Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B29/00—Monoazo dyes prepared by diazotising and coupling
  • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
  • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
  • C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
  • C09B29/3647—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms
  • C09B29/3652—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms containing a 1,2-diazoles or hydrogenated 1,2-diazoles
  • C09B29/366—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms containing a 1,2-diazoles or hydrogenated 1,2-diazoles containing hydroxy-1,2-diazoles, e.g. pyrazolone
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
  • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
  • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
  • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
  • C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
• • 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
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
  • G03C1/83—Organic dyestuffs therefor

Definitions

• This invention relates to a multi-layer color photo graphic material, more particularly it relates to a multilayer color photographic film having an improved spectral sensitivity distribution of the blue-sensitive emulsion layer thereof. That is to say, the invention relates particularly to a color photographic film or a color paper suitable for making color prints from a transparent positive or a color negative having insuflicient masking.
• Dyes composing the color photographic image in the subtractive color process usually comprise a yellow dye having an absorption maximum at 420-460 nm., a magenta dye having an absorption maximum at 520- 570 nm., and a cyan dye having an absorption maximum at 640-700 nm.
• the shape of the spectral absorption curve of each of the dyes used in practice is broad with respect to the wavelength, and each of the dyes has an undesirable absorption at a region other than the necessary absorption region. This undesirable absorption by the dye is one of the factors which induces a reduction in the color reproduction property of color photographic images. Further, when such a color photographic image is used for making color prints, the color reproduction property is further reduced.
• the spectrally sensitive region of each' of the emulsion layers is sharply separated by the use of a proper sensitizing dye and thereby the desirable maximum wave-length region of the spectral sensitivity is determined.
• the absorption region intrinsic to the silver halide in the emulsion is utilized and thus the spectrally sensitive region of the blue-sensitive layer is broad, a factor greatly different from the green-sensitive layer and the red-sensitive layer which are each spectrally sensitized with a dye.
• the reduction in the color reproduction property of the blue-sensitive layer caused by the undesirable absorption of the dye described above has heretofore been considered unavoidable.
• One object of this invention is to provide a multi-layer type color photographic light-sensitive material illustrating lowered color mixing which also has a color reproduction almost the same as the original.
• a further object of this invention is to provide a multilayer type photographic silver halide light-sensitive material for prints wherein the spectrally sensitive maximum wavelength of the blue-sensitive emulsion layer is a wavelength region which includes less undesirable side absorptions of the cyan dye and magenta dye and which is almost the same as the absorption maximum of a yellow dye, that is to say, in the region of substantially from 440 nm. to 460 nm.
• Another object of this invention is to provide a process of producing such a multi-layer type color photographic light-sensitive material.
• R represents an amino group, a hydroxyl group, or -OR' (where R is a methyl group or an ethyl group) and X, represents -COO"M+ or SO -M+ (M+ is a cation such as a hydrogen ion, an alkali metal ion such as a sodium ion or a potassium ion, or an ammonium ion, preferably M+ is a potassium ion).
• any combination of groups R and X may be used.
• the position (wavelength) of the absorption maximum may shift, but it is in the range of from about 360 nm. to about 430 nm.
• any combination of the groups of R and X can be used and the absorption maximum is at about 500 nm.
• the amount of the dyes of the General Formula I, II, and III is not critical and generally a range of these dyes in an amount of from about 3 10- to about 3X10 mole/mole silver halide based on the silver halide present in the blue-sensitive silver halide emulsion layer can be used.
• pyrazolone was dissolved in a mixture of 100 cc. of 10% and, under stirring, the aqueous diazo compound solution prepared above was added dropwise to the solution thus prepared, whereby a coupling reaction occurred to form a dye. 1000 cc. of aqueous saturated sodium chloride solution was added to the solution of the dye to cause salting out. The dye was recovered by filtration and then subjected to salting out again to obtain 25 g. of the desired product.
• the aqueous solution of the dye has its desired absorption maximum at 430 nm.
• the aqueous solution of the dye had its absorption maximum at 384 nm.
• Dyes other than the above can be produced by methods similar to those of Syntheses 1, 2 and 4.
• color reproduction is markedly improved, in particular the mixing of yellow dye into a cyan dye and a magenta dye when a cyan dye and a magenta dye of an original are printed, i.e., the occurrence of undesirable coloring in the blue-sensitive emul sion layer, is greatly reduced.
• the color photographic light-sensitive materials of this invention have never been known, and even if it would be anticipated that the color reproduction might be improved if the region of sensitivity distribution was narrowed, a method of accurately controlling the spectrally sensitive region as in the present invention has never been known.
• the incorporation of the dye referred to above in a color photographic material for prints means that a bluesensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer are insensitive to light of the Wavelength region cut by the dye, and thus the dye of this invention may be incorporated in the bluesensitive silver halide photographic emulsion layer and/or in any emulsion layer of the light-sensitive material coated on the blue-sensitive silver halide photographic emulsion layer. It is particularly preferable to incorporate the dye of this invention in the blue-sensitive emulsion layer or in a protective gelatin layer coated on the bluesensitive emulsion layer.
• the dyes previously described may be added to the emulsion layer alone, but better results can be obtained when a combination of suitable dyes is added as shown in examples of this invention.
• the dyes used in this invention are not limited to the dyes shown in the examples, but any dyes satisfying the conditions previously indicated can be used in this invention.
• Example 1 A red-sensitive emulsion was prepared in the following manner. 300 g. of a 5.2 wt. percent aqueous gelatin solution was added to 700 g. of a negative photographic emulsion consisting of 77 g. of silver iodo-bromide grains containing 3 mole percent iodide ions and having a mean grain size of 0.35 micron, 49 g. of gelatin and 574 g. of water and then the mixture was maintained at 35 .0 C. to yield a sol.
• the silver halide emulsion for the red-sensitive emulsion layer thus prepared was coated on a cellulose triacetate support (so that the dry thickness of the layer was 4.0/1.) having an antihalation layer, and then a thin gelatin layer was coated on the red-sensitive emulsion layer.
• a green-sensitive emulsion was prepared in the following manner. 300 g. of a 5.2 wt. percent aqueous gelatin solution was added to 700 g. of a negative photographic emulsion consisting of 77 g. of silver iodo-bromide grains containing 3 mol percent iodide ions and having a means grain size of 0.43 micron, 49 g. of gelatin and 574 g. of water, and the mixture was maintained at 35.0 C. to yield a so 110 ml.
• the photographic emulsion for the green-sensitive emul- S1011 layer thus prepared was coated on the thin gelatin layer on the red-sensitive emulsion layer formed above so that the dry thickness of the layer was 4.5 microns.
• a yellow colloidal silver gelatin layer containing colloidal silver of a 0.03 micron mean grain size was uniformly coated to a dry thickness of 1.0 micron.
• Specimen 1.- g. of a 5.2% aqueous gelatin solution was added to 850 g. of the same silver halide emulsion (the mean grain size of the silver halide was 0.43
• the coupler dispersion obtained was added to the silver halide emulsion mixture prepared above so that the content of the coupler was 0.22 mole per mole of silver halide. Moreover, the same hardening agent and surface active agent as used in producing the green sensitive emulsion layer were added to the blue-sensitive photographic emulsion.
• the blue-sensitive emulsion thus prepared was coated onto the yellow colloidal silver-gelatin layer formed on the green-sensitive emulsion layer (as indicated above) to a dry thickness of 5 microns, and then a thin gelatin layer was coated onto the blue-sensitive layer as a protective layer to give Specimen 1.
• Specimen 2.l50 g. of 5.2 wt. percent aqueous gelat n solution was added to 850 g. of a negative photographic emulsion consisting of 93 g. of silver halide grains containing 3 mole percent iodide ions and having a mean grain size of 0.6 micron, 60 g. of gelatin, and 697 g. of water, and the mixture was maintained at 35 C. to yield a sol. Then, 100 ml.
• the blue-sensitive emulsion thus prepared was coated onto the yellow colloidal silver-gelatin layer on the green-sensitive emulsion layer formed above to a dry thickness of 5 microns, and then a thin gelatin layer was coated uniformly onto the blue-sensitive layer as a protective layer to yield Specimen 2.
• compositions of the developing solution were as follows:
• Black and white developing solution Water ml.. 800 N-methyl-p-aminophenol g 4.5 Hydroquinone g 5.5 Anhydrous sodium sulfite g 50 Sodium carbonate (mono-hydrate) g 30.5 Potassium bromide g 1.5 0.1% aqueous potassium iodide solution ml 10 Potassium thiocyanide (10% aqueous soln.) ml 20 Water added to make the total volume 1 liter.
• the reversal processing for the specimens was conducted in the following manner.
• the specimen was developed by the black and white developing solution having the above composition for 10 minutes at 24 C., then washed with water, and the whole area of the specimen was exposed uniformly to intense white light. Then, the specimen was developed by the color developing solution having the above-mentioned composition for 15 minutes at 24 C., washed with water, bleached, fixed, and washed with water.
• a light-sensitive film having only a red-sensitive emulsion layer containing the cyan coupler as described hereinbefore in Example 1 was prepared, exposed to a tungsten lamp of a color temperature of 2854 K. through a conventional optical wedge, and subjected to the above-mentioned reversal processing using the developing solution indicated above, whereby a cyan colored strip, was obtained.
• Each of Specimen 1 and Specimen 2 was exposed to a tungsten lamp of a color temperature of 2854 K. using the cyan-colored strip obtained above instead of the optical wedge to obtain a print image.
• the color mixing of the print was evaluated by comparing the gradient ratio of the R density and the G density 'y /y and also the gradient ratio of the R density and the B density /7 of the specimens with those of the cyan colored strip which is designated the original. The results are shown in Table 1.
• Example 1 The specimen identified as Specimen 1 in Example 1 was prepared as Specimen 1 of this example.
• Specimen 3 was prepared by coating a blue-sensitive emulsion prepared as below onto the yellow colloidal layer on the same green-sensitive emulsion layer as in Specimen 1, Le, both specimens were identical except for the blue-sensitive emulsion.
• 150 g. of a 5.2 wt. percent aqueous gelat1n solution was added to 850 g. of a negative photographic emuls on-consisting of 93 g. of silver iodo-bromide grains contain ng 3 mole percent iodide ions and having a mean grain size of 0.8 micron, 60 g. of gelatin, and 697 g. of water, and the mixture was maintained at 35 C. to yield a so ml.
• This blue-sensitive emulsion was coated onto the yellow colloidal silver-gelatin layer on the green-sensitive emulsion layer which was further formed on the red-sensitive emulsion layer of the same structure as in Specimen 1 to a dry thickness of 5 microns.
• Specimen 1 in this example was the same as Specimen l in Example 3.
• Specimen 4 was prepared by coating the photographic emulsion for the blue-sensitive emulsion layer prepared as below onto the green-sensitive emulsion layer having the same composition as Specimen 1.
• 150 g. of a 5.2 wt. percent aqueous gelatin solution was added to 850 g. of a negative photographic emulsion consisting of 93 g. of silver iodo-bromide grains containing 3 mole percent iodide ions, 60 g. of gelatin, and 697 g. of water, and the mixture was maintained at 35 C. to yield a sol.
• the ratios 'y /q and 'y l'y of the lightsensitive materials of this invention are far nearer the values of the originals as compared with the light-sensitive materials containing no dyes of this invention.
• the dye of this invention yellow dye mixing in the case of printing an image composed of a cyan dye and a magenta dye as an original can be remarkably reduced and a color print having color tones substantially the same as that of the original can be obtained.
• a multiple layer type color photographic silver halide light-sensitive material for color prints having at least a blue-sensitive photographic emulsion layer in which the spectral sensitivity of the blue-sensitive silver halide emulsion layer is limited to the region of about 440 to about 460 nm. wherein at least one dye having its absorption maximum at a wave length region shorter than about 440 nm. and/or in a region of about 460 to about 520 nm. is incorporated in said blue-sensitive photographic layer and/ or in at least one layer coated on said blue-sensitive photographic emulsion layer of the lightsensitive material.
• R represents an amino group, a hydroxyl group, or OR', wherein R is a methyl group or an ethyl group and X represents COOM or SO M+, wherein M+ is a cation.
• R represents a methyl group, COOC H or -COO-M X and Y each represents a hydrogen atom or -SO M+, wherein M+ and M each is a cation.
• R represents an amino group, a hydroxyl group, or -OR', wherein R is a methyl group or an ethyl group and X represents COO-M+ or --SO M wherein M+ is a cation.
• M+ is selected from the group consisting of a hydrogen ion, an alkali metal ion and an ammonium ion.
• M is selected from the group consisting of a hydrogen ion,an alkali metal ion and an ammonium ion.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=11610165

Family Applications (1)

Country Status (6)

Cited By (10)

Families Citing this family (5)

Family Cites Families (6)

• 1971
  • 1971-02-09 JP JP46005403A patent/JPS511419B1/ja active Pending
• 1972
  • 1972-02-08 FR FR7204155A patent/FR2124565B1/fr not_active Expired
  • 1972-02-08 CA CA134,237A patent/CA994766A/en not_active Expired
  • 1972-02-08 GB GB591572A patent/GB1385371A/en not_active Expired
  • 1972-02-09 US US00224933A patent/US3746539A/en not_active Expired - Lifetime
  • 1972-02-09 DE DE2206112A patent/DE2206112C3/de not_active Expired

Also Published As

Similar Documents