml of anhydrous dioxane were added 18 g of l-hydroxy-4- (4-nitrophenoxy) -2-naphthoyl chloride ( Intermediate product 2 of coupler 2) was added with stirring. The reaction mixture was stirred at room temperature overnight, after which it was poured into 1 liter of cold water containing 5 ml of acetic acid. The desired color coupler failed. It was filtered off, washed with cold water and dried. The coupler was then recrystallized from a mixture of hexane and benzene.

Preparation of coupler 24 (l-hydroxy-fr-C ^ -acetamflidophenoxy) - ' N-octadecyl-3 ^! .5'-dicarboxy-2-naphthanilide)

Intermediate: l-Hydroxy-iJ-CJj-acetarnidophenoxyJ-N-octadecyl-3 ', 5'-dicarbomethoxy-2-naphthanilide:

'! -Aicar'bori' To a solution of 9 »l 6 β-hydroxy-4- (4-aminophenoxy) -N-octaaeoyl-3 ^1, 5 athox / ~ 2-naphtIumilld (Zwicchi-nprodukt

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BATH ORIGINAL

4 of the coupler 2) and 1.5 g of anhydrous sodium acetate in 100 ml of acetic acid became 1.1 g of acetyl chloride with stirring admitted. The reaction mixture was at room temperature Stirred for 1 hour after which it was poured into 800 ml of water. A solid precipitate separated out, the was filtered off and air dried. The precipitate consisted of the desired intermediate. The product was recrystallized from acetonitrile.

Coupler 24:

To a solution of 3 g of the intermediate product in 50 ml of ethyl alcohol were 2 ml of an aqueous, 40% sodium hydroxide solution given. Another 5 ml of water was added and the solution was stirred for 2 hours. The received The solution then became 200 ml of 5% hydrochloric acid added, the spiced coupler separating out in the form of a solid precipitate. The precipitate was filtered off, washed with water and dried. The color coupler obtained was then recrystallized twice from acetonitrile.

Preparation of coupler 25 (l-hydroxy-4- (4-nitrophenoxy) -M-octadecyl-S *, 5 ^> -disulfo-2-naphthanilide, disodium salt)

Intermediate: l-hydroxy-4- (4-nitrophenoxy) -N-octadecyl-. 3 », 5'-difluorosulfonyl-2-naphthanilide:

009816/18 52

BATH ORIGINAL

To a solution of 1.3 g of 1-hydroxy-4- (4-nitrophenoxy) -2-naphthoyl chloride (Intermediate product 2 of coupler 2) and 10 drops of Dimethylanilln in 20 ml of anhydrous dioxin were 1.4 g of N-octadecyl-SjS-difluorosulfonylaniline with stirring admitted. The mixture was stirred at room temperature overnight, after which it was poured into 150 ml of dilute acetic acid became. A solid precipitate consisting of the desired intermediate precipitated out, which was filtered off and was recrystallized twice from acetonitrile.

Coupler 25:

The intermediate obtained was converted to the sodium salt in the manner described in the preparation of coupler 24 .

The other described color couplers which can be used according to the invention were produced according to the method described in the production of the color coupler 3, the following Table «indicated intermediates were used.

Coupler Acid Chloride Intermediate Amine Component No Binding ___________________

1 l-hydroxy-4- (4-methy I sulfonyl-

phenoxy) -2-napthoylchlocid ammonia

4 1-Hydroxy-4- (2,4-diniferophenoxy) -2-naphthoyl chloride Ethylamine

5 l-Hydroxy-4-phenoxy-2-naphthoyl chloride 2-methoxyanlline

009816/1652

ORIGINAL INSPECTED

l-hydroxy-4- (4-nitrophenoxy) 2-naphthoyl chloride

1-Hydroxy-4- (4-nitrophenoxy) ■ 2-naphthoyl chloride

penta

1-Hydroxy-4-diBExacfluorophenoxy) -2-naphthoyl chloride

1-hydroxy-4- (1-naphthyloxy) -2-naphthoyl chloride

1-Hydroxy-4-acetoxy-2-naphthoyl chloride

Phenethylamine

ß- (2-nitrophenyl) ethylamine

(The obtained nitro compound became catalytic reduced, whereupon the two amino groups acetylated with acetic anhydride became).

ß- (4-nitrophenyl) ethylamine

(The nitro compound obtained was catalytically reduced, whereupon the amino compound obtained was acetylated with α- (2, ⁱ l-di-t.-amylphenoxy) acetyl chloride).

Dioctylamine

4- (4-t-butylphenoxy) aniline

(The l-hydroxy-4-acetoxy-iJ 'obtained as an intermediate - (4-t -butylphenoxy) -2-naphthanilide was converted into the corresponding 1-benzyloxy compound converted to the corresponding Jl-hydroxy compound was hydrolyzed. This compound was then made by reaction with 4-fluoropyridine converted into the 4-pyridyloxy derivative, the was then converted into the coupler by hydrogenolysis of the 1-benzyloxy group).

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2-tetradecyloxyaniline

1-Hydroxy-4- (4-chlorophenoxy) -2-naphthoyl chloride

1-Hydroxy-4- [3- (N-methyl-N-pro-N-C pylsulfamyl) phenoxy]] -2-2-naph-methoxy aniline thoylchloride

(The 'ester initially obtained as an intermediate compound became the coupler' hydrolyzed).

3-nitroaniline

(The nitro compound obtained as an intermediate compound became catalytic. reduced, whereupon the Re- *. production product with a- (§- I Pentadecylphenoxy) -butyrylohlorid was acylated)}

N-octadecyl-4-sulfoaniline, Sodium salt ι

1-Hydroxy-4- Q- (4-hydroxyphenylsulfony1) phenoxy] -2-naphthoyl chloride

l-hydroxy-4- (4-nitro-3-pentadecylphenoxy) -2-naphthoylchlo- rid

1-hydroxy-4- (3-nitrophenoxy) -2-naphthoyl chloride

1-Hydroxy-4-phenoxy-2-naphthoyl chloride N-octadecyl-3,5-di-carbomethoxyaniline .

(The ester initially obtained as an intermediate compound was hydrolyzed).

ß- (4-nitrophenyl) ethyl j amine j

(The obtained as Zwtehenverbindung nitro compound was catalytically reduced, after which the reduction product with 2-I (2,4-di-t--amylphenoxy) - ■ 5-nitrobenzoyl \ acfliert was "The ER \ haitene Nitroderlvat wur-> de catalytically reduced whereupon the reductlon product was aoylated with 3 * 5 ^ Dlohloro8Ul * fonylbenzoylochloride. The chloro-aulphonyl groups were then converted into sulphonated sodium salt groups by hydrolysis). .

009816/1852

1-Hydroxy-1J-acetoxy-2-naphthQ-ylchlorld

1-Hydroxy-4- {4-chlorosulfonylphenoxy) -2-naphthoyl chloride

1-hydroxy- ^J 1-phenoxy-2-naphthoyl chloride

1-Hydroxy-4- (4-nitrophenoxy) 2-naphthoyl chloride 4- (4-t-butylphenoxy) ani lin

(The 1-hydroxy-4-acetoxy-4 '~ (4-t-butylphenoxy) -2-naphthanilide obtained as an intermediate compound was converted into the corresponding 1-benzyloxy derivative, which was hydrolyzed to the corresponding 4-hydroxy derivative found in the 4-J3- (4-sulfophenylazο) phenoxy! derivative by reaction with 4- (4-fluorophenylazo) -benzenesulfonic acid was convicted. The latter was made by hydrogenolysis of the 1-benzyloxy group transferred to the coupler

Octadecylamine

(The Cfilorosulfonyl Intermediate was converted into the coupler by alkaline hydrolysis).

Morpholine

Cyclohexylamine

4,4 ^f -Bis (1-hydroxy-2-chlorocar-ethylarain vonyl-4-naphthyloxy) -dipheny1-sulfone

1,4-bis (1-hydroxy-2-chlorocarbony1-4-naphthyloxy) benzene

2-nitroaniline

(The nitro compound obtained from all intermediate compounds was catalytically reduced, whereupon the reduction product obtained was acetylated with acetic anhydride ^{! Xcyxis)}

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23 l-llydroxy-iJ-CiJ-chlorosulfonyl-N-methylaniline phenoxy) -2-n ^ aphthoyl chloride

(The intermediate compound containing a chlorosulfonyl group was converted into the coupler by alkaline hydrolysis).

26 l-Hydroxy- ⁱ l-phenoxy-2-naphtho-2-aminobenzimidazol yl chloride

27 1-Hydroxy-4- (4-nitrophenoxy) -N-Xthylmethylamine 2-naphthoyl chloride

28 l-hydroxy - ^ - phenoxy ^ -naphtho-dimethylamine yl chloride

The 2-equivalent couplers used according to the invention differ differs from known 2-equivalent couplers through an aryloxy group in the coupling position of the coupler molecule. According to the invention The color couplers used are distinguished by excellent coupling properties and also by the fact that they have no or at least a greatly reduced color haze produce. The color images produced using the color couplers have excellent heat and light stability.

The color couplers used according to the invention can also be dispersed in emulsions, with the color coupler solvent used and the ratio of color coupler to solvent : ■ - ■ - ■■
can vary within wide limits.

Many of the nondifference used in accordance with the invention Color couplers can be used in photographic emulsions without an

009816/1852

Bring in a turn of a high-boiling solvent. at The use of these color couplers has the particular advantage that the color couplers are accommodated in thin emulsion layers that deliver particularly sharp images. The color couplers used according to the invention are furthermore with others known color couplers compatible, so that they can be used together with either 4- or 2-equivalent couplers, Compensating couplers and the like in emulsion layers or color developer solutions can be used.

009816/1652

Claims (4)

Claims 1. Use of color couplers which contain at least one 4-hydroxy-3-carbamyl-1-naphthyl group, in which the hydrogen atom in the! position of the naphthyl ring is replaced by an aryloxy group is, have, for the production of dyes by coupling with the oxidation product of an aromatic Amine existing developer compound in the development of Color photographic material. 2. Use of color couplers according to claim 1, characterized in that that they correspond to the following formula: CON ^J \ r3 where mean: Around Hydrogen atoms, alkyl, aryl or heterocyclic Radicals or together the atoms required to complete a heterocyclic ring, 009816/1852 η = 1 or 2 and R is an aryl radical if η = 1 or an arylene radical, when η = 2. 3. Use of color couplers according to claims 1 and 2, best- (penta starting from l-hydroxy-4- & hexatfluorophenoxy) -N- {ß- {4- [^ - (2, ^ Ι-αΙ-ί.-amylphenoxyJacetamidoQphenyläthyll ^ -naphthamidj 1-Hydroxy.il- (4-nitrophenoxy) -N - [δ- (2, 4-di-t. -amylphenoxy) butyl] -2-naphthamide; l-hydroxy-4 - (^ - acetamidophenoxy) -N- [ß- (2-acetamidophenyl) ethyl] -2- naphthamide; l-hydroxy-4- (4-chlorophenoxy) -2 ^! - tetradecyloxy-2-naphthanilide or l-IIydroxy-4- [4- (M-sulfophenylazo) phenoxy]] - i | ^| - ( ⁱ lt-butylphenoxy ) -2-naphthanilide _> sodium salt. 4. Use of color couplers according to claims 1 to 3 »in photosensitive Silver halide emulsion layers of a photographic material. 009316/1852