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
• • 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
  • G03C7/392—Additives
  • G03C7/39208—Organic compounds
  • G03C7/3924—Heterocyclic

Definitions

• the present invention generally relates to color photography. More particularly, the present invention relates to a process for increasing the color contrast of multilayer type color photographic light-sensitive materials by the interimage effect.
• the dye formed by the reaction of the oxidation product of an aromatic amino photographic developing agent and a color former or a coupler generally has the capability of absorbing to some extent other light than the light to be absorbed.
• a magenta dye absorbs blue light and red light to some extent besides the green light to be absorbed.
• a yellow dye and a cyan dye absorb to some extent, light other than the blue light and the red light respectively to be absorbed.
• the reduction of the saturation of color by the unnecessary absorption by the dye can be improved to some extent by the interimage effect.
• the interimage effect is a phenomenon occurring in a multi-layer type color photographic light-sensitive material, wherein the formation of a dye image in one emulsion layer influences the formation of the dye image in other emulsion layers. With the interimage effect the color contrast can be increased.
• the interimage effect which increases color contrast can be defined as follows.
• the sample thus obtained is cut into two "Ice samples and one sample (Sample I) is wedge exposed to red light only, while the other sample (Sample II) is exposed to the same amount of red light and also to blue light capable of causing the same photographic eifect as that due to red light exposure.
• Sample I the lowermost redsensitive emulsion layer only is exposed to the wedge image in Sample I
• the blue-sensitive emulsion layer and the red-sensitive emulsion layer are exposed to the wedge image in Sample II.
• the image density of Samples I and II is measured to observe the contrast of the cyan dye image formed in the redsensitive emulsion layer.
• the interimage effect is said to have occurred if the contrast of the cyan dye image in Sample I is higher than the contrast of the cyan dye image in Sample II. Furthermore, with a multi-layer type 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, it is possible using this interimage effect to increase the contrast of the yellow dye image and the magenta dye image.
• the term interimage effect as used in the specification is intended to encompass this interimage effect capable of increasing the color contrast.
• this interimage effect is important for increasing the color contrast but the manner of increasing this interimage effect is not well known.
• the interimage effect can be caused by using a coupler capable of releasing a development inhibitor, such as benzotriazole, a mercapto compound, and the like, at coupling or a compound such as a hydroquinone, and the like, which can release an inhibitor, such as iodine ion, a mercapto compound, and the like, at development.
• a development inhibitor such as benzotriazole, a mercapto compound, and the like
• an object of the present invention is to provide a color photographic image in which unnecessary absorption by dyes is corrected by the interimage effect.
• Another object of this invention is to provide a color photographic image having a high saturation unaccompanied with a reduction in sensitivity.
• heterocyclic ring and a substituted heterocyclic ring and R is a member selected from the group consisting of an alkyl group having 1-6 carbon atoms, a substituted alkyl group having 1-6 carbon atoms, a phenyl group, and a substituted phenyl group.
• the ring containing the atomic group necessary for forming a heterocyclic ring which may be substituted and illustrated by Q in the Formula I, there are illustrated, for example, an imidazole ring, an imidazoline ring, a thiazole ring, a thiazoline ring, a thiadiazole ring, a benzothiazole ring, a benzoimidazole ring, a benzoxazole ring, a beuzoselenazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a triazole ring, a triazine ring, a tetrazole ring, a tetraazaiudene ring, and the like.
• R in Formula I is a hydrogen atom (and not alkyl) which is different from the case of this invention
• the compound represented by Formula I becomes a compound having a mercapto group.
• Such a compound having the mercapto group tends to frequently inhibit strongly the development of silver halide this causing the reduction in sensitivity of a photographic light-sensitive material in development.
• R and Q are as defined above
• the compound of this invention represented by Formula I can be incorporated in at least one of the layers consisting of the silver halide emulsion layer of a multi-layer type color photographic light-sensitive material and the layers adjacent to the silver halide emulsion layers, such as a yellow filter layer, an antihalation layer, intermediate layers, and a protective layer. Furthermore, the compound can be incorporated in a developer solution for the multi-layer type color photographic light-sensitive material. Still further, the above two modes of the addition of the compound can be used in combination.
• the amount of the compound used in this invention varies depending to the nature of the multi-layer type color photographic light-sensitive material to be employed and also the manner of development but the amount generally ranges from 0.006 to 1.5 g. per mole of silver halide when the compound is incorporated in the silver halide emulsion layer of a rnulti-layer type color photographic light-sensitive material, from 0.006 to 1.5 g. per 100 g. of gelatin when it is incorporated in a layer adjacent to the above-mentioned silver halide emulsion layer, and further, from 0.1 mg. to 1 g., preferably from 5 mg. to 500 mg. per liter of developer solution when the compound is added to the developer solution.
• the ranges set forth above for this compound are not to be interpreted as limiting.
• a solvent which does not adversely atfect the silver halide photographic emulsion such as water, methanol, and acetone, can be used.
• any developer solution which can reduce silver halide particles to silver can be employed.
• a developer solution containing polyhydroxybenzenes, N-alkylaminophenols, l-phenyl-B-pyrazolidones, or a mixture thereof, as the developing agent, can be used.
• suitable ones are, for example, hydroquinone, pyrocatechol, pyrogallol, and the like; as the N- monoalkylaminophenol, suitable ones are N-methylaminophenol, N-ethylaminophenol, and as the 1-phenyl-3-pyrazolidone, suitable ones are 1-phenyl-3-pyrazolidone, 1- phenyl-4,4-dimethyl-3-pyrazolidone, and the like.
• the compound of this invention can be added to a developer solution containing, as a developing agent, a p-phenylenediamine derivative, such as 4-amino-N,N-diethylaniline 4-amino-3-methyl N methyl-N-(beta methylsulfoneamidoethyDaniline, 4 amino-3-methyl-N-ethyl-N-(betahydroxyethyl)aniline, and the like.
• a p-phenylenediamine derivative such as 4-amino-N,N-diethylaniline 4-amino-3-methyl N methyl-N-(beta methylsulfoneamidoethyDaniline, 4 amino-3-methyl-N-ethyl-N-(betahydroxyethyl)aniline, and the like.
• the multi-layer type color photographic lightsensitive material can be processed at ordinary processing temperatures, i.e., at from 20 to 30 C., but can be processed at higher temperatures, i.e., at 30 to C. or at an even higher temperature, if desired.
• the compound of this invention can be used in any of the processes capable of forming color photographic images. That is to say, in processes for developing multilayer type color photographic light-sensitive materials having at least two photographic silver halide emulsion layers containing silver halide dispersions in hydrophilic colloids to form dye images according to the reduced ratio of silver halide into silver.
• the compound of this invention is used in the so-called reversal color photographic process, i.e., a process wherein, after exposing a multi-layer color photographic light-sensitive material having at least two silver halide photographic emulsion layers sensitized to different wavelength regions, respectively, the light sensitive material is first developed in a black and white developer solution to provide a negative silver image and then the silver halide particles in the areas which have not been developed in the black and white development are developed by a color developer solution to provide positive dye images.
• reversal color photographic process i.e., a process wherein, after exposing a multi-layer color photographic light-sensitive material having at least two silver halide photographic emulsion layers sensitized to different wavelength regions, respectively, the light sensitive material is first developed in a black and white developer solution to provide a negative silver image and then the silver halide particles in the areas which have not been developed in the black and white development are developed by a color developer solution to provide positive dye images.
• coupler-in-developer type color system wherein a dye image is formed by successively developing a multi-layer type color photographic light-sensitive material using color developer solutions, each containing a dilfusible coupler to be coupled in each different color
• coupler-in-emulsion layer color system wherein a dye image is obtained by incorporating each diffusion resisting coupler capable of being coupled, in each different color in each silver halide emulsion layer of the multi-layer type color photographic light-sensitive material and processing the light-sensitive material by color developer solutions containing no couplers.
• the compound of this invention can be used effectively in both systems of the reversal color photographic processes.
• the compound of the present invention can also be used in a system wherein a negative dye image is obtained by developing a multi-layer type color photographic light-sensitive material having at least two silver halide photographic emulsions sensitized to different wavelength regions, each containing a diffusion resistant coupler, directly after exposure in a color developer solution.
• the compound of this invention can be used in the color diffusion transfer process, as described in the specifications of US. Pats. 2,559,643, 2,698,798 and 3,227,551, having the feature that a developer solution, a coupler, or a dye is diffused from a light-sensitive layer to a reception layer in contact with the light-sensitive layer in proportion to the images in the light-sensitive ayer.
• the compound of this invention can be used in the silver dye bleaching color photographic process, as described in the specification of US. Pats. 2,020,- 775 and 2,410,025, in which a dye image can be obtained by bleaching the dye in the areas containing silver.
• the multi-layer type color photographic light-sensitive material to be used in the present invention it is desirable to apply a red-sensitive silver halide photographic emulsion layer, a green-sensitive silver halide photographic emulsion layer and a blue-sensitive silver halide photographic light-sensitive emulsion layer to a support in this order.
• silver halide emulsion used in this invention there are employed photographic emulsions containing silver halides, such as silver bromide, silver iodide, silver chloride, silver chlorobromide, silver iodobrornide, and silver chloroiodo bromide.
• silver halides such as silver bromide, silver iodide, silver chloride, silver chlorobromide, silver iodobrornide, and silver chloroiodo bromide.
• silver chloroiodide, silver iodobromide, or silver chloroiodobromide having an iodine content of from 1 to molar percent.
• the silver halide photographic emulsion to be used in the present invention can be chemically sensitized'by methods well known in this field, such as, by using a compound containing an unstable sulfur atom, such as sodium thiosulfate, allylthiocarbazide; a gold compound such as a gold (1) complex salt of thiocyanic acid; a reducing agent, such as stannous chloride; or a polyalkylene oxide derivative.
• the silver halide photographic emulsion to be used in the present invention can be spectrally sensitized using a cyanine dye, such as 1,1- diethylcyanine iodide, 1,1'-diethyl-9-methylcarbocyanine bromide, anhydro-S,5-diphenyl-9-ethyl-3,3-di(2-su1foethyl)-benzoxazolocarbocyanine hydroxide, and the like, used alone or in combinations thereof.
• a cyanine dye such as 1,1- diethylcyanine iodide, 1,1'-diethyl-9-methylcarbocyanine bromide, anhydro-S,5-diphenyl-9-ethyl-3,3-di(2-su1foethyl)-benzoxazolocarbocyanine hydroxide, and the like, used alone or in combinations thereof.
• the silver halide photographic emulsion to be used in this invention can contain a developing agent capable of releasing a developing inhibitor, such as 2-iodo-5-pentadecyl-hydroquinone or 2-methyl-5(l-phenyl-S-tetrazolylthio)-hydroquinone; a stabilizer, such as 4-hydroxy-6- methyl-1,3,3a, 7-tetraazaindene, benzimidazole, or l-phenyl-S-mercaptotetrazole; a hardening agent, such as formaldehyde or mucobromic acid; and a wetting agent, such as saponin or sodium alkylbenzene-sulfonate.
• a developing inhibitor such as 2-iodo-5-pentadecyl-hydroquinone or 2-methyl-5(l-phenyl-S-tetrazolylthio)-hydroquinone
• a stabilizer such as 4-hydroxy-6-
• Coupler-in-developer type color system To a cellulose triacetate film base were applied, successively, the following different emulsion layers:
• Red-sensitive silver halide emulsion layer A layer formed by coating a high speed gelatino silver iodobromide emulsion having red sensitivity due to a sensitizing dye and containing no coupler so that the amount of silver is mg./ 100 cm.*.
• Green-sensitive silver halide emulsion layer A layer formed by coating a high speed silver iodobromide emulsion having green sensitivity due to a sensitizing dye and containing no coupler. so that the amount of silver is 15 mg./cm.
• Third layer Yellow filter layer A layer formed by coating a yellow colloidal silver dispersion containingv colloidal silver in gelatin so that the amount of silver is 2.5 mg./ 100 cm
• Fourth layer Blue-sensitive silver halide emulsion layer A layer formed by coating a high speed silver iodobromide emulsion having blue sensitivity and containing no coupler so that the amount of silver is 20 mg./
• the multi-layer type photographic light-sensitive material was processed using the following procedures:
• Coupler-in-emulsion layer type color system To a cellulose triacetate film base are successively applied the following different emulsion layers.
• Second layer Intermediate layer A layer formed by coating gelatin in an amount of 13.4 mg./100 cmP.
• a cyan coupler a coupler emulsion prepared by dissolving a cyan coupler, 1- hydroxy-4-chloro-N-dodecyl-Z-naphthamide in tricresyl phosphate and dispersing the solution in gelatin
• Green-sensitive silver halide emulsion layer A layer formed by coating a high speed gelatino silver iodobromide emulsion having green sensitivity due to a sensitizing dye and containing a magenta coupler (a coupler emulsion prepared by dissolving a magenta coupler, 1-(2,6-dichloro-4-methoxyphenyl) 3 [3-alpha-(2,4-ditert-amylphenoxy)propionamide benzamido] 5 pyrazolone in dibutylphthalate and dispersing the solution in gelatin) so that the amount of silver is 15 mg./ cm.
• a magenta coupler a coupler emulsion prepared by dissolving a magenta coupler, 1-(2,6-dichloro-4-methoxyphenyl) 3 [3-alpha-(2,4-ditert-amylphenoxy)propionamide benzamido] 5 pyrazolone in dibutylphthal
• Blue-sensitive silver halide emulsion layer A layer formed by coating a high speed gelatino silver iodobromide emulsion containing a yellow coupler (a coupler emulsion prepared by dissolving 2-benzoyl-2'- chloro 5 tridecanoyloxyacetanilide in dibutylphthalate and dispersing the solution in gelatin) so that the amount of silver in the coated layer is 15 mg./100 cm.
• a yellow coupler a coupler emulsion prepared by dissolving 2-benzoyl-2'- chloro 5 tridecanoyloxyacetanilide in dibutylphthalate and dispersing the solution in gelatin
• the multi-layer type color photographic light-sensitive material was processed using the following procedures:
• Benzyl alcohol cc 5.0 Sodium sulfite g 5.0 Hydroxylamine hydrochloride g 2.0 3 methyl 4 amino-N-ethyl-N-(beta-methylsulfonamidoethyl)aniline sulfate g 1.5 Potassium bromide g 1.0 Sodium phosphate g 30 Sodium hydroxide g 0.5 Ethylene diamine (70% aqueous solution) cc 7 Water added to make the volume to 1,000 cc.
• Ferricyanide g 100 Sodium acetate g.. 40 Glacial acetic acid g 20 Potassium bromide g 30 Water added to make the total volume to 1,000 cc.
• One of them was prepared as a control sample and the second one has the same composition as the control sample except that Compound 2 described hereinbefore was incorporated in the first emulsion layer, the second emulsion layer, or the fourth emulsion layer of the lightsensitive material in an amount of 100 mg. per mol of silver halide.
• Each of the multi-layer type color photographic lightsensitive materials thus prepared was subjected to the following two types of sensitometric exposure, i.e., red exposure alone and white exposure (red light-i-green light-l-blue light).
• red exposure alone i.e., red exposure alone
• white exposure red light-i-green light-l-blue light
• the amount of red light in the former was controlled to be the same as the amount of red light in the latter and further the amount of each component of the green light and the blue light in the white light was controlled to provide the same photographic effect as that with the red light.
• each of the samples thus exposed was developed according to the developing procedure as described above for the coupler-in-developer type color system. After development, the density of the cyan dye in each sample was measured and expressed as a function of the red exposure amount.
• the interimage effect of each sample can be evaluated using the ratio of gamma values of the characteristic curves of the cyan dye images exposed to red light alone and exposed to white light m/7 wherein 7 represents the gamma value of the cyan dye image when the sample is exposed to red light, while 7 represents the gamma value of the cyan dye image when the sample is exposed to white light).
• the compounds of this invention have the advantages of increasing the interimage elfect without causing desensitization to a great extent.
• EXAMPLE 3 A multi-layer type color photographic light-sensitive material for the coupler-in-developer type color system was subjected to four types of sensitometric exposures, i.e., red light, green light, blue light, and white light (red 1ight+green light+blue light) separately.
• the amount of each of the red light, the green light, and the blue light in the white light was the same as that of the red light, the green light and the blue light, respectively when the light-sensitive material was exposed to each component alone.
• each of the red light, the green light and the blue light was controlled so that the same photographic effect was provided.
• EXAMPLE 4 According to the above-described procedures for the coupler-in-emulsion layer type color system, 11 types of multi-layer type color photographic light-sensitive materials were prepared. One of them was prepared as a control sample and the remaining ten had the same composition as the control sample, except that Compounds 4, 5, 31 and 33 were incorporated in either the protective layer (the eighth layer), the blue-sensitive silver halide emulsion layer (the seventh layer), the yellow filter layer, (the sixth layer), or the intermediate layer (the fourth layer) as shown in Table 4 and in the amount shown in Table 4.
• the multi-layer type color photographic light-sensitive materials thus obtained were exposed in the same manner as in Example 3 and then the light-sensitive materials thus exposed were developed according to the above described developing procedures for the coupler-in-emulsion layer type color system.
• a process for the formation of color photographic images by processing a multi-layer type color photographic light-sensitive material having at least two silver halide emulsion layers on a support which comprises developing said light-sensitive material in the presence of a compound of the Formula I:
• Q represents an atomic group necessary to complete a heterocyclic ring which may be substituted with a member selected from the group consisting of a hydrogen atom, an alkyl group, a substituted alkyl group whose substituent is a hydroxy group, an aryl group, or an alkoxycarbonyl group
• R is selected from the group consisting of an alkyl group and a substituted alkyl group having 1-6 carbon atoms whose substituents are selected from the group consisting of a hydroxy group and a phenyl group and an unsubstituted or substituted phenyl group whose substituent is a carboxy group, said compound serving to impart high saturation to the images thus obtained, unaccompanied by attendant reduction in sensitivity.
• the heterocyclic ring completed by Q is in the series selected from the group consisting of the imidazole ring series, the imidazoline ring series, the thiazole ring series, the thiazoline ring series, the thiadiazole ring series, the benzothiazole ring series, the benzoimidazole ring series, the benzoxazole ring series, the benzoselenazole ring series, the pyridine ring series, the pyrimidine ring series, the quinoline ring series, the triazole ring series, the triazine ring series, the tetrazole ring series, and the tetrazaindene ring series.
• R is selected from the group consising of an alkyl group and a substituted alkyl group containing 1-6 carbon atoms whose substituents are selected from the group consisting of a hydroxy group and a phenyl group and an unsubstituted or substituted phenyl group whose substituent is a carboxy group;
• U and V each represent a member selected from the group consisting of a hydrogen atom, an unsubstitutedor substituted alkyl group whose substituent is a hydroxy group, aryl group, alkoxycarbonyl group, hydroxyl group and an atomic group necessary for forming a saturated or unsaturated ring, which may have been substituted with a member selected from the group consisting of a methyl group and a chlorine atom having from 5 to 6 carbon atoms;
• W represents a member selected from the group consisting of a hydrogen atom and an alkyl group;
• X represents a member selected from the group consisting of S, Se, 0, NR
• -CR CR
• R and R are each a member selected from the group consisting of a hydrogen atom and an atomic group necessary for forming by bonding with each other a ring
• CR R-, where R; is a member selected from the group consisting of a hydrogen atom, an alkyl group and an S-substituted alkyl group
• Y and Z each represent a member selected from the group consisting of a nitrogen atom and where R is a member selected from the group consisting of a hydrogen atom, an alkyl group and an S-substituted alkyl group; at least one of Y and Z being a nitrogen atom.
• At least one of the silver halide emulsion layers contains a member selected from the group consisting of silver chloroiodide, silver iodobromide and silver chloroiodo-bromide, said layer having an iodine content of from 1 to 10 molar percent.

Landscapes

• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=13859565

Family Applications (1)

Country Status (4)

Cited By (9)

Families Citing this family (2)

• 1970
  • 1970-09-29 JP JP45085463A patent/JPS4923895B1/ja active Pending
• 1971
  • 1971-09-28 GB GB4522271A patent/GB1368257A/en not_active Expired
  • 1971-09-29 DE DE19712148667 patent/DE2148667A1/de active Pending
  • 1971-09-29 US US00184951A patent/US3756821A/en not_active Expired - Lifetime

Also Published As

Similar Documents