DE1953372A1 - Light-sensitive, color photographic silver halide emulsion - Google Patents

Description

46 ö1b

Applicant: Konishiroku Photo Industry Co. ltd.

Light-sensitive, color photographic silver halide emulsion

The present invention relates to a light-sensitive, color photographic emulsion containing new cyan couplers, which in water-immiscible high-boiling solvents are soluble.

As a coupler for use in light-sensitive, color photographic Emulsions are known as the so-called Agfa-type couplers, which are soluble in water. Also known are the so-called protected couplers, which are soluble in water-immiscible high-boiling solvents. It is well known that color images formed after color development of protected couplers that are in the emulsion layers of the color photographic light-sensitive material are obtained, generally an excellent one Resistance to light, heat, moisture and the developing chemicals, in contrast to the

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those materials with the Agfa-type couplers.

There are already numerous compounds as protected couplers has been synthesized. However, all of these compounds have disadvantages in that they have poor solubility in high-boiling solvents, easily separated from emulsions and coatings, the starting materials for the production of which is difficult to access and expensive and the production processes are complicated, so that these substances so can only be produced with difficulty. For example, has the coupler of the formula

OH

COHNCH ₂ CH ₂ HHCOCh ₂ O - ^ Λ - ^tC 5 ^H 11

published in U.S. Patent No. 2,474,493, excellent solubility in high-boiling solvents. However, this coupler must be made using extremely difficult to access and therefore expensive raw materials can be produced, and it is difficult to clean. A coupler which can be made from a higher fatty acid or a higher aliphatic amine, e.g. Couplers represented by the following formula

CO (CH ₂ ) ₅ CH ₅ COHNCH ₂ CH ₂ ITHCOCH ₂ Ch ₂ II

which in Japanese Patent Publication ITr. 2, ÖJ9 / 64, has excellent solubility. But even this solubility is still insufficient. In addition, an oleophilic component is used in this coupler, which must be synthesized in several stages. Therefore, a ¹ Ch of this coupler is difficult to access and expensive, although the starting materials used for it are easily accessible and _ * *

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8A0

are cheap.

In view of this prior art, the inventors of the present invention have made numerous studies carried out to find couplers made using readily available starting materials can. In pursuit of this research, surprisingly found, the cyan couplers take the following general terms Formulas that have quite excellent solubility in high-boiling solvents can be easily prepared can.

The present invention accordingly provides a photosensitive, Color photographic .silver halide emulsion, which is characterized in that it is a compound as a cyan coupler the general formula

OH

COHK-OH-C CH ₂ ) _n -COOCHCOOR ₃

where R .. is hydrogen or a methyl group, R2 is a hydrogen atom or an aliphatic hydrocarbon radical with 1-16 carbon atoms, R, for an aliphatic hydrocarbon radical with 1-16 Carbon atoms, η the Zatil O or 1 means and X is a hydrogen atom, a halogen atom or a substituted or unsubstituted phenylazo group, contains. Pie used according to the present invention Couplers: may not include the components of the known couplers of the Staude der Technik and seichner, the following ones did it Features from:

1 . They are easily soluble in high-boiling solvents like Dibut "iphthrlat, Tricresyiphosphat and Ν-, Η-DibUtyllaur.vlamid, so that the amounts of high-boiling solvents

00 9 821/1889
BATH

which must be added to the couplers can be reduced and stable dispersions of high concentration can be obtained.

2. They have a low melting point and do not form deposits from emulsions or coatings.

3. They can be produced synthetically in a short manufacturing process, and can be easily separated and cleaned. the Yields are high and the starting products are easily accessible, so that the manufacturing process is technically simple and therefore is cheap.

4. They give color images that have desirable spectral absorb ti ons properties and against light, heat, Resistant to moisture and chemicals.

Therefore, the couplers used in the present invention are extremely useful as protected couplers.

Photosensitive, color photographic emulsions containing the couplers thus contained according to the present invention can be stably stored without deterioration the photographic properties occurs due to the deposition of the coupler.

Below are some typical examples of the Invention used coupler called. These are only examples. Those useful according to the invention Couplers are not limited to these examples.

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_ 5 -

(1) N-dodecyloxycarbonyl-methoxycarbonylmethyl-1-hydroxy-2-naphthamide

COeICH ₂ COOCH ₂ COOC ₁₂ H ₂₅

(F. 74 ° - 74.5 ⁰ C)

(2) N- [1- (ethoxycarbonyl) pentadecyloxycarbonylmethyl] 1-hydroxy-2-naphthamide

GOHETGH ₂ COOCHCOOc ₂ H ₅

^C 14 ^H 29

.. 57 ° - 59 ⁰ C)

(3) N- [(1-Methyllieptyl) -oxycarbonyl-methoxycarbonylmethyl] l-hydroxy-2-naphthalene lamiά

OH

COmICH ₀ COOCH ₀ COOCHC ^ H _n _ 2 2 1 ο

CH,

(P. 66 ° - 67 ⁰ C)

(4) Ii- [! - (Dodecyloxycarbonyli-athoxycarbonylmethyl] 1-hydroxy-2-naphthamide:

OH

COHNCh ₂ COOCHCOOC ₁₂ H ₂₅ CH,

55 ° - 58 ⁰ C.)

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(5) N- [1- (butoxycarbonyl) -heptyloxycarbonylmethyl jl-hydroxy-2-naphthamide

OH

'(p. 57 ° - 58 ° C.)

(6) N-fl-iDodecyloxycaxbonyl-methoxycarbonyli-ethyl] 1-hydro3iy-2-naphthaniide

OH

kXJ

(P. 55 ° - 56 ⁰ C.)

(7) N- ^ - (Dodecyloxycarbonyl-methoxycarbonylJ-ethylj. l-hydroxy-2-naphthamide '

(P. 65 ⁰ C.)

(8) K-dodecyloxycarbonyl-methoxycarbonylnietliyl-l hydroxy-4-chloro-2-naphthamide

69 ° - 7O ⁰ C.)

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(9) N-Dodecyloxycarbonyl-methoxycarbonylmethyl-1-hydroxy-4- (2-acetylphenylazo) -2-naphthamide

COHNCH ₂ COOCh ₂ COOC ₁₂ H _{2 5}
_ * (F. 133 ° - 137 ⁰ C.)

COCH ₅

(10) N- [1- (dodecyloxycarbonyl) ethoxycarbonylmethyl] 1- hydroxy-4- (2-acetylphenylazo) -2-naphthamide

OH

COHIiCH ₂ COOCHCOOC ₁₂ H ₂₅

^{N = N} ~ \ _ / ^{(F 106} ° " ¹⁰⁹ ° ^c )

COCH ₃

(11) N- [1- (Butoxy carbonyl) -heptyloxycarbonylmethyl] 1-hydroxy-4- (2-acetylphenylazo) -2-naphthamide

OH

COHIiCH ₂ COOCKCOOC ₄ H ₉

^{N = NT} - \ / (F. 117 ° - 118 ⁰ C.)

/
COCH °

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(12) N- [1- (dodecyloxycarbonyl-metb.oxycarbonyl) -ä 1-hydroxy-4- (2-acetylphenylazo) -2-naphthamide

COHNCH ₂ COOCH ₂ COOc ₁₂ H ₂₅

CH,

(P.93 ° - 95 ° C.)

COCH ₃

(13) N- [2- (dodecyloxycarbonyl-methoxycarbonyl) -ethyl] -l-hydroxy-4- (2- ethoxycarbonylphenylazo) -2-naphthamide

OH

(P. 137 ° - 138 ⁰ C) '

COOC ₂ H ₅

(14) N- [(1-Methylheptyl) -oxycarbonyl-methoxycarbonylmethyl)] 1-hydroxy-4- (2-ethoxycarbonylphenylazo) -2-naphthamide

OH

COHNCH ₀ COOCH ₀ COOCHC ^ H _n 2 2 ι ο

CH

N = N- '

(P. 141 ° - 142 ⁰ C.)

COOC ₂ H ₅

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The couplers used in accordance with the present invention are generally prepared synthetically by using a Amino acid such as glycine, α-alanine or γ-alanine with one Naphthoic acid derivative such as Ph.enyl-1-hydroxy-2-naphth.oate condensed being an N- (1-hydroxy-2-naphthoyl) amino acid the following formula is obtained:

COHNCH- (CH ₂ ) _n -COOH R ₁

where X, R. and η have the same meaning as above, and then this intermediate is converted into its potassium salt and converted into dimethylformamide with an allyl ester implemented o6-halogen fatty acid or this intermediate reacted in dimethylformamide with an alkyl ester of a halogenated fatty acid in the presence of potassium hydrogen carbonate will.

The synthetic preparation of the couplers is described in detail below by means of examples.

Synthesis of the coupler (1)

a) 1-Hydroxy-2-naphthoyl glycine

84 g of potassium hydroxide are dissolved in a solvent mixture of 200 ml of water and 400 ml of alcohol. Then 112 g of glycine are dissolved in it. 164 g of phenyl i-hydroxy-2-naphthoate and 400 ml of alcohol are added to the resulting solution, and the solution is refluxed for 3 hours. The still hot solution is poured into 3 kg of ice water and then filtered in the usual way using activated charcoal. 160 ml of concentrated hydrochloric acid are added to the filtrate, and the precipitate formed is filtered off with suction, washed with water and pressed off. The wet precipitation -10-

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is then taken up in 2 l of alcohol and heated to boiling under reflux so that it dissolves completely. The solution is then filtered in a conventional manner using activated charcoal. The piltrate is mixed with 3 liters of warm water and left to stand. The crystals formed are drained, washed with 30 # ethyl alcohol and dried to give 140 g of pale orange needle-shaped crystals are obtained with a melting point 207-209 ⁰ C.

The following compounds are obtained in an analogous manner:

1-hydroxy-2-naphthoyl-ck-alanine

F. 188-190 ⁰ C: granular sugar-like crystals

pale pink in color. 1-hydroxy-2-naphthoyl-ß-alanine

F. 149-150 ⁰ C: needle-shaped crystals of pale pink coloring.

b) Dodecyl-e ^ chloroacetate

94 · 5 g of C-chloroacetic acid and 186.3 g of dodecyl alcohol dissolved in 1.5 l of dehydrated benzene. The solution is mixed with 5 g of p-toluenesulfonic acid and refluxed for 2-3 hours heated to boiling. The water formed during the reaction is removed by azeotropic distillation with benzene. The reaction solution is then mixed with aqueous sodium carbonate solution shaken and the benzene solution is dehydrated and distilled under reduced pressure to remove the benzene. In this distillation under reduced pressure, 155 g of dodeeyl-ol-chloroacetate with a boiling point of 187-1ö8 c / 14 mmHg obtained. This product can be used for the next stage immediately after the benzene has been distilled off, without further distillation being carried out.

The following compounds are obtained in an analogous manner:

1 -Methyl-heptyl-oi-chloroacetate

Kp 12O-123 ° C / 13 mmHg _ _Λλ _

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Dodecyl cL-bromopropionate

K.p. (Decomp.) J used without distillation. Butyl cUbromcaproate,

used without distillation.

c) N-dodecyloxycarbonyl-methoxycarbonylmethyl-i-hydroxy-2-naphthamide.

123 g of 1-hydroxy-2-naphthoylglyein are dissolved in 600 ml of methanol and mixed with a solution of 56 g of potassium hydroxide in 600 ml of methanol. The methanol is distilled off under reduced pressure. The residue is mixed with one liter of dimethylformamide and 131 g of dodecyl-06-chloroacetate, and the mixture is heated for 2 hours with stirring. To an external temperature of 95-10O ⁰ C. After allowing to cool, the reaction mixture is poured into 10 l of water. The deposited precipitate is filtered off with suction, washed with water and dried. Recrystallization from 1.5 l of methanol gives 200 g of the desired product and repeated recrystallization from 5 l of η-hexane gives 170 g of pale pink, flaky crystals.

The above-mentioned couplers (2) - (7) are obtained in an analogous manner.

Synthetic production of the coupler (ö):

1ÜÖ g of the coupler (1), N-dodecyloxycarbonyl-methoxycarbonylmethyl-1-hydroxy-2-naphthamide, are dissolved in 500 ml of chloroform. The solution obtained is ^{cooled to below 0} ° C. and mixed with a mixed solution of 66 g of sulfuryl chloride and 200 ml of chloroform. The solution is then left to stand at room temperature for one hour and the solvent is removed by distillation under reduced pressure. The residue is mixed with 1 liter of η-hexane and left to stand. The deposited precipitate is filtered off with suction, washed with η-hexane and dried, 13 g of N-dodecyloxycarbonyl-7- · βthoxycarbouylmethy 1-1 -hydroxy-4-chloro-2-naphthamide being obtained.

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6AO ORIGINAL

will be. Recrystallisation from 1.5 1 η-hexane gives 90 g of powdery crystals of pale brown color, which melt at 69-7O ⁰ C.

Synthetic production of the coupler (9):

115g of o-aminoacetophenone are dissolved in dilute hydrochloric acid and diazotized with aqueous sodium nitrite solution. The resulting solution becomes a solution of 471 g of the coupler (1), N-dodecyloxycarbonyl-methoxycarbonylmethyl-i-hydroxy-2 naphthamide in a solvent mixture of 4 1 pyridine and 10 1 acetonitrile at a temperature below 1ü ° C with stirring given. Stirring is continued for 50 minutes at room temperature. Then 400 ml of concentrated hydrochloric acid are added added to the reaction solution, and the deposited precipitate is filtered off with suction, washed with water and dried, 5bO g of N-dodecyloxy-carbonyl-methoxycarbonylmethyl-ihydroxy-4- (2-acetylphenylazo) -2-naphthamide can be obtained. Recrystallization from ethyl acetate gives 510 g of red feather-like Crystals.

In carrying out the method described above, using couplers (4), (b) and (6) instead of Coupler (1) used as a starting product, the above-mentioned couplers (10), (11) and (12) are obtained.

The Kuppir (15) and (14) can be made of diazotized! Ethyl oaminobenzoate and the couplers (5) and (7) are prepared in a corresponding manner.

Of the couplers used in the invention, those in which X is a halogen atom, can be prepared by a coupler in which X is a hydrogen atom means treated with a halogenating agent such as sulfuryl chloride. This creates the hydrogen atom replaced by a halogen atom. Those couplers in which X is a substituted or unsubstituted phenylazo group

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■ · ■ .. '·; ί (.i.Fii, / 0 ·' · <ι

stands, can by coupling a coupler in which X is a hydrogen atom, with a substituted or unsubstituted aromatic diazonium compound can be produced.

The coupler of the general formula I in which R ₁ and R ₂ 3 ^e ~ weils mean and R., is a straight chain alkyl group of atoms hydrogen, possess an excellent solubility in high-boiling solvents. However, the solubility can be remarkably increased if R _{1 is changed} to a methyl group, R ₂ to an alkyl group, R- to a branched alkyl group, or η to 1. R ₁ can be changed by selecting glycine, <j £ -alanine or ^ -alanine as the starting material. R ₂ can be changed by choosing oi-chloroacetic acid, Qi-bromopropionic acid, ct-bromo-n ~ butyric acid, oί, -bromo-i-butyric acid, oi ~ bromocaprylic acid or θέ-bromolauric acid as the starting material. R ~ can be changed by choosing lauryl alcohol, 2-ethylhexyl alcohol, 2-octyl alcohol or Y-ethyl-methyl-undecyl alcohol as the starting material. η can be changed by choosing glycine or ß-alanine as the starting material. All of these starting products are extremely easily accessible and commercially available products. Even in the production of fresh products, the alkyl esters of ß-halogen fatty acids are easily produced in high purity and yield by reacting an ot-halogen fatty acid with an equimolar amount of an aliphatic alcohol. Furthermore, the reaction of this intermediate product with 1-hydroxy-2-naphthoylamino acid can also be easily carried out, as mentioned above, and the desired product can be obtained in high purity and yield by simple isolation and purification methods.

The couplers used according to the invention thus have the advantage that they are produced synthetically in three to four stages, without the need for complicated process stages eref orderlica warm, and the easily accessible and therefore ..

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ΘΑΟ ORIGINAL

cheap starting materials can be used, so that the. Production is considerably easier and cheaper in comparison with the known couplers of the prior art.

Using the couplers synthetically prepared as described above, light-sensitive, color photographic materials can be prepared as follows: For example, a cyan coupler used according to the invention is in a high-boiling solvent with a boiling point of more than IbO ⁰ C such as tricresyl phosphate or dibutyl phthalate either alone or if necessary, dissolved in a mixture with a low-boiling solvent, vae butyl acetate or butyl propionate. The solution is mixed with an aqueous IG-elatin solution containing a surface-active agent and then emulsified using a high-speed rotary mixer or a colloid mill. The coupler dispersion prepared in this way is then added directly to a photographic silver halide emulsion which is applied to a film support, baryta paper or a similar support. It is then dried in order to remove most of the low-boiling solvent. Alternatively, the above-mentioned coupler dispersion is allowed to harden and then extruded into nude-shaped structures, which are freed from the low-boiling solvent by washing with water or by similar processes. The noodles are then added, with heating, to a silver halide photographic emulsion which is then coated on the aforementioned support. Then it is dried.

The methods of incorporating the coupler described above are illustrative in nature and not restrictive. The one added to the silver halide photographic emulsion The amount of the coupler is preferably in the range of 10-100 g per mole of silver halide. However, the crowd is not always limited to this. Silver salts such as silver chloride can be used as silver halides for the photographic emulsions. silver iodide or silver iodobromide can be used. the

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chemical sensitizers, e.g. Schvdiel sensitizers, Contain natural sensitizers, reductive sensitizers and precious metal salts present in the gelatin. The emulsions can also contain conventional photographic additives such as antifoggants, stabilizers, anti-yellowing agents, Contain anti-diffusion antihalation agents, coating aids, and other high molecular weight additives. You can also use known carbocyanine dyes, Merocyanine dyes etc. as optical sensitizers keep.

The light-sensitive, color photographic materials obtained in this way are radioactive rays, X-rays, exposed to visible light and infrared radiation and developed with a color developing solution that is a developer of the p-phenylenediamine type. Then it is bleached and fixed, whereby a cyan image is obtained, that a favorable one Transparency and high resistance to the effects of light, heat and moisture. That color formation has excellent spectral absorption properties and a maximum absorption near 6bU - 69U mp. If in alternatively, a light-sensitive, color photographic material which contains an arylazo-type coupler incorporated, which itself has a reddish orange or red color as in the case of the above-mentioned coupler No. 10, for example and then according to the usual color development process is treated, a cyan regative color image is created at the same time and obtained a reddish orange to red positive color image. This positive color image is used for copying of the negative image on a positive material, a mask for correcting undesirable absorptions in the area of the blue and green light inherent in the cyan negative color image. reside. Preferred couplers of this type are the substituted phenylazo compounds which are in the ortho position to the azo bond have an alkoxycarbonyl group or a fatty acyl group.

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Typical developing agents used for developing the photosensitive, Color photographic materials that can be used in accordance with the invention include sulfates, sulfites and hydrochlorides of Ν, Ν-diethyl-p-phenylenediamine, N-ethyl-N- / 3-methane-sulfonamidoethyl-3-methyl-4-aminoaniline, N-ethyl-N-hydroxy-p-phenylenediamine, N-ethyl-N-hydroxy-2-methyl-p-phenylenediamine and NjN-diethyl ^ -methyl-p-phenylenediamine.

The present invention will now be explained in detail by means of examples. These examples are for convenience only to illustrate and not to limit the invention.

example 1

20 g of the coupler mentioned above under No. 1, for example, are converted into a liquid mixture containing 20 ml of dibutyl phthalate and 60 ml of butyl acetate are added, and the mixture is completely converted into a solution at ÖO ° C. This solution was treated with 10 ml of a 10% aqueous solution of alkanol B (Alkylnaphthalene sulfonate manufactured by Du Pont) and 200 ml of a 5 # aqueous gelatin solution mixed, and this Mixture was processed into a coupler dispersion in a colloid mill. This coupler dispersion became 1 kg a highly sensitive gelatin-containing silver iodobromide emulsion given, which was then applied to a layer support and dried, whereby a light-sensitive, color photographic material with a stable coating was obtained.

The light-sensitive material thus prepared was made according to the usual Process illuminated and then developed for 10 minutes at 20 C with a developer solution of the following composition »

Ν, Ν-diethyl-p-phenylenediamine hydrochloride 2.5 g

anhydrous sodium sulfite 2.0 g

Sodium carbonate (monohydrate) 82.0 g

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Potassium bromide 2.0 g

Water up to 1000 ml

The developed material was then subjected to the usual and subjected to fixation treatments, washed with water for 10-15 minutes, and then with a for 5 minutes Treated bleach bath of the following composition:

Potassium ferricyanide 100 g

Potassium bromide 50 g

Water up to 1000 ml

The bleached material was then washed with water for 5 minutes and then with a fixing bath for 5 minutes the following composition fixed:

Uodium thiosulphate (pentahydrate) 250 g water up to 1000 ml

The fixed material was then washed with water for 20-25 minutes and dried, giving a brilliant cyan color image with a maximum absorption at 6ö5 mp.

Example 2:

10g of the above as no. 8 coupler, for example, referred to were added to a liquid mixture containing 10 ml of tricresyl phosphate and 30 ml of butyl acetate, and the mixture was completely converted durcn heating to 60 ⁰ C in a solution. This solution was mixed with 5 ml of a 10% aqueous solution of alkanol B and 200 ml of a 5% aqueous gelatin solution, and the mixture was then processed into a coupler dispersion in a colloid mill. This dispersion was added to 500 g of a gelatin-containing silver iodobromide emulsion , which was then applied to a layer support and dried in order to produce a light-sensitive, -Ia-

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- 1ö -

to produce color photographic material in which there is no danger exists that the coupler could separate out.

The photosensitive material thus prepared was then exposed and developed for 10 min at 20 ⁰ C with eii following composition.:

and then for 10 minutes at 20 ^° C. with a developer solution of the

Methyl 3.0 g

anhydrous sodium sulfite 60.0 g

Hydroquinone 6.0 g

anhydrous sodium carbonate pO.O g

Potassium bromide 1.0g

Water up to 1000 ml

Then the developed material was processed in the usual manner the stopping and film hardening treatments and the washer, exposed to water. After the material was given a second exposure to white light, it became Developed for 12 min. At 20 ° C with a devolatilizing solution of the following composition:

N ^ -diethyl-p-phenylenediamine hydrochloride 5.0 g

anhydrous sodium sulfite 2.0 g

Sodium carbonate (monohydrate) b2.0 g

Potassium bromide 1.0 g

Water up to 1000 ml

The material was then exposed to the usual treatments such as stopping, fixing, washing with water and lead. Finally, it was washed with running water for 20 minutes and then dried, a brilliant cyan color positive image with a maximum absorption at bc? mp was obtained.

Example 5:

10 g of the coupler mentioned above as No. 3 for example wv.r-

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mixing the 20 ml of dibutyl phthalate, and the mixture was transferred by heating to 50 ⁰ C in a complete solution. This solution was mixed with 5 ml of the above aqueous solution of Alkanol B and 200 ml of a beige aqueous gelatin solution, and the mixture was passed through a colloid mill several times to prepare a dispersion. This dispersion was added to 500 g of a gelatin-containing silver chlorobromide emulsion, which was then coated on a baryta paper and dried to prepare a color photographic light-sensitive material.

The light-sensitive material produced in this way was exposed to light and then for 10 minutes at 20 ° C. with a developer solution the following composition:

N-ethyl-N-hydroxyethyl-p-phenylenediamine sulfate 2.5 g

anhydrous sodium sulfite 2.0 g

Hydroxylamine hydrochloride 1.0 g

Sodium carbonate (monohydrate) 82.0 g

Potassium bromide 2.0 g

Water up to 1000 ml

The material was then immersed in a stop bath containing 10 ml of glacial acetic acid, 3 × 0 g of caustic soda and 1000 ml of water and then immersed in an acidic, film-hardening fixer bath for 4 minutes. Danalx the material was washed for 10 min with water and long bleached at 20 ⁰ C for 8 min in a bath of the following composition..:

EDTA 2Na disodium salt of ethylenediaminetetraacetic acid 40.0 g

Perrichloride 30.0 g

Sodium carbonate (monohydrate) 20.0 g

Potassium bromide 30.0 g

Sodium thiosulfate (pentahydrate) 200.0 g

Water up to 1000 ml

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After washing with water for 20 minutes, the bleached material was immersed in a stabilizing bath for 2 minutes and then dried, leaving a cyan color image with a maximum Absorbance at 68b mp was obtained, which is good resistance to light and heat and is extremely stable.

Example 4:

2.0 g of the coupler mentioned above as No. 10, for example, was mixed with a liquid mixture consisting of 2 ml of dibutyl phthalate and 6 ml of butyl acetate were mixed, and the mixture was converted into a complete solution by heating to ÖO ° C convicted. This solution was mixed with 1 ml of a 10% aqueous Solution of alkanol B and 20 ml of a 5% aqueous gelatin solution mixed and the mixture was processed in a colloid mill to prepare a coupler dispersion. These Coupler dispersion was added to 100 g of a highly sensitive gel, atine-containing silver iodobromide emulsion coated on a support and dried to prepare a highly sensitive color photographic material

The light-sensitive material produced in this way was exposed to light by conventional methods and then with the same developer solution, which * Example 1 was described, developed * in whereby a red positive image with a maximum absorption at 500 mu and a cyan color image with a maximum absorption at 685 mp.

Example 5:

2.0 g of the coupler exemplified above as No. 7 were dissolved in 5 ml of butyl acetate. This solution was made with 1.5 ml of a 10 # aqueous solution of Alkanol B and 20 ml a 5 # aqueous gelatin solution, and the mixture was processed in a colloid mill to obtain a coupler dispersion to manufacture. The coupler dispersion became 100 g of a red color-sensitive, high-sensitivity gelatin-containing one

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Silver iodobromide emulsion was added, which was then coated on a splint support and dried to prepare a color photographic light-sensitive material. The light-sensitive material produced in this way was exposed in the usual way and then developed with the developer solution used in Example 1, a brilliant cyan color image with a maximum absorption of 685 τψ being obtained.

Example 6;

5.0 g of the above as the no. 2, for example, said coupler was a liquid mixture containing mixed with i> .0 ml of dibutyl phthalate and 15 ml of butyl acetate, and the G-emic was transferred by heating to 60 ⁰ C in a complete solution. This solution was mixed with 2.5 ml of a 10% aqueous solution of Alkanol B and 50 ml of a 5% aqueous gelatin solution, and the mixture was processed in a colloid mill to prepare a coupler dispersion. The coupler dispersion was added to 500 g of a red-sensitized silver chloride emulsion, which was then coated on a film support and dried.

On the other hand, 5 · 0 g of £ - £ 3- (2,4 ~ di-tert-amylphenoxyacetamide) -benzoylJ-2-methoxy-acetanilide dissolved and mixed with a gelatin solution in the same way as described above to make a dispersion. The dispersion was added to 500 g of a silver bromide emulsion, which was then applied to the above-mentioned coating to produce a photosensitive, to produce color photographic material.

The light-sensitive material produced in this way was exposed to X-rays in the usual way, developed for 10 minutes at 20 ^° C. with the same developer solution as was used in Example 1, and subjected to the usual stopping and film hardening treatments and then with water washed. After performing the second exposure with yellow light (using the Agfacolor separation filter Ji. \

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Exposure time 30 seconds), the material was developed again for 10 minutes at 20 ^° C. with the above-mentioned developer solution, stopped in the usual way, fixed, bleached and washed with water and then dried, a yellow color image with a blue background being obtained.

Example V;

i) .O g of the above as no. 5, for example, said coupler were added to a liquid mixture comprising 5.0 ml of dibutyl phthalate and 15 ml of butyl acetate, and the mixture was completely dissolved by heating at 6O ⁰ C. This solution was mixed with 2.5 ml of a 10% aqueous solution of Alkanol B and 50 ml of a 5% aqueous gelatin solution, and the mixture was processed in a colloid mill to prepare a coupler dispersion. The coupler dispersion was added to 500 g of a high-sensitivity silver iodobromide emulsion, which was then coated on a support and dried to prepare a color photographic light-sensitive material.

On the other hand, a gelatin scan having a thickness of about 5 γ was prepared on a cellulose triacetate film support. A thymidine solution which had been marked with tritium was dabbed onto this gelatin sc: .icht so that

the amount of which corresponded to 10 pe per cm. The dabbing was then repeated with a doubling dilution of the above-mentioned solution in order to produce a radioactive standard source with a step wedge of Ψ1 based on the radioactivity.

The surface of this gelatin film became in close contact brought to the film surface of the above-mentioned color photographic light-sensitive material. After for 15 hours was left in contact, the light-sensitive material of the same development as described in Example 1 was carried out subjected to a brilliant cyan color image was obtained indicating the presence of radioactive substance

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at the points corresponding to the radioactive source.

Patent claims:

008821/1689

Claims (1)

Claims ι Al light-sensitive, color photographic silver halide emulsion, characterized in that, as the cyan coupler, it is a compound of the general formula OH COHN-CH- (CH ₉ ) _n -COOCHCOOR ^ I j, 3 R ₁ R ₂ X where R _{1 stands} for hydrogen or a methyl group, R _{2 is} a hydrogen atom or an aliphatic hydrocarbon radical having 1-16 carbon atoms, R, stands for an aliphatic hydrocarbon radical having 1-18 carbon atoms, η is the number 0 or 1 and X is what. erstoffatom, a halogen atom or a substituted or unsubstituted Phenylazο group contains. Silver halide emulsion according to Claim 1, characterized in that that they are used as cyan couplers of the formula I N-fl- (dodecyloxycarbonyl-methoxycarbonylj-ethyl-i-hydroxy-2-naphthamide the formula OH (F. 55-56 ^u C) contains. 3. Silver halide emulsion according to claim 1, characterized in that that they are used as cyan couplers of the formula I N-f2- (dodecyloxycarbonyl-methoxycarbonyl) -ethylJ-1-hydroxy-2-naphthamide the formula -25-009821 / 1689 (F. 65 ⁰ C) contains. 4. silver halide emulsion according to claim 1, characterized in that that they are N-dodecyloxy as a gyan coupler of the formula I car "bony 1-methoxycarbonylmethyl 1-1 -hydroxy -4-chloro-2-naphthamide the formula COHIiCH ₀ COOCH ₀ COOC- _O H c. d ad (F. 69-7O ⁰ C) contains. Silver halide emulsion according to Claim 1, characterized in that it has as cyan coupler Ή- Cnpodecyloxycarbonylmethoxycarbonyl) -äthyIj-1-hydroxy-4- (2-acetylphenylazo) -2-naphthamide of the formula GOGH, (F. 93-95 ° G) contains. 6. silver halide emulsion according to claim 1, characterized in that that they are N-f-2- (dodecyl oxycarbony1-methoxycarbonyl) -ethylJ-1-hydroxy-4- (2-ethoxycarbonylphenylazο) -2-naphthamide as the cyano coupler the formula 009821/1689 8AD ORIGINAL OH (F. 137-138 ⁰ C) contains. 7. Photosensitive, color photographic material used in at least one silver halide not a cyan coupler contains, characterized in that the cyan coupler has the general formula I. 009821/1689