DE2035382A1 - Prevention of color mixing in reversal color photographic light-sensitive materials with multiple layers - Google Patents

Description

DR..E. WIEGAND DIPL-JNG. W. NIEMANN 2035382 DR.M.KOHLER DIPUING. C. GERNHARDT WONCHEN HAMBURG TELEPHONE: 55 547 «8000 MÖNCHEN 15, ■ ^l6 · JUli 1970 TEtEGUAMME ₅ KARPATENT NUSSBAUMSTRASSE 10

W. 14 975/70 -

. - ■ ■ ■: · J

FujiPhoto PiIm Co., Ltd. . *

Ashigara, Kamigun, Kanagawa (Japan)

Prevention of color mixing in color photographic, reversal photosensitive materials with multiple layers

The invention relates to a method for preventing color mixing in color photographic, light-sensitive reversal materials with multiple layers, developed according to the coupler-in-the-developer process will.

As a color photographic, light-sensitive material with multiple layers, which is a red-sensitive Emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer on a surface have, there is a type of photographic light-sensitive material in which the photographic emulsion layers have couplers capable of forming colors through Reaction with the oxidation product of silver halide and

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a photographic primary developing agent from aromatic amino type capable of containing, and a kind of light-sensitive material which the photographers can freely see Emulsion layers do not contain such couplers.

When the latter type of color photographic light-sensitive material after exposure in color-forming Developing solutions containing couplers are developed, the sharpness of the color images is better than that of the former type of color photographic light-sensitive materials. However, in an ordinary procedure not just one type of dye, but others as well Dyes not present in the emulsion layer should, formed in the emulsion layer in the development process, resulting in color mixture, what damage to the color rendering in the development of the color photographic light-sensitive material results. If z. B. the latter type of color photographic, reversible photosensitive material with a red-sensitive Emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer on top of one Supports in this order after exposure to black and white development, gyan color development, yellow color development and magenta color development, hereinafter referred to as color photographic reversal treatment

ment of the coupler-in-developer type is called a cyan image or a yellow image in the green-sensitive Emulsion layer is formed except for the magenta dye and therefore, 4a's magenta image becomes purple-like to some extent or reddish, and a magenta color with high color purity cannot be obtained.

This mixture of colors is caused by the development fog

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caused «namely by the phenomenon that in the Color formation development of an emulsion layer over them Halide grains in the unexposed parts of the emulsion layer be developed with the formation of an undesirable dye. Venn, for example, the one listed above Kind of color photographic reversing light-sensitive material in the order given above is developed, the green-sensitive emulsion layer to be developed by a magenta color developing solution is subject before exposure to magenta color development, cyan color development, thereby cyan mist development occurs, which results in a mixture of cyan colors, and further- | the emulsion layer then becomes the yellow color development subjected, whereby yellow mist development occurs, which causes yellow color mixture.

Various methods have been proposed to overcome these difficulties. For example, there has been proposed a method in which an anti-fogging agent is incorporated into the cyan developing solution to prevent the occurrence of a mixture of cyan colors, but this improvement also suppresses the cyan color development treatment and increases the undeveloped grains which are then used in the subsequent yellow or yellow color Magenta developing solution, thereby causing yellow and magenta colors to mix in the cyan image. %

There is also a method in which an anti-fogging agent is incorporated in the yellow developing solution to prevent yellow blending from occurring, however This method also suppresses the yellow color formation treatment, thereby causing a magenta color mixture in the Yellow image is caused.

Furthermore, it may be possible to develop leverage in a green-sensitive emulsion layer by a

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Cyan color image development or a Geb color image development prevent by adding an anti-fogging agent to the; green-sensitive emulsion layer is incorporated, however this addition generally has bad influences the other important properties of the photographic light-sensitive material, so the choice of such Additions is very limited .. Therefore it is very difficult the appearance of a cyan color mixture and a tanning color mixture in the magenta color forming emulsion layer in the coupler-in-developer type reversal color photographic treatment without preventing further bad effects.

The object of the invention is to provide a color photographic reversal photosensitive material of the coupler in the developer type, which is capable of forming a magenta color image of high color purity without cyan color mixing and yellow color mixture after developments in the coupler-in-developer type reversal color photographic process appear.

Another object of the invention is to provide a color photographic light-sensitive material with multiple layer, which is used to develop a high color density according to the developments in color photography Coupler-in-decelerator type processing capable; is.

In the context of the invention it was found that this Tasks can be achieved when a diffusion-resistant or ballasted magenta coupler into the thoroughly sensitive emulsion layer of the color photographic , reversal photosensitive material of the Kupperim developer type is incorporated.

Even if there is fog development on the silver halide grains takes place in the green-sensitive emulsion layer during the cyan development, according to 'the invention

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V ₅ , - '2035332

formation is the oxidation product of the primary developing agent astonishingly predominantly with the diffusion-resistant material present in the green-sensitive emulsion layer Magenta coupler implemented and not with the cyan coupler supplied from the developer solution, whereby an extreme reduction in the occurrence of the cyan color mixture results. Furthermore, in this case, even if fog is developed on the silver halide grains in the green sensitive emulsion layer in the yellow color developing solution occurs, the oxidation product of the primary developing agent predominantly with that in The diffusion-resistant magenta coupler present on the green-sensitive emulsion layer implemented and not with the yellow coupler supplied from the developing solution, so that a magenta image is obtained, which also extremely reduces the occurrence of yellow color mixture.

The summation of these effects makes a cheaper one Obtained magenta coupler with high color density and little color mixing according to the invention.

The diffusion-resistant magenta couplers used in the context of the invention can be selected from generally known magenta couplers (see W. Pelz, communications from the research laboratories of Agfa, Leverkusen-München, III ,: μ 126 to 156 (1961)). In particular, the compounds represented by the general formulas I and II below give better results

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R - C - CH - X N C - O

»'- CI)

and

R ₀ - C - CH- CH-CCR ₀ (II)

C. H ι I Il *?

NC «OO a C H

• i ^

where R ^ a group of the aryl series, a group of the heterocyclic ring series »a group of the carbamyl series or a group of the thiocarbamyl series, R ^ a hydrogen atom, a group of the alkyl series, a group of the aryl series * a group of the amino seriesi a group of the lireido series, a Group of the carbonamide series, a group of the sulfonamido series or a group of the sulfamyl series, R ^ a lower alkyl group or an aryl group and X denotes a hydrogen atom or a group released during the coupling, at least one of the groups R ₄ .. and R _{2 being} at least one hydrophobic Qruppe having 8 to 30 carbon atoms, which is necessary to achieve the diffusion resistance properties of the coupler ^.

In the above formula, R> in detail. in the general formulas I and II an aryl group or one with an alkyl group of 1 to 1β carbon atoms substituted aryl group, an alkoxy group, an aryloxyl group, an alcoholic carbonyl group. an amino group, a carbonamide group, a sulfonamide group, a carbamyl group, a sulfamyl group, a sulfone group, a Sulfonyl group, a hydroxyl group, a carboxyl group

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or a halogen atom, for example a phenyl group, a 4-methoxyphenyl group, a 2-octadecoxyphenyl group, a 4-phenoxyphenyl group, a 2-chlorophenyl group, a 2,4-chlorophenyl group, a 2,4,6-trichlorophenyl group, a ^ -chlorine ^ ie-dimethylphenyl group, a 4-bromophenyl group, a ^ methoxy- ^ je-dichlorophenyl group, a 4-fluorophenyl group, a 2- (ailor-5-tetradecyloxycarbonyl- · phenyl group, a 2-chloro-5- / ä- (2i4- di-tert-amyl-phenoxy) -acetamidp7-phenyl group, a 2-chloro-5- ( ^2- t-ittethylphenyl-V ßulfonamido) -phenyl group, a 3 »5-dicarbamylphenyl group, a 4-N- (phenylethyl) -N - (p-tolyl) -sülfamyl-pheny! group, | a 4-sulfophenyl group, a 4-phenoxy-3-sulfophenyl group, a 4-methoxysulfonylphenyl group, a 4 ^ -HyUrOXyphenyl group or a J-carboxyphenyl group, a 5- or 6- membered heterocyclic ring or a 5- or 6-membered heterocyclic ring substituted with substituents of the same kind as in the case of those listed above n aryl groups such as a furanyl group, a benzothiazolyl group, an oxazolyl group, an imidazolyl group, a quinolinyl group and the like., a group of the carbamyl series such as a carbamyl group, a methylcarbamyl group, a phenylcarbamyl group and the like

series, for example a SMocarbamyl group, an Ethyl ™ thiocarbamyl group, a phenylthiocarbamyl group, the Rp is a hydrogen atom, an alkyl group with 1 to 30 Carbon atoms, optionally with substituents, for example alkoxyl groups, aryl groups, aryloxy groups, Halogen atoms, hydroxyl groups and the like, for example a Hethy! group, a 2-propenyl group, a pentadecyl group, a 2-Metdioxyäthylgruppe, a benzyl group, a 2-phenoxyethyl group, a hydroxyethyl group and the like., A

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Aryl group or one having the same substituent as R ,. substituted aryl group, a group of the amino series such as a primary amino group, a benzylaraino group, a 3,5-dicarboxyanilino group, a 4-nitroanilino group, a 2,4-dichloroanilino group, a 2-chloro-4- / ä - (2> 4 -di-tert. ^ amylphenoxy) -butylamid7-anilino group, a -5- "Ζίί- · (-2» - ¹ Hitert.-amylph.enoxy) -acetamido-2-methoxyanilino group and the like, a group of ureidoreins, for example an N '- (a, ß-dicarboxyethyl) -ureido group, an octylureido group, a 3- / ä- (2, A-di-tert * -amylphenpxy) -acetamido7-phenylureido group and the like *, a group of the carboriamido series, for example one Octadeeylamido group, an octadecylsuccinmonoamide group, a 3- (octadeyl-succinmonoamido) -benzamide group, a 5 / ä- (i2 »4 - di-tert-amylpb.enöxy) -acetamido7-benzamide group, an a- (4-tert. -butylplienoxy) -propionamide group, a J- ^ a-Cj-pentadecyl - ^ - sulfoplienoxy) -acetamidßZ-benzamidgruppe ^ a γ- (4-N-Butyl ~ H-pentadecyl-oxycarbonylamino) -propionamidgruppe and the like., a group of Sulfonamide pure, for example 4-methylphenylsulfonamido group and the like, or a sulfamyl group, for example the sulfamyl group itself, an N-ethylsulfamyl · -. group, an N-phenylsulfamyl group and the like.

The radical R is an alkyl group with 1 to h carbon atoms, for example a methyl group, an ethyl group and the like, or an aryl group, for example a phenyl group and the like Halogen atom, a group -SCN, -OR ₄ , -SR ^, -OCOR ₄ or -OSO ₂ R ₄ , wherein R _{4 represents} an alkyl group, an aryl group or a heterocyclic group, for example a fluorine atom, chlorine atom, bromine atom, iodine atom, a -SClI group, a phenoxy group :, a 4-methrophenoxy group, an acetyloxy group, a 4-nitro-

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phenylthio group, a benzothiazolthio group, a methylsulfonyloxy group, a 3-nitrophenylsulfonyloxy group
and the like.

Examples of diffusion-resistant magenta couplers im
The scope of the invention is given below, but the magenta couplers in the context of the invention are not limited to these.

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19th

O H C. O U O • 11 -ο X O O- O O

O = O ■ "*

rev

α>

i-l

f-i ω

P <

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ORIGINAL INSPECTED

.Γ

O Ü

do

2;

a: ο

■ ο

O " E rs ο— ο ο ο do

J5.

O -o

U (U

U ο

P.

009886/1549

co

ft

ORlQ) NAL INSPECTED

Ο .O _ιΛ \; ..; .-τ

U φ

γΗ

ρ.

§ ■

(J)

0 09886/1549

ORIGINAL INSPECTED

Ο)

tr \ ·

O) H

¹ p

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ORIGINAL INSPECTED

r -ζ ο

KD

§ * M

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The above-mentioned diffusion-resistant magenta couplers can be prepared by methods known per se getting produced. For example, they can be found in Fiat Final Report 943 and US patents $ 2 69,489 and 2,600,788, Japanese Patent 7039/5? » British patents 1 0 18 810 and 1 142 553 and US patent 2 618 641 Process are produced.

The above-mentioned magenta couplers can be incorporated into the photographic emulsion by the usual known method such as a method of direct addition in an alkaline Dissolving the same by a method in which the magenta coupler is in an organic solvent such as Dibutyl phthalate or tricresyl phthalate, which Solution in an aqueous medium, such as aqueous gelatin solution is dispersed and then the dispersion to the photographic emulsion is added (see, for example, C. E. K. Mees and T. H. James, The Theory of the Photographic Process, 3rd Edition, Macmillan Co., 1966) or a process in which the magenta coupler is melted by heating and the melted coupler directly in the photographic emulsion or is dispersed in an aqueous medium.

The Hagenta coupler can be seen to the photograph! Emulsion at each stage before de: a drawing up the photographic Emulsion are added, however, it is preferably added in the stages after the morduration and before the infusion.

The amount of to be added to the photographic emulsion Magenta coupler depends on the type of used pLotcgrapkisciien silver halide emulsion from is however favorably from C.0005 to 0.25 * "iol per mole

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«AD ORIGINAL

Silver halide in the green-sensitive emulsion layer. At fairphotograph !, see processing of the coupler-in-developer type For example, hardening pretreatment is generally carried out by a formaldehyde-containing pre-hardening bath. In this case, compounds with an active methine group, for example the magenta couplers, formation of yellow spots through reaction with the formaldehyde and therefore the amount of the magenta coupler is limited in this case. The density of yellow spots depends on the type of magenta coupler used, the type of incorporation of the magenta coupler into the photographic Emulsion, the composition of the hardening bath and the like. However, result in the above-mentioned Amounts of the magenta coupler do not interfere with yellow stain. Of course, the crowd can can be further increased if this yellow staining is little formed.

Furthermore, the above-mentioned magenta couplers can be used alone or as a combination of two or more couplers.

As to be used in the green sensitive emulsion layer Silver halide emulsions are silver iodobromide emulsions most suitable, but other silver halide emulsions, such as silver chloride emulsions, Silver chlorobromide emulsions or silver bromide emulsions be used.

The silver halide photographic emulsion used in the present invention can be prepared by known methods chemically sensitized, for example with unstable sulfur-containing compounds, such as ammonium thiosulfate or allyl thiocarbanide, gold compounds, like complex salts of monovalent gold and.

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Thiocyanic acid, reducing agents such as tin (II) chloride, Polyalkylene derivatives or combinations thereof. The . photographic emulsion can also contain stabilizers, such as z. B. ^ -Hydroxy-e-methyl-ijjjja ^ -tetrazaindole, benzimidazole or i-phenyl-5-ittercaptotetrazole and a curing agent, such as formaldehyde or hydrobromic acid. Furthermore, the emulsion can contain a wetting agent, such as saponin or a sodium alkylbenzenesulfonate.

Cyan dyes capable of sensitizing the wavelength range from 500 to 600 ma, for example 1., 1'-diethyl-2,2'-cyanine iodide, anhydro-5> 5 ', can be used as sensitizing dyes to achieve the green sensitivity of the photographic emulsion. -diphenyl-9-ethyl-3,5'-di- (2-sulfoethyl) -benzoxazole carbocyanine hydroxide, anhydro-5,5 ', 6,6'-tetrachloro-1,1'-diethyl - ^, ^ ¹ -di ( 3-sulfobutyl) benzimidazole carbocyanine hydroxide and the like can be used alone or as combinations.

It is favorable if the griinempfindliche emulsion layer contained the magenta couplers listed above is located between the rotemp'findlichen layer and the blue-sensitive layer, that is the order of the drawn onto the carrier emulsion layers is red-sensitive emulsion layer, green-sensitive emulsifier Λ sion layer containing the magenta coupler, yellow Pilterschicht and blue sensitive emulsion layer.

It is also beneficial if the red-sensitive The emulsion layer and the blue-sensitive emulsion layer usually do not contain couplers, albeit the red-sensitive emulsion layer has a diffusion-resistant one Cyan coupler and also the blue-sensitive emulsion layer a diffusion-resistant yellow coupler may contain.

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The color photographic light-sensitive materials with a multiple layer according to the invention, which the green-sensitive emulsion layer with the magenta coupler are favorably "of the coupler-in-batwickler type" by the color photographic treatment treated.

Contain the cyan, magenta and yellow color developing solutions at least one color-forming, primary developing agent and diffusing couplers that couple to form cyan, magenta and yellow dyes, respectively.

Examples of color-forming, primary developing agents are the known p-phenylenediamine derivatives, such as 4 ~ amino-N,] Sr-diethylaniline,
methylaniline, ^ -amino
sulfonamidoethyl) aniline,

(ß-hydroxyethyl) aniline (see for example C. E. K. Mees and T. H. James, The Theory of the Photographic Process, 3rd Edition, Macmillan Co., "p. 387 (1966)) listed.

Examples of diffusing cyan couplers which are added to the cyan-forming developing solution are the known phenolic couplers such as 2-chloro-1-naphthol, 2,4-dichloro-1-naphthol and i-hydrosy-H-butyl-2-naphthami d, 1-Hydroxy-N- ( 2- ac etamidophenäthy1) -2-naphthamid and similar (ibid., page 38?) listed.

As a diffusing magenta coupler leading to the magenta-forming developing solution are added, be the ring-closed methylenic couplers, such as acylacetonitrile, 2-cyanoethyl-benzofuran, Benzylacetonitri ^ or cyclic methylene couplers, such as 1 ™ phenyl-3-iaethyl-5-pyrazolone, 1-phenyl-3- (4 - chlorobenzamido) -5-pyrazolone, 1-phenyl-3- (3 ~ nitrobenzoylamino) -5-pyrazolone, 1- (2,4,6-trichlorophenyl) -3- (4-nitroanilino) -5-pyrazolone and the like, listed «.

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As diffusing yellow couplers which are added to the yellow-forming developing solution, the known open-chain methylene couplers of the acylacetamide type, for example 2-acetoanilide, 2-aceto-2 *, V-dichloroacetoanilide, 2-benzoylaceto anilide, 2-benzoyl- 2 ^l ~ methoxyacetoanilide, 2-benzoyl- (4 ^f p-toluenesulfonamido) -acetoanilide, and the like (see ibid., Page 389 and GH Broun and coworkers, Journal of American Chemical Society, volume 79 * pages 2919 to 2927 (1957 )) listed.

The following examples are provided for further explanation the invention.

example 1

A gelatin silver iodobromide emulsion for a high-speed reversal color photographic light-sensitive material which was sulfur-sensitized and gold-sensitized was heated, and then the emulsion was ^{treated with anhydro-5 »5 l} -diphenyl-9-ethyl-3r3 ^l -di- (2- Eulfoäthyl) -benzoxazolcarbocyaninhydroxid and anhydro-5,5 ', e ^' - tetrachlor-i, 1 ^ -diäthyl-3,3'-cli- (3-sulfobutyl) benzimidazolcarbocyaninhydroxid green-sensitized and the green-sensitized emulsion divided into different proportions. An aqueous, alkaline solution of the magenta couplers and citric acid listed in Table I was added to the proportion of the green-sensitive emulsion, and the pH of the emulsion was then adjusted to 7.0. The green-sensitive etaulsion was coated on the red-sensitive silver halide emulsion layer for reversal color photographic material which did not contain a coupler and was formed on a cellulose triacetate film base so that the amount of silver was in

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green sensitive layer was 15 mg / 100 cm. One
yellow filter layer and a blue-sensitive emulsion layer containing no yellow coupler for a reversal color photographic material were further coated on the green-sensitive layer in this order and then dried.

• The sample dried in this way was uniformly subjected to magenta exposure, and then the
• Subjected to the following color photographic processing of the coupler-in-developer type:

1. Pre-hardening 27 ° C. 1' Min. 2. Wash with Vasser 27 ° C. 1 Min. 3 · Negative development 27 ° C. 4- Min. 4. Water wash 27 ° C. 3 Min. 5 · Reverse red light off
settlement 6. Cyan color development 27 ° C. 5 Min. 7 · Wash with water 27 ° C. 2 Min. 8. Reverse red light off
settlement 9 · Yellow color development 27 ° C. 5 Min. 10. Wash with water 27 ° C. 5 Min. 11. Reverse white off
settlement 12. Magenta color development 27 ° C. 2 Min. 13 · Wash with water 27 ° C. 2 Min. 14. Silver bleaching 27 ° C. 5 Min. 15 · Fixation 27 ° C. 3 There. 16 Water washing and drying.

The compositions of the above processing The treatment baths used were as follows:

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Pre-hardening solution

Concentrated sulfuric acid borax (10H ₂ O) potassium bromide sodium sulfate • 37 % formaldehyde sodium bisulfite water at 1000 ecm. Negative development solution ;;

N-methyl-p-aminophenol sulfate anhydrous sodium sulfite hydroquinone sodium carbonate (H ^ O) potassium bromide potassium thiocyanate 0.1 % potassium iodide sodium hydroxide water at 1000 ecm. Cyan color developing solution;

. i

j potassium bromide: j 0.1 % potassium iodide j potassium thiocyanate: anhydrous sodium sulfite sodium carbonate (Hg ^ sodium hydroxide 5-nitrobenzimidazole nitrate 2,4-bichloro-i-naphthal

1.7 ecm - '"" ■■■ G 20 g 2.3 G G 200 g S. G 10 ecm ecm G 1 g S. G 5 g S. 79 g 20 ecm 2 g 3.0 40 g 10 g 3.5 30 g 2.0 .2.0 12.5 0.5 1.0 2.0 2 »0

hydrochloride water at 1000 ecm.

3 »O g

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ORIGINAL INSPECTED

Yellow color development solution otherwise

Sodium sulfite 5.0 g H, H-diethy1-p-pheny1endi amine-
hydrochloride 1.2 g Sodium carbonate (HoO) 20.0 g Potassium bromide 0.3 g _v 0.1 % potassium iodide 2.0 ecm 2-Benzoyl- (Vp-toluenesulfon-
amido) acetoanilide 1.0 g Sodium hydroxide 4.0 g 1000 ecm of water. MaKenta color development solution: Sodium sulfite 5 »0 g 4-lmino-3-methyl-N, N-diethyl-
aniline hydrochloride 2.0 g Potassium bromide 0.2 g pyrazolone 1.4 g Sodium hydroxide 2.5 g n-butylamine 5 ecm 1000 ecm of water. Silver lead solution: J7erricyanide 60 g Potassium bromide. 20 B 1000 ecm of water. ÜxierlosunR: Sodium thiosulfate 100 g Sodium sulfite 15 g

1000 ecm of water.

The density of the Hagentabildee after development was measured using blue, green and hot filters {the results are summarized in Table I.

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QRlGiNAu

As a result, the density of the magenta image was increased while the densities of the cyan images and yellow images were significantly reduced. This shows that when the method according to the invention is used, the cyan color mixing and the yellow color mixing is greatly reduced and the density of the magenta dye is increased.

Table I.

Magenta- lot Yellow 0.80 Cyan Stomach coupler (Mol / Mol-Ag) density 0.74 density density without 0.73 0.50 2.12 Coupler (1) 0.005 0.75 0.45 2.20 0.02 0.75 0.41 2.42 Coupler (2) 0.005 0.76 0.42 2.18 H, 0.02 0.74 0.40 2.35 Coupler (3) 0.005 0.78 0.47 2.21 M. 0.02 0.77 0.42 2.30 Coupler (4) 0.005 0.74 0.48 2.13 Il 0.02 0.70 0.40 2.48 Coupler (5) 0.005 0.75 0.46 2.22 Il 0.02 0.71 0.45 2.35 Coupler (6) 0.005 example 0.43 2.20 Il 0.02 0.41 . 2.37 2 ■ - ■

The green sensitive gelatin-silver iodobrojaide emulsion for color reverse cook rate photographic material according to Example 1, the mixture was melted and the emulsion was divided into several parts. 5 g each of the Couplers listed in Table II were mixed in solution with 10 g of tricresyl phosphate and 20 g of ethyl acetate

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dissolved and the solution by emulsification in 50 g of a 10% aqueous gelatin solution together with a Dispersion aid dispersed. The received Coupler dispersion was made into the green sensitive emulsion prepared above in those given in Table II Quantities added and the pH of the mixture adjusted to 7.0.

Me thoroughly sensitive containing the magenta coupler Emulsion was applied to a red-sensitive emulsion layer for reversal color photographic material that did not have any Coupler contained and coated on a cellulose triacetate film, applied so that the amount of Silver in the green-sensitive layer 15 mg / 100 cm and a yellow filter layer and a blue-sensitive layer were put on the green-sensitive emulsion layer An emulsion layer containing no yellow coupler for reversal color photographic material was applied and then dried.

The dried samples were exposed to light, developed and assessed for density according to the method given in Example 1; the results are in Table II, which shows that the magenta density was increased, but the cyan and yellow densities were extremely reduced.

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Table II

Magenta- Amount of yellow Cyan Magenta- coupler Dispersion
(g / mol Ag) density density density Without _ 0.80 O.5O 2.12 Coupler (7) 50 0.73 0.46 2.18 I »' 100 0.72 0.42 2.30 Coupler (8) 50 0.73 0.47 2.20 Il 100 0.70 0.41 2.45 Coupler (9) 50 0.75 0.45 2.22 Il 100 0.72 0.43 . 2.35 Coupler (10) 50 0.76 0.45 2.20 ti 100 0.72 0.42 2.4Q Coupler (11) 30th 0.76 0.44 2.18 Il 100 0.74 O, 42 2 * 36 Coupler (12) 50 0.73 0.47 2.16 Il 100 0.71 0.42 . 2.30 ' Coupler (I3) 50 0.75 0.46 2.23 It 100 0.71. 0.42 2.33; Coupler (14) 50 0.78 | 0.46 2.25! 1" 100 0.72 0.41 2.35 Coupler (15) 50 0.75 0.43 2.19 M. 100 0.70 0.41 2.39 Coupler (16) 50 0.74 0.4A 2.25 Il 100 0.71 0.42 2.43 AtSDiel 5

It was used the same procedure as in Example 1, _t 1edoch the couplers shown in Table III used. The samples were uniformly

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Subjected to gentile exposure as in Example 1 and then treated in the same way as in Example 1, however the pre-curing treatment was carried out for J minutes at 27 ° C using a pre-hardening bath with the following composition:

i.
Pre-hardening solution:

i water 800 ecm Dimethoxytetrahydrofuran 4.5 ecm 5.41 cc 0.8 n-HpSO. 0.5 g • a · '*
isodium p-toluenesulfonate 155 g Sodium sulfate 2.5 g Potassium bromide 20 g Sodium acetate 27 ecm 37 % formalin

After the treatment, the density was determined by the same method as in Example 1; the results are given in Table III, from which it can be seen that that the magenta density was high while the cyan and Yellow densities were extremely low.

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■ ■ '- .. ORIGINAL INSPECTED

Table III

Magenta- lot Yellow- Cyan Magenta- • Coupler (Mol / mol Ag) density density density Without • 0.76 0.47 1 * 95 Coupler (1) 0.0005 0.74 0.46 1.97 Il 0.005 0.70 0.44 2.08 Il. 0.05 0.69 0.41 2.28 Il 0.25 0.69 0.39 2.55 Example 4

The green sensitive gelatin-silver iodobromide emulsion according to Example 1 for high speed reversal color photographic materials was heated and the silver halide emulsion with an aqueous, alkaline solution of the coupler (2) in a range of 0.01 Hol per mole of AgX mixed and then the pH Uert adjusted to 7.0.

The green sensitive one containing the magenta coupler Emulsion layer was on top of a red-sensitive emulsion layer for uni color photographic material containing no coupler and on a polyethylene terephthalate film was applied, applied so that the silver content of the green sensitive layer was 15 mg / 100 cm and on the emulsion layer were a yellow filter layer and a blue-sensitive emulsion which did not contain a yellow coupler contained, applied for color photographic reversal material and then dried. The samples obtained in this way were exposed, developed and checked for density determined according to Example 1, but different diffusing couplers for the cyan, yellow and magenta color developing solutions used according to Table IV.

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The "combinations used in this example of diffusing couplers and those in carrying out the color photographic treatment of the coupler-in-developer type Results obtained are summarized in Table IV.

The numerical values given in Table IV show the difference in yellow density, cyan density and magenta density in the results obtained with the addition of the diffusion-resistant magenta coupler to the green ^ sensitive emulsion layer and were obtained without adding this magenta coupler.

The designation (+) shows that the density is increased by the addition of the diffusion-resistant magenta coupler while the designation - (-) shows that its addition decreased the density.

In the case of using the method according to the invention the magenta density was increased and the cyan and yellow density extremely reduced when the color photographic, light-sensitive material according to the invention was developed in the color developing solutions, any contained diffusing couplers in comparison with the case where the diffusion-resistant gastric coupler according to FIG of the invention was not added to the green-sensitive emulsion layer.

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Table IV Diffusing coupler used in the color developer

Trial cyan no. coupler
g / l

Yellow coupler

, -I- 2-Benzoylacetnaphthol 2 g / l anilide 1.8 g / l

1-Hydroxy-N-buty 1-2-naphthamide 2 g / l

1-Hydroxy-N- (2-acetamidophenethyl) -2-napithamide
1.8 g / l

dichloroacetanilide 1.8 g / l

2-Benzoyl-2 ^ - methoxy-acetanilide 1.5 g / l

2-acetanilide 1.3 g / l magenta coupler

1-phenyl - ^ - (4-chlorobenzamiao) -5-pyrazolone 1.7 g / l

1- (2,4,6-Trichloroph.enyl) -3- (4-nitroanilino) -5-pyrazolone 1.7 g / l

2- (cyanoacetyl) benzofuran 1.5 g / l

Difference in the density of the magenta images

Trial no.

1
2

.3
4th

Yellow density Gyan density

-0.06

-0.05

-0.07
-0.05

-0 08 -0.08 -0.10 -0.07 magenta density

+0.18 +0.19 +0.22 +0.20

009886/1649

If other diffusion-resistant magenta couplers,
than those used in Examples 1, 2, 3 and 4,
were used, practically equally good results were obtained. Similarly, if similar procedures to the above were repeated using coupler-in-developer type developing solutions for color photographic processing having different compositions from those used in the above Examples, very good results would be obtained in the same manner.

009886/1549

Claims (6)

Claims 1J method to prevent color mixing at color piotographic, photosensitive reversal material of the coupler-in-developer type with several layers, characterized in that at least one diffusion-resistant Magenta coupler into the green-sensitive emulsion layer of the color photographic light-sensitive material is incorporated which has a red-sensitive emulsion layer, the green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support and the color photographic material with color developing solutions, containing three types of diffusing couplers is being developed. 2. The method according to claim 1, characterized in that that as a diffusion-resistant magenta coupler in the green-sensitive emulsion at least one compound of the following general formulas (I) or (XI): B ₀ -O-CH-X B ₀ -C-CH-OH-CCE ₀ (II) N C-OO »C K wherein B ^ is a group of the aryl series, a group of the heterocyclic series Ring series, a group of carbamyl series or 009886/1549 a group of the xhiocarbamyl series, Bp a hydrogen atom, a group of the alkyl series, a group of the aryl series, a group of the amino series, a group of the ureido series, one group of the carboamide series, one group of the sulphonamid (v * series or a group of the sulfamyl series, IU an alkyl group having 1 "to 4 carbon atoms or a Aryl group and X denote a hydrogen atom or a group released during the coupling, where at least at least one of the groups IL and Ep, one hydrophobic Best with 8 to 30 carbon atoms, the sur achievement the diffusion resistance properties of the coupler is necessary, contains, is incorporated - 3- The method according to claim 1 or 2, characterized in that E. in the general formulas I and II from an aryl group «> one with an alkyl group with 1 to 18 carbon atoms, one alkoxyl group, one Aryloxy group, an alkoxycarbonyl group, an amino group, a carbonamide group, a sulfonamide group, a carbamyl group, a sulfamyl group, a sulfon group, a sulfonyl group, a hydroxyl group, a carboxyl group or a halogen atom Aryl group, a furany group, a benzothiazolyl group, an oxazolyl group, an imidazoly group, a quinolinyl group each optionally substituted with the same substituent as the above Aryl group, a carbamyl group, a methylcarbamyl group, a phenylcarbamyl group, a shiocarbamyl group, an ethylthiocarbamyl group or a phenylthiocarbamy group is. 4. The method according to claim 1 or 2, characterized in that that Rp is a hydrogen atom, a. Alkyl -33- 2035381 group with 1 "to JO carbon atoms, which is optionally substituted with an alkoxy group, aryl group, an aryloxy group, a halogen atom or a hydroxyl group, an aryl group, an aryl group substituted with the substituent as in IL according to claim 3, a primary amino group, a Benzylamino group, a 3 * 5-dicarboxyanilino group, a 4-nitroanilino group, a 2,4-dichloroanilino group, a 2-chloro-4 ~ ^ cc- (2 »4-di- ^: tert-amylphenoxy) -butylamid27-anilino group, a 5- ^ a- (2,4-di-1 ert -amylphenoxy) -ac etamido-2-methoxyanilino group, an N '- (a, ß-dicarboxyethyl) -ureido group, an oetylureido group, a 3- / a- (2,4-Di-tert-amylphenoxy) -acetamido7-phenylureido group, an octadecylamide group, an octadecylsuccinmonoamide group, a 3- (° ' ^fc adecylsuccinmonoamido) benzamido group, a 3-Z ^ -C 2,4-di-tert. -amylphenoxy) -acetamidoy-benzamido group, an a- (4-0? ert.-butylphenoxy) -propioamidogruppe _i a 3- / PC (3-pentadecyl-4-sulfophenoxy) -acetamido7 ^l ben2iami do group, a γ-CA-N-butyl-lSi-pentadecyloxycarbonyl- 'amino) propioamido group, a 4-methylphenylsulfone; amido group, a sulfamyl group ^, an H-ethylsulfamyl group or an H-phenylsulfamyl group. 5. The method according to claim 1 or 2, characterized in that X is a hydrogen atom, a halogen atom, a group -SCN, -OB ^, -SH ₂ ^, -OCOfi ^ or -OSOgB ^, where H ^ is an alkyl group, represents an aryl group or a heterocyclic group. 6. The method according to claim 1 to 5 »characterized in that that a diffusion-resistant magenta coupler the structural formulas i to 16 is used. 7. The method according to claim 1 to 6, characterized in that that a lot of the diffusion-resistant 009886/1549 ORlGiNAL INSPECTED is gen magenta coupler to the photographic Bralsion from 0.0005 Ms 0.25 mol per mol of silver halide in the grünempfindliaben BnulsionsscMcht " IN