DE1940719A1 - Light sensitive silver halide emulsion for color photography - Google Patents

Description

46 765

Applicant: Konishiroku Photo Industry Co., Ltd,

Photosensitive halogen silver emulsion for parbene photography

The invention relates to a photosensitive emulsion for parbene photography, namely a light-sensitive one Halogen silver emulsion for parbene photography containing a new compound as a protected coupler.

There are numerous connections considered protected for this purpose Couplers have been proposed. The known connections however, they usually have certain disadvantages. In particular, little is known about a protected Coupling connection that could be produced with a reasonable level of purity with justifiable little effort.

For example, a coupling compound of the formula "

—NHCOCH - 0
⁰ A

those described in US Pat. No. 2,801,171 is. Although this compound has an advantageously good solubility in high-boiling solvents, must a very expensive starting material is used in their manufacture and the joint is difficult to clean.

009809/1529

Another coupling compound of the formula OH

CONHCH ₂ Ch ₂ NHCOCH ₂ GH ₂ N:

is known from Japanese Patent Publication No. 2835/1964. This also knows good solubility in high-boiling solvents. However, it can only be produced in a very complex manner because it is more oleophilic Proportion must be produced starting from expensive starting material over several process stages.

The invention is based on the object of providing a light-sensitive To create an emulsion for parbene photography which does not have the disadvantages described above and which is one Coupling compound contains which compared to known conventional coupling compounds, improved photographic Has properties and which can be produced in high purity by means of inexpensive processes at low cost leaves.

This object is achieved by a light-sensitive halogen silver emulsion for parbene photography of the initially introduced described type, which is characterized according to the invention in that it contains a compound as a protected coupler the general formula

B - (X) _n . - NHCO - (CH) ,, - COOR ₀ ^v q-1 t η 2

^R l

is included in which
B represents a remainder capable of coupling,

nR, for η hydrogen atoms or at most one aliphatic C ₁ to Ch hydrocarbon radical and (n-1) hydrogen atoms attached to the terminal C atom of the alkylene chain,

denotes an aliphatic C " to C ^ -hydrocarbon radical,

009 009/152

X one to establish the bond between the couplable Radical and an acylamino group is capable,

η for 2 or 5 and $ represent 1 or 2. .

The light-sensitive silver halide emulsion for color photography according to the invention has the advantage that, after it has been applied as a layer, it forms a stable film which remains free from crystallization of the coupler contained therein. The coupling compounds present in the emulsion according to the invention have the following advantages:

1. You can do it in a simple and economical way, ' starting from long-chain ones readily available on the market Manufacture alcohols,

2. They have good solubilities in dibutyl phthalate, tricresyl phosphate or the like high-boiling solvents, so that a highly concentrated, stable Coupler dispersion is available and the possibility exists, which is required for the coupling connection Reduce amounts of solvent, and

3. due to their low melting point they show no

* tendency to get out of the emulsion or a coating in which they are available to crystallize out.

These coupling compounds are particularly useful as protected couplers in color photography, and they can be synthesized in the following manner.

It becomes a long chain alcohol and an anhydride one dibasic carboxylic acid (e.g. succinic anhydride or QIutaric anhydride) reacted with one another, so that a monoalkyl ester of a dibasic carboxylic acid is formed, and this is then reacted with thionyl chloride. The acid chloride obtained in this way is with a one

009809/152 5

Amino group-containing coupling compound condensed, and you get the desired coupling connection. The method described above can be carried out by the following chemical formulas are illustrated.

R ₁ - CH - CO _v

I \ p
^ ⁵ ° " ^00σ - ^(σΗ ^ _η - ^C00H

CH ₂ -CO

SOCIo. H ₀ W - (X), - B - 000 - (CH) _n - COCl - 2: - - = ±

R ₂ -r.'00C - (CH) _n - COHN - (X) _4-1 - B

In the above formulas, R ,, Rp, B, X, η and q have the meanings given above, and ρ stands for 1 or, 2.

In the general formula; by the invention Coupling compounds are reproduced, the couplable radical (B) means a group of a phenolic Hydroxide-bearing compound (such as phenol, naphthol and the like) or its derivative or a active methylene-bearing compound (such as pyrazolone, indazolone, acylacetanilide, and the like) or their derivatives. Furthermore, the group X for

OXl, 9 80 9 / T S 2

any group that has the ability to link the couplable radical with an acylamino group, and such groups are, for example, an imino group or a residue of an alkylene group bearing an imino group or arylene derivative,

Typical examples of coupling compounds which can be used for the emulsion according to the invention are listed below, without expressing any limitation.

Cl (2)

(3) i V-NHCO-CH-CO

OCH ₃ ⁰¹

(4) ' (\ - , NHCO - CH - CO

OCOCH ₃

ÖlMöt / ifii

(5)

- 6-

CH ₂ -C

ο = σ

\ "/

CH.

(6)

O = C

- σ - Mco

Cl

(7)

CH ₀ -C- MCO

I ² Il c sr

(8th)

cn

CH.

CHp-C-M

0 = C N

οι

Cl IJHCOCH ₂ CH ₂ COOc ₁₂ H ₂₅

(9)

CH ₉ - C - NHCO I ^ά 1 O = CN

Cl

NHCOCH-Ch ₂ COOC CH,

O = C

- C - NHCO

Il

Cl

NHCOCH ₂ Ch-COOC ₁ - CH,

(10)

CHp - O - NHCQ- £ \ - NHCOCHCH ₀ COOc ₀ H, rj

I. O = C

Ii N O ₄ H ₉

COOC ₂ H ₅

CH ₀ -C-

* ² Ιο = CN

- ^ "V-NHCOCH ₂ CHCOOc ₈ H ₁₇

4 ^H 9

COOC ₂ H ₅

0 098 09 / Ί

- 8 (11). CH ₂ -CJ - NHCO - \ _ J

0 =

σ ν

(12) CH ₃ O

N = N-CH-C-NH

I II O = C N

Cl

Cl

H ₃ CO "£"*> - N = N-CH-C-NH

I Π

.: ': O = CN

Cl

OH

CH,

JkJ

Cl

009609/1 ^ 3

OH

COHHCH ₂ CH ₂ MCo (CH ₂ ) 2-

CONHOiLCH,

.-TVi

, -IECOOH ₂ Oh ₂ OOOO ₁₃ H ₃₅

OH

COIIHCH ₂ Ch ₂ NHCO (CH ₂ ) ^ -COOCH ₅ CH-C ₄ H ₉

^C 2 ^H 5

Typical synthetic methods for these coupling compounds are described below.

Synthesis example (1)

105 g of succinic anhydride were heated on an oil bath, 187 g of n-dodecyl alcohol are added to the resulting melt was added and the mixture was allowed to stir for 3 hours Stirred from 22o-125 ° C. After cooling, the solidified Recrystallized mass from hexane. Succinic acid mono-n-dodecyl ester which melts at 44.5 ° to 45 ° C. is obtained. l45 g of this ester were mixed with l40 g of thionyl chloride, and the mixture was allowed to stand overnight. The thionyl chloride was reduced by distillation under reduced pressure Pressure removed. The remaining mass, succinic acid mono- -n-dodecyl ester chloride, was then 4 acylation subject.

00980971523

28.0 g of ct- (3-aminobenzoyl) -2-methoxyacetanilide and 40.0 g of the chloride recovered as described above became the mixture of 500 ml of glacial acetic acid and 9 * 0 g of anhydrous Sodium acetate added. The mixture was heated on a water bath for 2 hours and then poured into water. The precipitate that formed was "filtered off, washed with water and then dried. The crude product was made from a mixed solvent of benzene and hexane recrystallized, and thereby the above under (I) P reproduced coupling compound as a white powder, which melted at 103-104 ° C, obtained. The yield was 4 0.0 g ($ 74 of theory). The elemental analysis showed the following Result:

Calculated! 5.07 %

Found: 4.78 %

In the same way as described above, the coupling compounds specified above under (2), (3) and (4) can be obtained.

Analysis for nitrogen

Coupling melting point

link ( Ql ...'-. calculated found

No. (2) 92-93 5.22 5.32 '

No. (3) oil 4.77 5.25

No. (4) 61-62 4,59 4,: 8ö

Synthesis example (2)

39.8 grams of 1- (2,4,6-trichlorophenyl) -3- (3-aminobenzamido) -5-pyrazolone was made in the mixture. 200 ml of acetonitrile and 40 ml of pyridine were suspended and added to the suspension 42.0 g of succinic acid mono-n-dodecyl ester chloride were added, followed by boiling for one hour. Afterward this suspension was added to water, and

009809/1529

- 11 -: ■ :.

the oil which separated out was extracted with ethyl acetate. The extract was washed with water, dried and then the solvent was stripped off. The remaining oil was in Dissolved methyl alcohol and the resulting solution became sent through ion exchange columns, each individually with • AmberllteCG 120 and Amberlite CO 400 from Röhrt ft Haas Co., U.S.A., were filled. The solvent was distilled off from the treated solution, and the remaining mass was made from a mixed solvent Benzene and hexane recrystallized. It became a pale yellow obtained at 77-78 ° C melting powder. This was the coupling connection previously listed under (6). The yield was 39 g (595ί of theory).

The previously described procedure was in essence of the same kind repeated, and the previously under (5) to (11) and (15) to (l6) specified coupling compounds obtained.

Analysis for nitrogen

Clutch (5) Melting point calculated found link: '(6) ( ⁰ C) 8.30 8.15 No. (7) 51 ^ 52. 8.17 No. (8th) 77-78 8.96 8.70 No. (9) 85-87 8.33 8.20 No. (XO) 132-133 9.16 8.92 No. (11) 65-68 8.83 9.09 No. (15) 182-183 7.88 7.86 No. (16) 156-157 3.37 3.3 * .--- "■ No. 61-64 4.27 4.29 No. 152-155

00 9 809/152

: ■ '' ■ - - '■■■ - 12 - ^; :

Synthesis example (3)

22.9 g of 2-amino-4,6-dichloro-5-methylphenol hydrochloride were mixed with 550 ml of acetone and 25.0 g of diethylaniline. The resulting mixture was added to 40.0 g of succinic acid mono-n-dodecyl ester chloride, followed by stirring for one hour, followed by boiling for one hour. The reaction mixture was filtered and the filtrate was concentrated. Then the remaining oil was added to a mixture of conc. HCl and water added. The solidified oily mass was filtered off, washed with water, dried and then recrystallized from acetonitrile, 30.0 g (yield 65 #) of a white ^{powder melting at 72 74 °} C. being obtained. The product was the coupling compound listed under (14). The analysis for nitrogen gave the following values

Calculated: $ 3.04

Found: * 3.19 %

Synthesis example (4)

3.6 g of p-aniside, 40.0 ml of water, 10.0 ml of con " centered hydrochloric acid and 2.4 g sodium nitrite "reacted with each other, and then 80 ml Ethyl alcohol added.

The diazotized solution obtained in this way was at 5 - 10 ° C ' added to a solution of 12.8 g of the coupling compound (8) in 128 ml of pyridine. The resulting mixture was stirred for 3 hours and then diluted with 300 ml of water, 128 ml of concentrated hydrogen chloride were added off acid added and the precipitate that separates out was filtered off, washed with water, dried and then recrystallized from ligroin. There were

009809 / 1S ^ 9

11.6 g (yield 85%) of an orange-colored powder melting at 106-107 ° C. were obtained. This product was the coupling compound listed above under (13).

The procedure described above was repeated in the same way, but instead of the coupling connection (8) 1- (2,4,6-trichlorophenyl) -j5 ~ Z ~ 4- (ß-do- " decyloxyearbonyläthylcybamyl) -anilino_7-5-pyrazolone used, and the coupling compound listed under (12) was obtained.

Furthermore, when the procedure described above was repeated in the same way, however, using of diazotized! O-aminoacetophenone and the coupling compound (15) instead of diazotized! p-anisidine and the coupling compound (8) that listed under (17) Coupling connection won.

The melting points and those determined during the analysis for nitrogen Values of these coupling connections are illustrated below.

Analysis for nitrogen ■■ <*). '

Coupling melting point

compound (C) calculated found

No. (13) 106-107 10.42 10.26

No. (12) 85-87 10.88 10.70

No. (17) 126-127 9.68 9.41

For the preparation of a photosensitive emulsion for parbene pho'tography according to the invention, any of the coupling compounds prepared as described above can be used in a high-boiling solvent (boiling point 175 ^° C. or higher), such as, for example, tricresyl phosphate, dibutyl phthalate or the like, or in a low-boiling solvent, such as butyl acetate, butyl propionate or the like * or in a mixture

00 98 09/1529

- l4 -

these two types can be resolved. The solution prepared in this way can be mixed with an aqueous gelatinous solution, which is a contains surfactant, can be mixed.

Subsequently, the thus obtained coupler dispersion is emulsified by means of a high-speed rotary mixer or a colloid mill and then added directly to a photosensitive halogen About emulsion * on a suitable carrier support (beigielsweise movie film, baryta paper, or ψ like) is applied as a layer and then dried to give to remove most of the low-boiling solvent. Alternatively, the emulsified coupler dispersion is allowed to solidify and extruded into nude shaped pieces which are then subjected to a water wash or similar process to remove the low boiling point solvent. Thereafter, the product is added to a photosensitive silver halide emulsion, which in turn is coated onto a support and dried, whereupon a silver halide photosensitive material is obtained. It is understood that the type of introduction of the coupling as previously described. The compound into a light-sensitive photographic emulsion is used as an example only and does not limit the scope of the invention in any way.

The preferred amount in which the coupling compound im The ratio to the photographic emulsion used is usually 10-100 g per mole of halogen silver. However, this is not essential to the invention; depending on the ; Intended use of the finished product, the amount may vary. The photosensitive halogen silver emulsion can any silver salt such as silver chloride, silver iodide or silver chloroiodide. In addition, the emulsion can contain any sensitizer, for example sulfur sensitizer, polyalkylene oxide sensitizer, Sensitizers based on

009809/1529.

of precious metal or the like. It can too other photographic additives in the photographic emulsion be present, such as agents to prevent a gray haze, stabilizers, anti-stain agents, Anti-overexposure agents, film promoting agents, and the like. Known optical sensitizers, such as cyanine paraffin, Merocyanine dyes and the like may also be included.

A photosensitive silver halide material for the Color photography made using those previously described light-sensitive halogen silver emulsion for color photography can be exposed to active radiation (α-rays, ß-rays, X-rays, visible light, and infrared rays the like) and then treated with a liquid developer which is a p-phenylenediamine type compound contains. The resulting developed image is bleached and fixed to become a highly transparent dye image with good spectral absorption properties won.

Typical compounds of the p-phenylenediarain type which the liquid developer as the main effective ingredient Contains are the sulfates, sulfites and hydrochlorides of N, N-diethyl-p-phenylenediamine, N-ethyl-N-ß-methanesulfonamidoethyl-3-methyl-4-aminoanllin, N-ethyl-N-hydroxyethyl- -p-phenylenediarain, N-ethyl-N-hydroxyethyl-2-methyl-p-phenylenediamine, NiN diethyl-a-methyl-p-phenylenediamine, and the like.

Below in Table I are the melting points of the Coupling compounds present in emulsions according to the invention compare with those of known coupling compounds that have similar structure.

00 9 809/1 52 9

CTI CO

Coupling connection coupler (I)

Table I structure

^C 12 ^H 25 ^{C00 CH} 2 ^{CH 2 CO NH}

Coupler in accordance with American patent specification 2.8t5 * P57

Coupler (6)

OCH ₂ CONH

CH ₀ -C- HHCO

C ² ! I

O = C N

Cl

OCBL v-5

oc:

COCH ^ COHH

OCH ₂

Melting point ( ⁰ C)

103-, 104

126-127

77-78

940719

. . OOι.

t CM

I H

J »

rf ¹

oa.H ι

Ot d +>

Q) <sj φ

JL | (D (Ij -1-5 VO '

ω Ε «η ·>

H 3 (j -HOO

ft <D U H

ft £ h XS XS VO

3 φ ο ο · »

W Ό W u) cvi

bO>

09809/152

The above data clearly show that the in the couplers contained in the emulsions according to the invention have significantly lower melting points than the known couplers commonly used.

Furthermore, some test results are shown in Table ZI, which demonstrate the high solubility of the couplers present in the emulsions according to the invention. The IiÖsiichfceitsgrad is indicated as the amount art * ^ ibutylpHthalat (ml) required to I ₄ O grams of the coupler at 60 ° C to dissolve.

98 09/152

'Table II

Coupling connection

Structure amount of
Dibutyl phthalate (ml)

Coupler (1)

COCH ₂ CONH

5.0

Coupler according to tCcH-v of the American patent

OCH ₂ CONH

GOCH ₂ CONH

7.5

Coupler (6) CH ₂ ^ c-HHCO

I H

O = C N

Cl

Cl

Cl 1.5

CV

O-

Il O

> Γ "

S I. MS

IsI

M ¹ U (D

00980971529

The above data clearly show that the couplers present in the emulsions according to the invention the usual and known coupling compounds with regard to solubility in high-boiling solvents are superior, and this confirms that the invention used couplers as protected couplers for the Color photography are particularly useful. .

As a result, one can explain that a light-sensitive A halide silver emulsion for color photography according to the invention, which comprises a coupler of the above contains general formula, is not subject to crystallization of the coupler, and this leads to the result that such an emulsion has excellent dye images good spectral absorption properties and good transparency gives what is due to the fact that random spectral absorption does not exist.

In the following examples, however, they are not intended as a limitation the scope of the invention are to be understood, the invention is explained in more detail.

example 1

20 g of the coupling compound previously listed in (1) were dissolved at 6O ⁰ C in the mixture of 20 ml of dibutyl phthalate and 60 ml of butyl acetate. The resulting clear solution was mixed with 10 ml of an aqueous solution of 10 # Alkenol B (alkylnaphthalene sulfonate, manufactured and marketed by Du Pont, USA) and 200 ml of an aqueous solution with 5 % gelatin. The mixture was treated with a colloid mill.

■■ .. '■■ - 22 -.; ■: ■.

The coupler dispersion thus obtained became 1 kg of one high-performance Gelatirio-Jodbromidsilber-Emulslon given, which in turn spread on a foil base and dried. It became a photosensitive photographic film having a stable photosensitive Layer received.

This photographic film was exposed in a conventional manner and then 10 minutes "at 20 ⁰ C with a liquid developer of the following composition treated: ^, N-diethyl-p-phenylenediamine hydrochloride 2.5 g Anhydrous sodium sulfite 2.0 g

Sodium carbonate monohydrate 82.0 g

Potassium bromide ♦ 2.0 g

Water, to fill up to 1000 ml.

The treated film was then treated with a breaker and a fixing solution for 10-15 minutes Washed water and then treated for 5 minutes with a bleach solution of the following composition:

Potassium ferricyanide 100 g

Potassium bromide 50 g

Water, to fill up to 1000 ml.

The film was washed with water for 5 minutes and then treated with a fixing solution of 250 g of sodium thiosulfate in 1000 ml of water for 5 minutes. It was then washed with water for 20-25 minutes and then dried. A glossy, yellow dye image with an absorption maximum at 440 m λχ was obtained.

The procedure described above was repeated, except that couplers (6) or couplers (15) were used instead of coupling compound (1). Clear magenta or cyan dye images with an absorption maximum at 540 m / U or 670 m λχ could be obtained. 0 09809/15 29

Example 2

10 g of the coupler previously listed in (2) were dissolved at 50 ⁰ C in 10 ml of tricresyl phosphate and 30 ml Bütylacetat. The resulting clear solution was mixed with 5 ml of an aqueous solution of 10% alkenol B and 800 ml of an aqueous solution with 5 % gelatin. The resulting mixture was treated in a colloid mill.

The coupler dispersion thus obtained became 500 g of one light-sensitive oilatino-iodobromide silver emulsion was added, with which a film substrate was coated. Afterward was dried.

The photographic "light-sensitive halogen!" LBER FiIm was exposed and treated for 10 minutes at 20 ⁰ C with a liquid developer of the following composition:

Methol 3.0g

Anhydrous sodium sulfite 60.0 g, hydroquinone 6.0 g

'""' trasserfr ^ Iea '! Sodium carbonate 50.0 g Potassium bromide 1.0 g

Water, to fill up to 1000 ml.

After interrupting, film hardness and water washing in the usual catfish, the film was exposed a second time and then behandeltt C for 10 minutes with a liquid developer of the following composition at 20 ⁰

Ν, Ν-diethyl-p-phenylenediamine-

Hydrochloride 5 »Qj &

Anhydrous sodium sulfite J ₁ Og Sodium carbonate (monohydrate) 1.0 g Potassium bromide 82,0g

Water, to fill up to 1000 ml *

0098.09 / 1 52

The film would then be interrupted and Treated fixing solution, washed with water and immersed in the bleached in the usual way and then soaked and dried under running water for 20 minutes. It was a yellow positive color image obtained that has good transparency and had an absorption maximum at 445 πΐ / U.

In practically the same procedure as described above, however, using the coupling compounds given under (8) or (16) instead of the coupler (2), were able to produce clear magenta or cyan color images with an absorption maximum at 535 m / rev and 680 m yu, respectively can be obtained.

Example 3

10 g of the coupling compound given above under (14) were dissolved in 20 ml of dibutyl phthalate ^{at 50 ° C.} The resulting clear solution was mixed with 5 ml of an aqueous! Above alkanol B solution and 200 ml of an aqueous 5 # gelatin solution. The resulting mixture was passed through a colloid mill several times.

The thus obtained coupler dispersion became 500 g of a gelatinous chlorobromide silver photosensitive emulsion
given, and this was applied as a coating on a Baryta paper and dried.

The photographic light-sensitive silver halide film produced in this manner was 10 minutes long treated in a developing bath of the following composition by exposing at 2O ⁰ C:

009809 / i 52 9

- ■ -.25 - ■■ .- '-...-. ■■

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

Anhydrous sodium sulfite 2.0 g

Hydroxylamine hydrochloride 1.6 g

Sodium carbonate (monohydrate) 82.0 g

Potassium bromide 2.0g

Water * to fill up to 1000 ml.

The film was then consisting of a break bath from 10 ml of glacial acetic acid, 3.0 g of sodium hydroxide and 1000 ml of water, immersed and immediately afterwards in a film hardening agent containing fixer for Λ minutes. After washing in water for 10 minutes the film was treated at 20 C for 8 minutes in a bleach bath with the following composition:

Ethylenediaminetetraacetic acid

Disodium salt kO g

Ferric chloride JO g

Sodium carbonate (mortohydrate) 20 g

Potassium bromide ". '30g

Sodium thiosulfate 200 g Water, to fill up to 1000 ml.

After washing with water for 20 minutes, the film was in a stabilizing ^ for 2 minutes bath dipped and then dried. It became a cyan dye image with good lightfastness and moisture resistance obtained, which had an absorption maximum at 680 nyu. .

Example 4

2.0 g of the coupling compound specified above in (13) were dissolved 2 ml of dibutyl phthalate and 6 ml of butyl acetate at 60 ⁰ C iri. The resulting clear solution was

00 98097 152

with 1 ml of an aqueous 1 above Alkanol B solution and 20 ml of an aqueous 5 # gelatin solution mixed.

The coupler dispersion thus obtained became 100 g of one added high-performance photographic light-sensitive gelatino-iodobromide silver emulsion, which in turn is applied as a coating to a film base and dried.

After exposure in the usual way, was the photographic photosensitive film with a Color developer as indicated in Example 1, treated. A yellow positive color image with an absorption maximum at 440 m / u and a magenta color image with a Absorption maximum obtained at 54Ό m / U.

Practically the same procedure as described above was carried out using the coupling compound shown in (17) above instead of the coupler (13), and this resulted in red positive color images with an absorption maximum at 520 m Ai and cyan dye images with an absorption maximum at 670 m Ai won.

Example 5

5.0 g of the coupling compound indicated under (15) warden dissolved at 60 ⁰ C in 5.0 ml of dibutyl phthalate and 15 ml of butyl acetate. The resulting clear solution was mixed with 2.5 ml of an aqueous 10% alkanol B solution and 50 ml of an aqueous 5% gelatin solution. The mixture was treated with a colloid mill.

The coupler dispersion thus obtained became 500 g of one photographic photosensitive chlorine silver emulsion,

00980 9/1529

which was sensitized in the wave range of red light was added. This emulsion was coated on a film base and then dried.

5.0 g of the couplings specified under (1) were separated compound loosened and treated with a gelatin solution in the same way as. described above to form a Dispersion mixed. The dispersion became 500 g of one Added silver bromide emulsion, which was then applied to the aforementioned coating on the film base to obtain a to produce light-sensitive color photographic film.

The photosensitive photographic film thus prepared was exposed to X-rays in the usual manner, and then, at 2O ⁰ G for 10 minutes with a developer,

.. """. ■ .. -. - ■■■ '""". · Ι as used in Example 1, treated. After interruption, film hardening and washing with water in the usual way, the treated film was exposed a second time to yellow light (exposure time 30 seconds, an Agfa reprocolor separation filter was used) and then exposed to 20 ⁰ O for 10 minutes treated with the same developer as indicated above. Breaking, fixing, bleaching, washing with water and drying were carried out as usual. A clear yellow dye image on a blue background became

reason received.

Example 6

5.0 g; "der'unter (d) ■■ specified coupling compound was dissolved at 60 ⁰ C in-the 'mixture of 5.0 ml of dibutyl phthalate and 15 ml Bütylaoetaf. The resulting clear solution 2.5 ml of an aqueous wuafrde iOxigen alkenol B-Iösung ./ and 50 ml of an aqueous 5 # gelatine solution were mixed. The resulting mixture was treated in a colloid mill.

9809/15 29

194071S

- 28 - ■ · γ-

The coupler emulsion obtained was 500 g of a hooh powerful photographic light-sensitive silver iodobromide emulsion »and with this one became a JFilmunt would be coated, and then dried, whereby a silver halide photographic photosensitive film was obtained. ·.

Separately, a gelatin layer with a thickness of about 5 / u in the dry state was applied to an oil-cellulose triacetate film. A thymidine solution marked with tritiated was spotted on this layer in an amount of 10 / µc (micro-count) per square centimeter. Afterwards the stippling was repeated using a double dilution of this solution

The gelatin layer of this radiation source has been brought into contact with the layer licnieinplSidliohen dee llohteapfindlichen fotografiechen Filiii, and the resulting composite structure liels ojui 15 hours laaj.4 ⁿ einek

e the £ ·· * became '; ,

standing dark room, latineichioht away, Treated according to you in Beie method, Bs rftdioaktiTen source d i w

Activate Bubstanr aneift

ier photographic time span written

in the place »neeohicht

the

Presence of the radio *

009809/1529

Claims (1)

Gi Light-sensitive halogen silver emulsion for colors photography, characterized in that it is protected as a Coupler a compound of the general formula B - (X) (J.! ^ NHCO - (CH) _n - COOR ₂ is contained in which. · "■ ■ B represents a remainder capable of coupling, nRj for η V hydrogen atoms or at most one at that terminal C ^ atom of the alkylene chain aliphatic C ^ to C ^ hydrocarbon radical and (n-1) hydrogen atoms,
Rg is an aliphatic Cy to C ^ g hydrocarbon radical means,
-X one capable of producing the bond between the group capable of coupling and an acylamino group Group is
η for 2 or ^ and
q stand for 1 or 2. 2. Photosensitive hemogenous silver emulsion for color photography according to claim 1, characterized in that it contains a compound of the structural formula as a protected coupler - "■ -" NHCOGH ₂ CO ICOCH ₂ Ch ₂ COOC ₁₂ H _{25 is} present. 3, Bänülsion according to claim 1, characterized in that that therein as a protected coupler a compound of Structural formula ; 'W: mm ji -? CpcÖ 0 aß 0 9/1 52 9; '■:: CH _n -C- HHGO-ν 'O = C N N .. i ^ Cl Ϊ T is included. 4. Emulsion according to claim 1, characterized in that therein as a split coupler a compound of the formula CH ₂ -C- ⁼ \ J NHCOCH ₀ CH ^ cCOG ₁₀ is included. 5. Emulsion according to claim 1, characterized in that therein as a protected coupler a compound of the formula ΟΉ , Ο-iV N = Ii-CH - C - NH - /> - l! IJOC'L · CH.COCJ, II O = C N Cl 1 .Cl Cl, is included. 009809/1529 6. Bnulsion according to claim 1 »characterized in that therein as a protected coupler a compound of the formula is present * a 7, EwuIsion according to claim 1, characterized in that «dafi therein as a protected coupler a compound of the formula Jj-OOOOH ₂ CH-C ₄ H ₉ C ₂ H ₅ is included. 8. Qeule ion according to claim 1, characterized in that dafi therein as a protected coupler a compound of the formula CONHCHjCHgtlHCO (CH ₂ ) COOH ,. ^? ; is included. 009009/152?