Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/32—Colour coupling substances
  • G03C7/34—Couplers containing phenols

Definitions

• ABSTRACT A reversal multi-layer color photographic lightsensitive material having on a support a red sensitive silver halide emulsion layer, a green sensitive silver halide emulsion layer, and a blue sensitive silver halide emulsion layer which is capable of forming after exposure upon development with color developing solutions containing a diffusible cyan coupler, a diffusible yellow coupler, and a diffusible magenta coupler, respectively, cyan, yellow, and magenta color images, in which the red sensitive silver halide emulsion layer of the color photographic material contains a diffusion resistant cyan coupler is disclosed.
• the present invention relates to a reversal multi-layer color photographic light-sensitive material and more particularly to a reversal multi-layer color photographic material showing less or substantially no color mixing from color developing solutions.
• the color photographic material of the type which does not contain couplers in the photographic emulsion layers is processed with color developing solutions containing couplers, it is superior in sharpness to the color photographic material of the type containing couplers in the photographic emulsion layers.
• undesirable dyes which should not be present are formed in a photographic emulsion layer together with the desired dye appropriate to that layer upon development to cause color mixing, and thus the color reproduction of the developed color photographic material is not good.
• a reversal color photographic light-sensitive material having on a support a red sensitive emulsion layer, a green sensitive emulsion layer, and a blue sensitive emulsion layer each of which does not contain a coupler is after image exposure subjected to (succesively) a black and white development, a cyan color development, a yellow color development, and a magenta color development (hereinafter, this is designated for brevity as reversal color development or reversal color developing process,") a yellow dye and a magenta dye are formed in the red sensitive emulsion layer in addition to a cyan dye to form a slightly greenish or purplish cyan dye image, and thus a cyan color having high color purity is not obtained.
• the cause of such color mixing is believed to be as follows: That is to say, when the above described reversal color photographic material of the type not containing couplers in the photographic emulsion layers is developed in the order described above, the red sensitive emulsion layer developed by a cyan color forming developing solution is further subjected to the subsequent yellow color development and magenta color development. Hence, if the development of the red sensitive emulsion layer has not been completely finished, the remaining development occurs in the red sensitive emulsion layer with the yellow color developing solution or the magenta color developing solution to cause a yellow color mixing or a magenta color mixing in the cyan image. In order to overcome such a difficulty, various methods have been proposed.
• a method in which in order to conduct the cyan color development as quickly as possible a diffusible developing accelerator is incorporated in the cyan color developing solution to complete the development of the red sensitive emulsion layer.
• This proposed method is an improvement in the developing solution.
• the red sensitive emulsion layer of a color photographic material is the lowermost layer on the support thereof and thus the development of the red sensitive layer generally tends to be delayed in comparison with the developments of the blue sensitive layer or green sensitive layer caused by delay in the diffusion of the color developing solution
• the addition of a developing accelerator to the red sensitive emulsion layer has also been proposed.
• such a technique is greatly limited since the addition of the developing promoter results in adverse influences on other important photographic properties of the color photographic light-sensitive material.
• An object of this invention is, therefore, to provide a reversal color photographic light-sensitive material of the type which does not contain couplers in the photographic emulsion layers capable of forming upon reversal color development a cyan dye image having high color purity unaccompanied by yellow color mixing and magenta color mixing.
• Another object of this invention is to provide a multilayer color photographic light-sensitive material capable of forming a high color density upon reversal color development.
• the diffusion resistant cyan couplers used in this invention can be selected over a very wide range of compounds, for instance, compounds having from 15 to 44 carbon atoms can be selected from the generally known cyan couplers described in, e.g., W. Pelz, Mit- 3 annonen aus den Anlagenslaboratorien der Agfa, Leverkusen, Kunststoff; lll 156-174(1961
• the compounds represented by the general formula (I) or (ll) give particularly good results:
• amyl isoamyl, hexyl, octyl, decyl, dodecyl, pentadecyl, octadecyl, eicosyl, docosanyl, triacontanyl, etc.
• a cyclic alkyl group such as a cyclohexyl group, a terpentyl group, and a norbornyl group
• an aryl group such as a phenyl group and a naphthyl group
• a heterocyclic group such as a benzimidazolyl group and benzthiazoyl group
• R together can combine to form a heterocyclic group comprising nonmetalic atoms
• R represents a hydrogen atom, an alkyl group, preferably having from 1 to 30 carbon atoms, an aryl group, a heterocyclic group, an amino group (such as an amino group, an alkylamino group, an arylamino group, and a heterocyclic amino group), a carbonamide group (such as an alkylcarbonamide group, an ary
• At least one of R R R R R R R R and R is advantageously further substituted by any of the ballasting groups well known in the art.
• Each of the above described alkyl group, aryl group, and heterocyclic group represented by R, or R may be substituted with a halogen atom, a nitro group, a hydroxyl group, a carbonyl group, an amino group (such as an amino group, an alkylamino group, a dialkylamino group, an anilino group, and an N-alkylanilino group).
• an aryl group such as a carboxyester group (such as a carboalkoxy group and a carboallyloxy group), an amide group (such as an acetamide group, a butylamide group, an ethylsulfonamide group, an N- methylbenzamide group, an N-propylbenzamide group and a 4-t-butylbenzamide group), a carbamyl group (such as a carbamyl group, an N-octadecylcarbamyl group, an N,N-dihexylcarbamyl group, an N-methyl-N- phenylcarbamyl group, and a 3-pentadecylphenylcarbamyl group) a sulfamyl group (such as an N- propylsulfamyl group and an N-tolylsulfamyl group), an alkoxyl group (such as an ethoxy group and an octade
• R may also Cdupler (1):
• Coupler (4)
• Coupler (9) n m
• Coupler (12) mtooomomomo-Q-Qm l CH3 CsHu Coupler (13):
• Coupler (14) CH3 CrsHar
• the diffusion resistant cyan couplers illustrated above may be prepared by well known methods. For instance, the production of the compound is illustrated in the US. Pat. Nos. 2,242,337; 2,324,832; 2,367,53l; 2,357,395; and 2,474,293; in German Patent No. 1,036,053; and in British Patent specification No. 727,693.
• the cyan coupler used in this invention may be incorporated in the photographic emulsion using wellknown methods which are conventionally employed. For instance, cyan couplers having acid, e.g., carboxyl or sulfonic group may be incorporated into photographic emulsion as an aqueous alkaline solution thereof. As an alternative, cyan couplers not having such acidic groups may be dissolved in an organic solvent such as described in US. Pat. No. 2,322,027, e.g. dibutyl phthalate and tricresyl phosphate, the solution is dispersed in an aqueous medium such as an aqueous solution of gelatin, and then the dispersion is added to the photographic emulsion (see, e.g., C.
• the cyan coupler can be melted by heating and the molten coupler directly dispersed in the emulsion or the aqueous medium.
• the diffusion resistant cyan coupler may be incorporated in the photographic emulsion in any step before coating but it is desirable to incorporate it in a step between post-ripening and coating.
• the amount of the diffusion resistant cyan coupler depends upon the nature of the silver halide photographic emulsion employed but in general ranges from 0.0005 to 0.5 mol per mol of the silver halide in the red sensitive emulsion layer, although the invention is'not limited to this range. Furthermore, the diffusion resistant cyan couplers used in this invention may be used alone or used as a combination of two or more such couplers.
• a gelatino silver iodobromide emulsion or a gelatino silver chloroiodobromide emulsion containing from 0.1 to l0 mol percent of iodide ion per mol of the silver halide is particularly preferred but other silver halide emulsions such as a silver chloride emulsion, a silver chlorobromide emulsion, or a silver bromide emulsion can also be employed.
• the silver halide photographic emulsion may have been chemically sensitized by method well known in the art, e.g., by a labite sulfur containing compound, such as ammonium thiosulfate and allylthiocarbamide; a gold compound such as a complex salt of univalent gold and thiocyanic acid; a reducing agent such as stannous chloride; a polyalkylene oxide derivative; or a combination thereof.
• a labite sulfur containing compound such as ammonium thiosulfate and allylthiocarbamide
• a gold compound such as a complex salt of univalent gold and thiocyanic acid
• a reducing agent such as stannous chloride
• a polyalkylene oxide derivative such as stannous chloride
• the silver halide photographic emulsion may contain a stabilizer such as 4- hydroxy-6-methyl -l,3,3a,7-tetrazaindene, benzimidazole, and l-phenyl-S-mercaptotetrazole and a hardening agent such as formaldehyde or mucobromic acid.
• the photographic emulsion may contain a coating aid such as saponin or sodium alkylbenzenesulfonate.
• a sensitizing dye for providing the red sensitivity to the silver halide photographic emulsion a cyanine dye and a merocyanine dye capable of sensitizing the emulsion in the wave length region of from 580 to 700 mp. may be used alone or as combinations thereof.
• the red sensitive photographic emulsion containing the diffusion resistant cyan coupler be first applied to a support and then a green sensitive emulsion layer, a yellow filter layer, and then a blue sensitivev emulsion layer be formed thereon in this order. It is also desirable that the green sensitive emulsion layer and the blue sensitive emulsion layer contain no couplers but the green sensitive emulsion layer may contain a diffusion resistant magenta coupler and the blue sensitive emulsion layer may contain a diffusion resistant yellow coupler.
• the reversal color photographic material having the red sensitive emulsion layer containing the diffusion resistant cyan coupler is desirably processed using the conventional reversal color photographic developing process.
• Each of the cyan, magenta and yellow color developing solutions contains at least a color developing agent and a diffusible coupler capable of being colored cyan,
• magenta and yellow, respectively.
• color developing agents used in the color developing solutions are generally the wellknown p-phenylenediamine derivatives 4-amino-N,N-diethylaniline, 4-amino-N,N-diethyl-3- methylaniline, 4-amino-3-methyl-N-methyl-N- (B-methylsulfonamidoethyl)aniline, and 4-amino-3-methyl-N- ethyl-N-(B-hydroxyethyDaniline (see, e.g.', C. E. K. Mees and T. H. James; The Theory of the Photographic Process; 3rd Edition, 387(1966), published by the Macmillan Co.).
• the diffusible cyan coupler examples include the well known phenolic couplers, such as 2-chloro-l-naphthol, 2 ,4-dichlorol -naphthol, l-hydroxy-N-butyl-Z- naphthamide, l-hydroxy-N-( 2-acetamidophenethyl )-2- naphthamide, etc., (see, Mees et al., supra, page 387).
• phenolic couplers such as 2-chloro-l-naphthol, 2 ,4-dichlorol -naphthol, l-hydroxy-N-butyl-Z- naphthamide, l-hydroxy-N-( 2-acetamidophenethyl )-2- naphthamide, etc.
• Examples of the diffusible magenta couplers are open chain methylenic couplers such as acylacetonitrile, 2-cyanoethylbenzofuran, and benzylacetonitrile and cyclic methylenic couplers such as l-phenyl-3-methyl- S-pyrazolone, 1-phenyl-3-(4-chlorobenzamide)-5- pyrazolone, l-phenyl-3-(3-nitrobenzoylamino)-5- pyrazolone, nitroanilino)-5-pyrazolone, etc.
• open chain methylenic couplers such as acylacetonitrile, 2-cyanoethylbenzofuran, and benzylacetonitrile
• cyclic methylenic couplers such as l-phenyl-3-methyl- S-pyrazolone, 1-phenyl-3-(4-chlorobenzamide)-5- pyrazolone, l-phenyl-3-(
• examples of the diffusible yellow couplers are acylacetamide type open chain methylenic couplers such as Z-acetanilide, 2- aceto-2'-4'-dichloroacetanilide, 2-benzoylacetanilide, 2-benzoyl-2'-methoxyacetanilide, 2-benzoyl-(4'-ptoluene-sulfonamido)-acetanilide, etc., (see, G. H. Broun et al; Journal of the American Chemical Society; Vol. 79, 2,9l9-2,927( 1957)).
• EXAMPLE 1 A gelatino silver iodobromide emulsion for reversal color photography which had been subjected to sulfur sensitization and gold sensitization was melted by heating, sensitized for the red region, and the red sensitive silver halide emulsion thus prepared was divided into several portions. To each of the red sensitive emulsions was added an alkaline aqueous solution of the cyan coupler shown in Table 1 and then the pH of the emulsuch as l-( 2,4,6-trichlorophenyl)-3-(4- sion was adjusted to 7.0 by adding citric acid.
• the red sensitive reversal color photographic emulsion containing the cyan coupler was applied to a cellulose triacetate film base so that the amount of silver was 15 mg/ cm2 and then a green sensitive reversal color photographic emulsion containing no magenta coupler, a coating composition for a yellow filter layer, and a blue sensitive reversal color photographic emulsion containing no yellow coupler were applied to the red sensitive emulsion layer in this order and dried.
• the silver iodobromide emulsion for the red-sensitive layer contained 5 mole percent iodide.
• the emulsions for the green-sensitive and blue-sensitive layers were also silver iodobromide emulsions containing 5 mole percent iodide.
• the yellow filter layer contained yellow colloidal silver.
• AgX denotes silver halide
• EXAMPLE 2 The red sensitive silver iodobromide emulsion for reversal color photography as employed in Example 1 was melted by heating and divided into several portions. 5 g of the diffusion resistant cyan coupler shown in Table 2 was dissolved in a mixture of g of tricresyl phosphate and 20 g of ehtyl acetate, the solution was dispersed in 50 g of aqueous gelatin solution together with a dispersion assistant (sodium dodecyl benzene sulfonate), and the coupler dispersion obtained was added to the above-described photographic emulsion prepared above in an amount as shown in Table 3. Then, the pH of the photographic emulsion was adjusted to 7.0.
• a dispersion assistant sodium dodecyl benzene sulfonate
• the red sensitive reversal color photographic emulsion containing the diffusion resistant cyan coupler was applied to a cellulose triacetate film base so that the.
• Example 1 a green sensitive reversal color photographic emulsion containing no magenta coupler, a coating composition for a yellow filter layer, and a blue sensitive reversal color photographic emulsion containing no yellow coupler in order were applied to the red sensitive layer and dried as in Example 1.
• These layers are the same as those used in Example 1 except the yellow filter layer contains a yellow dye.
• EXAMPLE 4 The gelatino silver iodobromide red sensitive emulsion for reversal color photography as used in Example 1 was melted by heating, an aqueous alkaline solution of Coupler (5) was added to the melt in an amount of 0.01 mol per mol of the silver halide and the pH of the mixture was adjusted to 7.0.
• the red sensitive silver halide emulsion containing the diffusion resistant cyan coupler, the green sensitive emulsion containing no magenta coupler, a coating composition for yellow filter, and the blue sensitive emulsion containing no yellow coupler were applied to a cellulose triacetate film and dried.
• Example 1 The samples thus prepared were exposed and processed in the same manner as described in Example 1 except that different diffusible couplers from those of Example 1 were used in the cyan, yellow, and magenta color developing solutions and then the densities of the cyan images were measured.
• the combinations of the diffusible couplers used in this example and the results of the reversal color developing procedures obtained are shown in Table 4.
• the numerical values in Table 4 are the difference in the yellow density, the difference in the cyan density, and the difference in the magenta density of the cyan images obtained in adding the diffusion resistant cyan coupler to the red sensitive silver halide emulsion layer and in not adding such a diffusion resistant cyan coupler to the red sensitive emulsion layer.
• the sign shows that the density increased by the addition of the diffusion resistant cyan coupler to the red sensitive emulsion layer, while the sign shows that the density decreased.
• the cyan density was increased and the yellow and magenta densities were decreased in the case of conducting reversal color developing procedures with the color developing solution containing a diffusible coupler shown in Table 4 as compared with the case of not adding a diffusion resistant cyan coupler to the red sensitive emulsion layer.
• a multi-layer reversal color photographic material having on a support a red sensitive silver halide emulsion layer, a green sensitive silver halide emulsion layer, and a blue sensitive silver halide emulsion layer capable of forming after exposure and black and white negative development cyan, yellow, and magenta dyed images respectively by the developments in three color developing solutions containing a diffusible cyan coupler, a diffusible yellow coupler, and a diffusible magenta coupler, respectively, the improvement comprising said red sensitive silver halide emulsion containing a diffusion resistant cyan coupler present in said red sensitive emulsion layer in an amount ranging from 0.005 to 0.5 mol per mol of the silver halide in said red sensitive emulsion layer wherein said blue-sensitive and said green-sensitive layers contain no color couplers after layer at the last line.
• X represents a hydrogen atom, a group capable of being split off at coupling, or a cyclic imide group.
• R represents a hydrogen atom, an allcyl group, an aryl group, a heterocyclic group, an amino group, a carbonamide group, a sulfonamide group, a sulfamyl group, a carbamyl group, or a ureido group
• R R and R each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, an aryl group, a heterocyclic group, an amino group, a carbonamide group, a sulfonamide group, a sulfamyl group, a carbamyl group, or a ureido group
• Y represents a hydrogen atom or a group capable of being split off at coupling.
• Coupler (6)
• Coupler (11) NHCO expo-Q-onm CH CsHn Coupler (12):
• Coupler 13 I NHCOCHOCaHm or Coupler (14):
• a process for forming color photographic images comprising image exposing a multi-layer reversal color photographic material including a support carrying a red sensitive silver halide emulsion layer, a green sensitive silver halide emulsion layer and a blue sensitive silver halide emulsion layer; developing said photographic material with a black and white developing solution and then subjecting said photographic material to color development with three color developing solutions, each containing a diffusible cyan coupler, a diffusible yellow coupler or a diffusible magenta coupler to form cyan, yellow and magenta dye'images, respectively, the improvement which comprises reducing color mixing by including 0.005 to 0.5 mol of diffusion resistant cyan coupler per mol of silver halide in said red sensitive emulsion layer.
• said diffusion resisting cyan coupler is a compound represented by the formula wherein R and R each represents a hydrogen atom, a straight chain alkyl group, a branched chain alkyl group, a cyclic alkyl group, an aryl group, a heterocyclic group, or a non-metallic atomic group necessary for'forming a heterocyclic group; R and R each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, an aryl group, a heterocyclic group, an amino group, a carbonamide group, a sulfonamide group, a sulfamyl group, a carbamyl group, or a ureido group; and X represents a hydrogen atom, a group capable of being split off at coupling, or a cyclic imide group.
• the diffusion resistant cyan coupler is a compound represented by the formula wherein R represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, a carbonamide group, a sulfonamide group, a sulfamyl group, a carbamyl group, or a ureido group; R R and R each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, an aryl group, a heterocyclic group, an amino group, a carbonamide group, a sulfonamide group, a sulfomyl group, a carbamyl group, or a ureido group; and Y represents a hydrogen atom or a group capable of being split off at coupling.

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• 1971
  • 1971-09-30 JP JP46076515A patent/JPS4842732A/ja active Pending
• 1972
  • 1972-09-28 US US00293276A patent/US3844784A/en not_active Expired - Lifetime
  • 1972-09-29 GB GB4520372A patent/GB1360713A/en not_active Expired

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