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
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/28—Sensitivity-increasing substances together with supersensitising substances
• • 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
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/10—Organic substances
  • G03C1/12—Methine and polymethine dyes

Definitions

• This invention relates to a novel technique for dye spectral sensitization of silver halide photographic materials. More specifically, the invention relates to a silver halide photographic material having greatly improved spectral sensitivity in the desired light-sensitive silver halide emulsion layer by incorporating a dye having a high luminousity and a relatively weak adsorptive property to silver halide in the dispersion medium of the spectrally sensitized light-sensitive silver halide emulsion and by co-existing a hydrophilic polymer having a mordanting power to the luminous dye or a dispersion of the hydrophilic polymer.
• This invention is a fundamental technique of spectral sensitization on the whole silver halide photographic materials and the utilization field thereof includes all silver halide photographic materials such as negative, positive, and reversal black and white and color photographic light-sensitive materials.
• a method of spectrally sensitizing silver halide emulsions by dye(s) is a well-known technique and as the sensitizing dyes, methine series dyes such as cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, etc., are generally used. Also, as the case may be, a combination of two or more kinds of these dyes are used for expanding the color sensitizing wavelength region or giving a super color sensitizing effect. These sensitizing dyes are required to have a property of being adsorbed on the surfaces of silver halide grains as electron injection type sensitizing dyes.
• sensitizing dyes there is a limit in the adsorbing amount of sensitizing dyes onto the surfaces of silver halide grains and if sensitizing dyes are adsorbed in a saturated adsorption state or near the state, they frequently cause a severe desensitization (intrinsic desensitization) as described, e.g., in W.C. Lewis et al, Photographic Science and Engineering, Vol. 13, 54(1969). Also, at the same time, the surface coating of silver halide grains sometimes causes problems of development inhibition, etc. Accordingly, the percent absorption (utilization efficiency) of incident photons onto each silver halide grain in the spectral sensitizing region is very low at present.
• Bird et al disclose a method of adsorbing plural dyes onto silver halide grains in multilayer state in U.S. Patent 3,622,316 or adsorbing sensitizing dye molecules having plural cyanine chromophores onto silver halide grains in U.S. Patents 3,622,317 and 3,976,493 to increase the amount of absorbed light, whereby the silver halide grains are sensitized by the contribution of a Forster type excitation energy transfer.
• the limitation of the adsorbed area and the restriction by the intrinsic desensitization cannot be avoid and in fact, sufficient effects are not obtained by these methods.
• Steiger et al disclose a sensitization method of chemically bonding fluorescent dyes such as cyanine dyes and xanthene dyes to colloid molecules which are a dispersion medium, such as gelatin, etc., and exciting the dyes adsorbed on the surface of silver halide grains or different kind of spectral sensitizing dyes by the Forster type energy transfer Th.
• Forster Disc. Faraday Soc., Vol. 27, page 7, 1959
• JP-A as used herein means an "unexamined published Japanese Patent Application”.
• dyes which are not directly adsorbed on silver halide grains also contribute to sensitization different from the Bird et al system.
• the aforesaid method is a means of dispersing spectral sensitizing dye having a strong adsorptive property in a medium, part of the dyes bonded to gelatin directly bond to silver halide grains. Accordingly, since the adsorbed dye acts as an energy acceptor, it is generally difficult to realize the optimum overlapping of the luminous band by a non-adsorbed dye and the absorption band of the adsorbed dye. This is a large restriction for attaining a high efficient energy transfer since the overlapping of a luminous band and an absorption band is principally necessary for the energy transfer in a Forster type energy transfer and the re-adsorption of luminescence.
• the freedom of synthesizing and selecting such a medium bonding type luminous dye material is greatly restricted as compared to a method of simply dispersing an optional amount of a water-soluble luminous dye in a hydrophilic medium.
• the water-soluble light-collecting dye can freely diffuses into other layer(s), the light-collecting dye diffused into an upper layer on the light-sensitive emulsion layer being subjected to light-collecting sensitization has a prolonged transfer distance of a light-exiting energy, whereby the sensitization can not be expected as well as the dye has a fault of causing desensitization as a simple filter. This is true in black and white light-sensitive materials.
• a protective layer is generally formed on a light-sensitive emulsion layer in a black and white light-sensitive material, if the light-collecting dye diffuses into the protective layer, the occurrence of a sensitivity loss to some extent is unavoidable.
• An object of this invention is, therefore, to provide a silver halide photographic material wherein the light utilization is increased and the color sensitizing sensitivity is greatly improved by using light-collecting dye-(s).
• Another object of this invention is to provide a silver halide photographic material giving good photographic images without introducing desensitizing factors such as intrinsic desensitization and development inhibition by using light-collecting dye(s) having weak adsorptive property to silver halide grains.
• a still other object of this invention is to provide a silver halide photographic material having plural layer structure, in which a light-collecting dye is fixed in a desired light-sensitive emulsion layer, functions the light-collecting sensitizing effect at light exposure, and is almost completely washed out at processing to give substantially no color residue.
• the inventors have succeeded in solving the aforesaid various problems by greatly increasing the utilization efficiency of light energy by a light-collecting sensitization method of utilizing the light absorption by a luminous dye dispersed in a hydrophilic medium and the subsequent light-exiting energy transfer, and also co-existing a cationic polymer in the medium, whereby the light-collecting dye is fixed in the desired light-sensitive emulsion layer to prevent the reduction of sensitivity by the diffusion of the light-collecting dye into other layer(s).
• a silver halide photographic material having at least one silver halide emulsion layer spectrally sensitized by spectral sensitizing dye(s), wherein the silver halide emulsion layer or other hydrophilic colloid contains in the hydrophilic dispersion medium a hydrophilic polymer having a cationic structure or a dispersion of the polymer and a luminous dye (light-collecting dye) which has a relatively weak adsorptive property to silver halide grains, is easily removed by photographic processing, and simultaneously meets the following conditions 1) to 3), with the proviso that the light-collecting dye and the spectral sensitizing dye may be the same compounnd;
• the luminous dye (light-collecting dye) for use in this invention is a dye having a high water solubility and a relatively weak adsorptive property to silver halide grains.
• the term "relatively weak adsorptive property" in this invention is defined as that the adsorptive power thereof is lower than 10- 6 moleim 2 to the outer surface of the ⁇ 111 ⁇ plane of silver bromide grain under the equilibrium concentration of 10 -4 mole/liter in an aqueous 5 wt.% gelatin solution at a temperature of 40°C and pH of 6.5 ⁇ 0.05.
• the adsorption amount is preferably less than 5 x 10- 7 mole/m 2 , and more preferably less than 10- 7 mole/m 2.
• the adsorption amount of a dye can be determined by a method of adding the dye to an emulsion containing 5% by weight gelatin, after stirring the emulsion for 18 hours at 40 C under safelight, separating the silver halide grains by centrifugal separation, and measuring the concentration of the dye in the supernatant liquid.
• the adsorption amount of the light-collecting dye for use in this invention is as defined above for silver bromide but the adsorption amount is also preferably low as above for silver halide grains containing iodine or chlorine.
• the luminous dye (light-collecting dye) for use in this invention has a sufficiently high water solubility, and preferably has a solubility of higher than 10- 2 mole/liter for water at 25° C and pH 7.0. Also, it is preferred that when the luminous dye molecule in this invention is dissociated in water medium, the total static charges are negative.
• a water-solubilizing group a sulfonic acid group and a carboxylic acid group are particularly preferred and when the dye has at least 4 such anionic hydrophilic groups, the dye is imparted with a particularly high water solubility and at the same time becomes substantially non-adsorptive to silver halide.
• the dye can be dissolved in a hydrophilic colloid of a silver halide emulsion layer at a high concentration as well as can be quickly and completely removed therefrom by water washing.
• the light-collecting dyes for use in this invention having a high water solubility and being substantially non-adsorptive to silver halide grains are not always limited to the molecule having the aforesaid structure but as the kind of the dyes, cyanine series dyes are particularly preferred in the points that water-solubilizing groups are easily introduced in the case of synthesizing the dyes and the dyes are excellent in luminous efficiency.
• the quantum yield of the luminescence of the light-collecting dye for use in this invention is required to be higher than 0.1, preferably higher than 0.8, and more preferably higher than 0.5 at a concentration of 10- 4 mole/dm 2 in dry gelatin medium at room temperature.
• the luminous quantum yield of the light-collecting dye in dry layer can be fundamentally measured by the same method for measuring the luminous quantum yield in a solution and usually by referring to a standard sample (e.g., rhodamine B, quinine sulfate, and 9,10-diphenylanthracene) having a known absolute quantum yield, the luminous quantum yield of the dye can be obtained by a relative measurement of comparing the intensity of incident light, the light absorption coefficient of the sample, and the luminous intensity of the sample.
• a standard sample e.g., rhodamine B, quinine sulfate, and 9,10-diphenylanthracene
• the relative measurement method is described, for example, in C.A. Parker and W.T. Rees, Analyst, Vol. 85, 587(1960).
• the luminous quantum yield of the light-collecting dye in dry gelatin defined in this invention can be easily obtained by performing the aforesaid relative measuring method by referring to a dry gelatin film (sheet form sample) having a known absolute quantum yield, in which a standard luminous dye is dispersed at an optional concentration.
• the inventors measured the luminous absolute quantum yield on a dry film of a standard sample by the following method.
• fluorescent N-phenyl-1-naphthylamine-8-sulfonic acid having no contribution of reabsorption by overlapping of the absorption band and the luminous band was selected and gelatin containing the compound was uniformly coated on a transparent support followed by drying to provide a standard sample having a dye concentration in the dry layer of 10- 2 mole/dm 2 and a gelatin coverage of 6 g/m 2 .
• the sample was set in the inside of an integrating sphere the inside wall of which was coated with white powder (BaS0 4 ), the sample was irradiation with monochromatic excited light of 380 n.m., and the intensities of the excited light and fluorescence were detected by a photomultiplier equipped to the window of the integrating sphere.
• the light absorption coefficient A of the sample was measured by mounting a fluorescent cutting filter on the photomultiplier and comparing the intensity of the excited light between the case of setting the sample and the case of not setting the sample.
• the fluorescent integrating intensity F was measured by mounting an excited light cutting filter in place of the aforesaid filter.
• the absolute fluorescent quantum yield was calculated from F/(I*A).
• a so-called stoke shift i.e., the distance between the wavelength of the absorption peak and the wavelength of the luminous peak is sufficiently small from the purpose of increasing the overlapping of the absorption band and the luminous band and also increasing the energy transfer efficiency.
• the stoke shift for increasing the energy transfer efficiency is preferably within 40 n.m., and more preferably within 20 n.m. at a concentration in dry gelatin layer of 10- 4 mole/dm 2 at room temperature.
• the stoke shift having sufficiently small value within 20 n.m. can be found in many cyanine dyes.
• the light-collecting dye for use in this invention gives a luminous band sufficiently overlapping the absorption band given by the adsorption seeds of blue, orthomatic, or panchromatic sensitizing dyes which are generally used for black and white and silver halide color photographic light-sensitive materials, and further it is preferred for effective purpose that the stokes shift is relatively short as described above, the maximum adsorption wavelength of the light-collecting dye is preferably longer than 400 n.m., more preferably longer than 420 n.m., and particularly preferably from 420 n.m. to 740 n.m.
• cyanine series dyes are particularly preferred in the points of the luminous quantum yield and the stokes shift as described above.
• D.F. O'Brien et al reported the fluorescent yields of the dyes in solution or other materials in Photographic Science Engineering, Vol. 18, 76(1974) and about oxacarbocyanine derivatives, the value of 0.75 was obtained in gelatin.
• other kind of dyes having a high luminous quantum yield there are typical dyes having a skeleton structure of dyes which are used for dye laser. Examples of these dyes are described, for example, in Mitsuo Maeda, Laser Kenkyo (Research), Vol.
• non-adsorptive luminous dyes particularly preferred in this invention are illustrated below but the skeletone structures and substituents are not limited to them.
• the adsorption amounts of the aforesaid light-collecting dyes A-1 to A-76 to silver bromide measured by a centrifugal separation method under the conditions described in the claim of this invention were all less than 10- 6 mole/m 2 and the luminous quantum yields thereof measured under the conditions described in the claim were all above 0.1.
• the luminous quantum yields of the dyes A-1 to A-11 and A-47 to A-54 were all high as above 0.7.
• cyanine dyes for use in this invention can be synthesized based on the various methods described, e.g., in F.M. Hamer, The Cyanine Dyes and Related Compounds, Interscience, New York (1964). Typical Synthesis methods are shown below.
• the light-sensitive silver halide grains for the silver halide photographic materials of this invention are a dispersion of fine grains, have an adsorbed layer of a spectral sensitizing dye on the surface thereof, and have been spectrally sensitized by the spectral sensitizing dye. Furthermore, outside of the adsorbed layer of spectral sensitizing dye, there exists a hydrophilic colloid medium in which the water-soluble light-collecting dye molecule in this invention is uniformly dispersed and the medium is in a body with the aforesaid light-sensitive silver halide grains to form a light-sensitive element. In this case the light-collecting dye dispersed in a hydrophilic colloid medium exists in a state that the chromophores thereof are not directly adsorbed on the light-sensitive silver halide grains.
• the light-collecting dye is preferably added to a silver halide emulsion layer containing an adsorptive spectral sensitizing dye.
• the addition amount of the light-collecting dye in a dispersion medium is preferably at least 2 x 10- 3 mole/dm 2 and more preferably at least 10- 2 mole/dm 2 as concentration.
• concentration is a concentration per dry amount of the dispersion medium exclusive of silver halide grains and adsorption seeds on the surface of the grains.
• concentrations is preferably less than 10- 1 mole/dm 2 in this meaning.
• the light-collecting dyes in this invention can be also used as a mixture of plural dyes and in this case it is required that at least a part of the luminous wavelength bands of these dyes overlaps the optical absorption band of the at least one kind of sensitizing dye adsorbing on silver halide grains.
• the maximum luminous wavelength of the light-collecting dye giving the maximum luminescence to the longest wavelength in these dyes is preferably disposed near the maximum absorption wavelength of the adsorbed sensitizing dye receiving energy transfer, and, in particular, is preferably disposed within 60 n.m., more preferably within 30 n.m. from the maximum absorption wavelength to a shorter wavelength side.
• the wavelength giving the luminous maximum of the luminous dye is preferably not over the wavelength of the maximum absorption of the dye having absorption at the longest wavelength region in the dyes adsorbedd on the silver halide.
• the overlap of the absorption band and the luminous band given by the light-collecting dyes in a medium is large, and the so-called stroke shift, e.i., the difference between the maximum absorption wavelength and the maximum luminous wavelength is preferably within 40 n.m., and particularly preferably within 20 n.m.
• the light-collecting dyes for use in this invention can be used together with a proper surface active agent and organic additives such as a solubilizing agent and an association preventing agent.
• the light-collecting dyes for use in this invention are quickly removed from the photographic light-sensitive materials by photographic processing or washing or are decomposed and bleached during processing.
• the light-collecting dyes are of the type of being discolored by hydrolysis, etc., in an alkaline aqueous solution after removed from the light-sensitive materials.
• the reduction potential of the light-collecting dyes for use in this invention is baser than 0.10 volt to a standard calomel reference electrode in a mixture of water and methanol (1 : 1).
• the reduction portential of dyes can be measured according to the description of Tadaaki Tani et al, Denski Kagaku (Electrochemistry), Vol. 34, 149(1966).
• polymers having a cationic structure which are preferably used in this invention, are shown by following formula (I), (II), or (lll);
• A represents a monomer unit having at least two copolymerizable ethylenically unsaturated groups and copolymerized with a copolymerizable monomer having at least one of the aforesaid ethylenically unsaturated groups at the side chain thereof;
• B represents a monomer unit copolymerized with a copolymerizable ethylenically unsaturated monomer;
• R represents a hydrogen atom, a lower alkyl group, or an aralkyl group;
• R 2 , R 3 , and R4 which may be the same or different, each represents a hydrogen atom, an alkyl group, or an aralkyl group.
• R 2 , R 3 , and R 4 may form a 5-membered or 6-membered ring or such a heterocyclic ring together with nitrogen atom.
• Q represents an alkylene group, a phenylene group, an aralkylene group, (wherein L represents an alkyl group, an arylene group, or an aralkylene group and R represents an alkyl group).
• Q may be a single bond.
• X e represents an anion
• D e represents a 5-membered or 6-membered heterocyclic ring having 1 or 2 nitrogen atoms, wherein the nitrogen atom is positively charged
• D 9 may have substituent
• x, y, and z represent mole percentage, and x is from 0 to 60 mole%, y is from 0 to 60 mole%, and z is from 30 to 100 mole%.
• examples of the monomer shown by A are divinylbenzene, ethylene glycol methacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, meopentyl glycol dimethacrylate, and tetramethylene glycol dimethacrylate.
• divinylbenzene and ethylene glycol dimethacrylate are particularly preferred.
• Examples of the ethylenically unsaturated monomer shown by B are ethylene, propylene, 1-vinyltoluene, monoethylenically unsaturated esters of alipathic acids (e.g., vinyl acetate and allyl acetate), amides of ethylenically unsaturated monocarboxylic acid or dicarboxylic acid (e.g., acrylamide, methacrylamide, N-methylacrylamide, and N-tert-butylacrylamide), esters if ethylenically unsaturated monocarboxylic acid or dicarboxylic acid (e.g., methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, n-butyl acrylate, n-hexyl acrylate, and 2-ethylhe
• B may contain two or more kinds of the aforesaid monomers.
• Ri preferably represents a hydrogen or a lower alkyl group having from 1 to 6 carbon atoms (e.g., methyl, ethyl, n-propyl, n-butyl, n-amyl, and n-hexyl) and is particularly preferably a hydrogen atom or a methyl group.
• R 2 , R 3 , and R 4 which may be the same or different, each is preferably a hydrogen atom, an alkyl group having from 1 to 20 carbon atoms, or an aralkyl group having from 7 to 20 carbon atoms.
• the alkyl group and the aralkyl group include substituted alkyl groups and substituted aralkyl groups, respectively.
• R 2 , R 3 , and R4. may combine with each other to form a 5- membered or 6-membered ring structure or such a heterocyclic structure together with nitrogen atom.
• alkyl group examples are unsubstituted alkyl groups (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-amyl, isoamyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, and n-dodecyl), the carbon atom number of said alkyl group being preferably from 1 to 6, and substituted alkyl groups such as alkoxyalkyl groups (e.g., methoxymethyl, methoxyethyl, methoxybutyl, butoxyethyl, butoxypropyl, butoxybutyl, and vinyloxyethyl), cyanoalkyl groups (e.g., 2-cyanoethyl), cyanoalky
• aralkyl group examples include unsubstituted aralkyl groups (e.g., benzyl, phenetyl, diphenylmethyl, and naphthylmethyl) and substituted aralkyl groups such as alkylaralkyl groups (e.g., 4-methylbenzyl, 2,5-dimethylbenzyl, and 4-isopropylbenzyl), alkoxyaralkyl groups (e.g., 4-methoxybenzyl, 4- ethoxybenzyl, and 4-(4-methoxyphenyl)benzyl), cyanoaralkyl groups (e.g., 4-cyanobenzyl and 4-(4-cyanophenyl)benzyl), perfluoroaralkyl groups (e.g., 4-pentafluoropropoxybenzyl and 4-undecanefluorohexyl- benzyl), and halogenated aralkyl groups (e.g., 4-
• Examples of the ring structure formed by the combination of optional two or three groups of R 2 , R 3 , and R 4 together with nitrogen atom are a pyrrolidine ring, a piperidine ring, a morpholine ring, and quinuclidine ring.
• Q is preferably a divalent alkylene group having from 1 to 12 carbon atoms (e.g., methylene or a group shown by -(CH 2 ) 6 ), a phenylene group, or an aralkyl group having from 7 to 12 carbon atoms (e.g., a group shown by or and also the groups shown by the following formulae are preferred as Q; (wherein L is preferably an alkylene group having from 1 to 6 carbon atoms, an arylene group, or an aralkylene group having from 7 to 12 carbon atoms and R is preferably an alkyl group having from 1 to 6 carbon atoms).
• Q is also preferably a single bond.
• X 9 represents an anion and examples of the anion are halogen ions (e.g., chloride ions and bromide ions), alkylsulfonate ions or arylsulfonate ions (e.g., methanesulfonate ions, ethanesulfonate ions, benzenesulfonate ions, and p-toluenesulfonate ions), acetate ions, sulfate ions, and nitrate ions and in these anions, chloride ions, acetate ions, sulfate ions, and nitrate ions are particularly preferred.
• halogen ions e.g., chloride ions and bromide ions
• alkylsulfonate ions or arylsulfonate ions e.g., methanesulfonate ions, ethanesulfonate ions, benzenesulf
• Examples D 9 are preferably as follows;
• X is from 0 to 60 mole%, preferably from 0 to 40 mole%, and more preferably from 0 to 20 mole%
• y is from 0 to 60 mole%, preferably from 0 to 40 mole%, and more preferably from 0 to 20 mole%
• z is from 30 to 100 mole%, preferably from 40 to 90 mole%., and more preferably from 50 to 90 mole%.
• the polymer mordant shown by formula (I) described above for use in this invention can be generally obtained by polymerizing the copolymerizable monomer (A) having at least two ethylenically unsaturated groups described above, the ethylenically unsaturated monomer (B), and an unsaturated monomer shown by the following formula (wherein R 1 , R 2 , R 3 , and Q have the same significance as described above), such as N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl acrylate, N-(N,N-dimethylaminopropyl)acrylamide, N-(N,N-dihexylaminomethyl)-acrylamide, 3-(4-pyridyl)propyl acrylate, N,N-diethylamino
• the polymer mordant shown by formula (1) for use in this invention can be obtained by polymerizing the copolymerizable monomer (A) having at least two ethylenically unsaturated groups, the ethylenically unsaturated monomer (B) described above, and an unsaturated monomer shown by the formula; (wherein Ri, R 2 , R 3 , R 4 , X and Q are same as defined above), such as N,N-dimethylaminoethyl methacrylate hydrochloride, N,N-diethylaminoethyl methacrylate sulfate, N,N-dimethylaminoethyl acrylate hydrochloride, N,N-diethylaminoethyl acrylate acetate, N-(N,N,N-trimethylaminopropyl)acrylamide chloride, N-(N,N,N-trihexylaminomethyl)acrylamide chloride, 3-(4-N-methylmethyl
• the polymer mordant shown by formula (I) for use in this invention can be obtained by polymerizing the copolymerizable monomer (A) having at least two ethylenically unsaturated groups, the ethylenically unsaturated monomer (B), and an unsaturated monomer shown by the formula
• the polymer mordant shown by formula (II) for use in this invention can be obtained by polymerizing the copolymerizable monomer (A) having at least two ethylenically unsaturated groups, the ethylenically unsaturated monomer (B), and an unsaturated monomer shown by the formula (wherein Ri is same as defined above and D represents a 5-membered or 6-membered heterocyclic ring having 1 or 2 carbon atoms, and D may have substituent), such as 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 1-vinyl-imidazole, and 2-methyl-4-vinylpyridine, and then converting the product into an ammonium salt by a compound shown by the formula R L - X (wherein x is same as defined above).
• the polymer mordant shown by formula (II) for use in this invention can be obtained by polymerizing the copolymerizable monomer (A) having at least two ethylenically unsaturated groups, the ethylenically unsaturated monomer (B), and an unsaturated monomer shown by the formula (wherein R i , D ⁇ , and X e are same as defined above), such as 2-vinylpyridine hydrochloride, 1-methyl-3-vinylpyridine chloride, 4-vinylpyridine sulfate, 1-vinylimidazole hydrochloride, and 2-methyl-4-vinylpyridine sulfate.
• 2-vinylpyridine hydrochloride 1-methyl-3-vinylpyridine chloride
• 4-vinylpyridine sulfate 1-vinylimidazole hydrochloride
• 2-methyl-4-vinylpyridine sulfate 2-methyl-4-vinylpyridine sulfate.
• the polymer mordant shown by formula (III) for use in this invention can be obtained by polymerizing the copolymerizable monomer (A) having at least two ethylenically unsaturated groups, the ethylenically unsaturated monomer (B), and an unsaturated monomer shown by the formula (wherein R i , R 2 , and Q are same as defined above), such as vinyl methyl ketone and diacetone acrylamide) and then converting the product into a guanidine salt by aminoguanidine bicarbonate and an acid shown by the formula H-X (wherein X is same as defined above).
• the aforesaid polymerization reaction may be performed by a solution polymerization, an emulsion polymerization, a suspension polymerization a precipitation polymerization, or a dispersion polymerization.
• a solution polymerization and an emulsion polymerization are preferred.
• the aforesaid solution polymerization is generally performed in the existence of a radical polymerization initiator (e.g., the co-use of potassium persulfate and sodium hydrogensulfite, the initiators commercially available as V-50 and V-65 from Wako Junyaku K.K.) at temperature of from 30 °C to 120°C, and preferably from 40° C to 100° C.
• a radical polymerization initiator e.g., the co-use of potassium persulfate and sodium hydrogensulfite, the initiators commercially available as V-50 and V-65 from Wako Junyaku K.K.
• the aforesaid emulsion polymerization is generally performed in the existence of at least one emulsifier selected from anionic active agents (e.g., sodium dodecylsulfate and Triton 770 (trade name, made by Rhom & Haas Co.), cationic surface active agents (e.g., octadecyltrimethyl ammonium chloride), nonionic surface active agents (e.g., Emulex NP-20 (trade name, made by Nippon Emulsion K.K.)), gelatin, polyvinyl alcohol, etc., and a radical polymerization initiator (e.g., the co-use of potassium persulfate and sodium hydrogensulfite, and V-50 commercially available from Wako Junyaku K.K.) at temperature of from 30° C to 100" C, and preferably from 40 C to 80° C.
• anionic active agents e.g., sodium dodecylsulfate and Triton 770 (
• the aforesaid reaction for converting into an ammonium salt or a guanidium salt is performed at temperature of from -10 C to 40° C, and preferably from 0° C to 30° C.
• the polymer dispersion mordant for use in this invention can be very easily produced in one reaction vessel.
• the mixture was cooled to 40°C, 108 g of distilled water and 62 g of isopropyl alcohol were added thereto, and after further adding dropwise 3.4 g of triethylamine to the mixture over a period of 15 minutes, the resultant mixture was stirred for 2 hours and 40 minutes followed by filtration to provide the polymer dispersion having a solid component concentration of 8.46 wt.%.
• the aforesaid cationic polymers may be used singly or as a mixture thereof.
• the amount of the cationic polymer being used is preferably from 0.5 to 100, and more preferably from 1 to 40 in gram equivalent as the cation of the cationic polymer per mole of the light-harvesting dye being used.
• hydrophilic dispersion medium which can be used for the emulsion layers or other layers of the photographic light-sensitive materials of this invention
• gelatin is advantageously used but other hydrophilic colloids can be used.
• proteins such as gelatin derivatives, graft polymers of gelatin and other polymers, albumin, casein, etc.; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfuric acid esters, etc.; saccharose derivatives such as sodium alginate, starch derivatives, etc.; and various synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl-pyrrolidone, polyacrylic acid, polymethacrylic acid polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, etc.
• gelatin limed gelatin as well as acid-treated gelatin and enzyme-treated gelatin as described in Bull. Soc. Sci. Phot. Japan. No. 16, 30(1966) can be used. Also, hydrolyzed products of gelatin can be used.
• the composition of the light-sensitive silver halide for use in this invention includes ordinary silver halides such as silver bromide, silver iodioromide, silver chloride, silver chlorobromide, silver chloroiodobromide, etc.
• the form of the light-sensitive silver halide grains may be spherical, tabular, octahedral, cubic, tetradecahedral, amorphous, etc., but tabular silver halide grains having a large area for adsorbing dyes and capable of attaining high spectral sensitization are particularly preferred in this invention, with particularly preferred the tabular silver halide grains, the tabular grains having an aspect ratio of at least 5, and particularly at least 8 account for at least 50% of the total projected area of the whole grains.
• the tabular grains described e.g., in Research Disclosure, No. 22534 (1983), JP-A-58-127921 and 59-99433, and U.S. Patent 4,585,729 can be preferably used in this invention.
• composition of the silver halide grains may be either homogeneous throughout the grain or heterogenous.
• heterogenous silver halide grains the double structure grains having different composition between the central portion and the surface portion as described in JP-A-58-113926, 58-113927, and 59-99433 can be preferably used.
• JP-B as used herein means an "examined Japanese patent publication"
• silver halide grains having sensitive specks in the side thereof near the surface are described in JP-A-62-123446, troglodyte nuclei type silver halide grains described in JP-B-58-1409 (the term "JP-B” as used herein means an "examined Japanese patent publication"), and silver halide grains having sensitive specks in the side thereof near the surface.
• the mean grain of silver halide grains for silver halide emulsions but the equivalent sphere diameter thereof is preferably less than 3 um, and more preferably less than 1.8 urn.
• the grain size distribution may be narrow or broad.
• the silver halide grains may be of the type of forming latent images mainly on the surface thereof or of the type of forming latent images mainly in the inside thereof.
• a cadmium salt a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, or an iron salt or a complex salt hereof may exist in the system.
• the silver halide emulsion may be used as a so-called primitive emulsion without being chemically sensitized but is usually chemically sensitized by well-known methods.
• chemical sensitization for example, the method described in H. Frieser, Die Unen der Photographischen Toomit Silber-Halogeniden, pages 675 - 734 (Akademische Veriadgsgeseiischaft, 1968) can be used.
• a sulfur sensitizing method using active gelatin or a sulfur-containing compound capable of reacting with silver e.g., thisulfates, thioureas, mercapto compounds, rhodanines
• a reduction sensitizing method using a reducing agent e.g., stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid, and silane compounds
• a noble metal sensitizing method using a noble metal compound e.g., gold complexes as well as complex salts of metals belonging to group VIII of the Periodic Table, such as Pt, Ir, Pd, etc.
• the sulfur sensitization and a combination of the sulfur sensitization and gold sensitization are particularly preferred.
• the silver halide photographic emulsions for use in this invention can contain various compounds for preventing the occurrence of fog during the production, storage, and/or photographic processing of the photographic light-sensitive materials containing the emulsions or stabilizing the photographic performance thereof.
• various compounds for preventing the occurrence of fog during the production, storage, and/or photographic processing of the photographic light-sensitive materials containing the emulsions or stabilizing the photographic performance thereof For example, there are many compounds known as antifoggants or stabilizers.
• azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazole, chloroben- zimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiazoles, aminotriazoles, benztriazoles, nitrobenzotriazoles, mercaptotetrazole (in particular, 1-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines; mercatptriazines; thioketo compounds such as oxazolinethione, etc.; azaindenes such as triazaindenes, tetraazaindenes (in particular, 4-hydroxy-substituted (1,3,3a,7)tetraazaindenes), pentaazaindenes, etc.; benzenethiosulfonic acid; benzen
• the silver halide emulsions for use in this invention may contain polyalkylene oxide or their derivatives thereof, such as the ethers, esters, amines, etc., thioether compounds, thiomorpholines, quarternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, etc., for increasing sensitivity and contrast and for further increasing the development acceleration.
• polyalkylene oxide or their derivatives thereof such as the ethers, esters, amines, etc., thioether compounds, thiomorpholines, quarternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, etc.
• the light-sensitive silver halide is spectrally sensitized by adsorptive spectral sensitizing dye(s).
• the surface coating ratio of the adsorbed dye is preferably at least 20%, and more preferably at least 40% of the saturated adsorption amount of monomolecular layer.
• sensitizing dye(s) are used as spectral sensitizing dye.
• positive type photographic light-sensitive materials there are light-sensitive materials of the type of obtaining positive images by the rupture of surface fog nucleus under light exposure using, for example, electron acceptive dyes.
• adsorptive super color sensitizing agents and various kinds of additives may be used together with adsorptive dyes for the purpose of specially sensitizing in an optimum sate according to the purpose of the photographic light-sensitive materials.
• the adsorptive dyes which are used for the spectral sensitization include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxonole dyes, xanthene dyes, triarylmethane dyes, phenothizine dyes, acryzine dyes, metal chelating compounds, etc.
• To these dyes can be applied nuclei which are usually utilized for cyanine dyes as basic heterocyclic nuclei.
• nuclei examples include pyrroline nuclei, oxazoline nuclei, thiazoline nuclei, pyrrole nuclei, imidazole nuclei, tetrazole nuclei, pyridine nuclei, etc:.; the nuclei formed by fusing an alicyclic hydrocarbon ring to the aforesaid nuclei or the nuclei formed by fusing an aromatic hydrocarbon ring to the aforesaid nuclei, i.e., indolenine nuclei, benzindolenine nuclei, indole nuclei, benzoxazole nuclei, naphthoxazole nuclei, benzothiazole nuclei, nephthothiazole nuclei, benzoselenazole nuclei, benzimidazole nuclei, quinone nuclei, etc.
• the nuclei may have a substituent on the carbon atom thereof.
• cyanine dyes having at least one of thiazole nuclei, selenazole nuclei, quinoline nuclei, and indolenine nuclei in the molecule or cyanine dyes having at least two of oxazole nuclei or at least two of imidazole nuclei in the molecule are preferably used in this invention.
• the nuclei formed by fusing an aliphatic hydrocarbon ring and/or an aromatic hydrocarbon ring to these basic heterocyclic nuclei are particularly preferably used.
• merocyanine dyes or complex merocyanine dyes can be applied 5- or 6-membered heterocyclic nuclei such as pyrazololin-5-one nuclei, thiohydantoin nuclei, 1-thio-oxazolidin-2,4-dione nuclei, thiazolidine-2,4-dione nuclei, rhodanine nuclei, thiobarbituric acid nuclei, etc., as nuclei having a ketomethylene structure.
• sensitizing dyes may be used singly or as a combination thereof.
• a combination of sensitizing dyes is frequently used for the purpose of super color sensitization. Typical examples thereof are described in U.S. Patents 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769,301, 3,814,609, 3,837,862, and 4,026,707, British Patents 1,344,281 and 1,507,803, JP-B-43-4936 and 53-12375, and JP-A-52-110618 and 52-109925.
• the silver halide emulsions for use in this invention may contain, together with the sensitizing dyes, a dye having no spectral sensitizing action by itself or a material which does not substantially absorb visible light and shows super color sensitization.
• a dye having no spectral sensitizing action by itself or a material which does not substantially absorb visible light and shows super color sensitization.
• examples of such compounds are aminostyilbene compounds substituted by a nitrogen-containing heterocyclic group (described, e.g., in U.S. Patents 2,933,390 and 3,635,721), aromatic organic acid-formaldehyde condensation products (described, e.g., in U.S. Patent 3,743,510), cadmium salts, and azaindene compounds.
• the combinations of the compounds described in U.S. Patents 3,615,613. 3,615,641, 3,617,295, and 3,635,721 are particularly useful in this invention.
• color coupler in this invention means a compound capable of forming a dye by causing coupling reaction with the oxidation product of an aromatic primary amine developing agent.
• Typical examples of the useful color couplers are naphtholic or phenolic compounds, pyrazoline or pyrazoloazole series compounds, and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta, and yellow couplers which can be used in this invention are described in the patents cited in Research Disclosure, No. 17643 (December, 1978), Paragraph VII-D and ibid., No. 18717 (November, 1979).
• two or more kinds of couplers can be used in a same light-sensitive emulsion layer for meeting the characteristics required for the color photographic materials or a same kind of coupler may be used for two or more different emulsion layers for the purpose as described above.
• magenta couplers and cyan couplers For correcting unnecessary absorptions at short wavelength region shown by the dyes formed by magenta couplers and cyan couplers, it is preferred to use colored couplers together with the aforesaid color couplers in color negative photographic materials for camera use.
• colored couplers are the yellow-colored magenta couplers described in U.S. Patent 4,163,670 and JP-B-57-39413 and the magenta-colored cyan couplers described in U.S. Patents 4,004,929 and 4,138,258 and British Patent 1,146,368.
• the graininess of color images formed can be improved by using a coupler giving a colored dye having a proper diffusibility together with the aforesaid couplers.
• a coupler giving a colored dye having a proper diffusibility together with the aforesaid couplers.
• Specific examples of such properly controlled smearing are described in U.S. Patent 4,366,237 and British Patent 2,125,570 for magenta couplers and in European Patent 96,570 and West German Patent Application (OLS) No. 3,234,533 for yellow, magenta, and cyan couplers.
• the dye-forming couplers and specific couplers described above for use in this invention may form dimers or more polymers.
• Typical examples of the polymerized couplers are described in U.S. Patents 3,451,820 and 4,080,211.
• examples of polymerized magenta couplers are described in British Patent 2,102,173, U.S. Patent 4,367,282, and JP-A-62-54260 and Japanese Patent Application 60-113596.
• Couplers releasing photographically useful residue with coupling can be also used in this invention.
• DIR couplers releasing a development inhibitor with coupling are described in Research Disclosure, No. 17643, Paragraph VII-F.
• couplers imagewise releasing a nucleating agent or a development accelerator, or a precursor therefor at development can be also used. Specific examples of such couplers are described in British Patents 2,097,140 and 2,131,188. Also, couplers releasing a nucleating agent having an adsorptive action to silver halide are particularly preferable and typical examples thereof are described in JP-A-59-157638 and 59-170840.
• the photographic light-sensitive materials of this invention may contain an inorganic or organic hardener in hydrophilic colloid layers forming the photographic emulsion layers, etc., and back layer.
• Typical examples thereof are chromium salts, aldehydes (e.g., formaldehyde, glyoxale, and glutar aldehyde), and N-methylol series compounds (e.g., dimethylolurea).
• Active halogen compounds e.g., 2,4-dichloro-6-hydroxy-1,3,5-triazine
• active vinyl compounds e.g., 1,3-bis-vinylsulfonyl-2-propanol, 1,2-bis- vinylsulfonyl acetamide ethane and vinylic polymers having a vinylsulfonyl group at the side chain thereof
• active vinyl compounds e.g., 1,3-bis-vinylsulfonyl-2-propanol, 1,2-bis- vinylsulfonyl acetamide ethane and vinylic polymers having a vinylsulfonyl group at the side chain thereof
• N-carbamoylpyridinium salts and haloamidinium salts are excellent in the point of giving quick hardening.
• the silver halide emulsions for use in this invention can further contain various additives such as surface active agents, tackifiers, dyes, ultraviolet absorbents, antistatic agents, whitening agents, desensitizers, developing agents, fading preventors, etc.
• photographic emulsion layer(s) and other layer-(s) are formed on a flexible support such as plastic films, papers, cloths, etc., or a solid support such as glass plates, ceramics, metals, etc.
• a flexible support such as plastic films, papers, cloths, etc., or a solid support such as glass plates, ceramics, metals, etc.
• Useful flexible supports are films of semisynthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc., and papers having a baryta layer or a layer of an a-olefin polymer (e.g., polyethylene, polypropylene, and ethylene/butene copolymer).
• the support may be colored by dyes or pigments.
• the support may, as the case may be, blacked for light-shielding.
• the surface of the support is generally subjected to a subbing treatment for improving the adhesion for a photographic emulsion layer, etc.
• a subbing treatment for improving the adhesion for a photographic emulsion layer, etc.
• the surface of the support may be subjected to a glow discharging treatment, corona discharging treatment, ultraviolet irradiation, a flame treatment, etc.
• the light exposure for obtaining photographic images may be performed by an ordinary manner. That is, various light sources such as natural light (sunlight), a tungsten lamp, a fluorescent lamp, a mercury lamp, a xenon arc lamp, a carbon arc lamp, a xenon flash lamp, a cathode ray tube, a flying spot, etc., can be used.
• the exposure time is as a matter of course from 1/1000 sec. to one second which are usually used for camera as well as may be shorter than 1/1000 sec., for example from 1/10 4 to 1/10 9 sec. in the case of using a xenon flash lamp, a cathode ray tube, or a laser light or may be longer than one second.
• the spectral composition of light for use the exposure can be controlled using color filters.
• the exposure may be performed by light emitted from a fluorescent substance excited by electron beam, X-rays, y-rays, a-rays, etc.
• the photographic light-sensitive materials of this invention can be processed by any known processed using known processing solutions as described, e.g., in Research Disclosure, No. 17643, Vol. 176, pages 28-30.
• the photographic process may be a photographic process of forming silver images (black and white processing) or a photographic process of forming dye images (color photographic processing) according to the purpose.
• the processing temperature is usually selected between 18 C to 50° C but, as the case may be, may be lower than 18 * C or higher than 50 C.
• a process of processing photographic light-sensitive materials containing-a developing agent in, for example, the photographic emulsion layers thereof in an alkaline aqueous solution may be used.
• a hydrophobic developing agent can be incorporated in the emulsion layer by various methods as described in Research Disclosure, Vol. 169. No. 16928, U.S. Patent 2,739,890, British Patent 813,253, and West German Patent 1.547,763.
• Such a development process may be combined with a silver salt stabilization process by a thiocyanate.
• fix solution for use in this invention, an ordinary composition can be used.
• the fixing agent thiosulfates, thiocyanates as well as organic sulfur compounds which are known to have an effect as fixing agent can be used.
• the fix solution may contain a water-soluble aluminum salt as a hardener.
• a color developer which is used for developing the color photographic materials of this invention is generally composed of an alkaline aqueous solution containing a color developing agent.
• a color developing agent there are primary aromatic amine developing agents such as phenylenediamines (e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-4-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesul- foamidoethylaniline, and 4-amino-3-methyl-N-ethyl-N- ⁇ -methoxyethylaniline).
• the color developer may further contain a pH buffer, a development inhibitor or an antifoggant.
• the color developers may contain a water softener, a preservative, an organic solvent, a development accelerator, a dye-forming coupler, a competing coupler, a fogging agent, an auxiliary developing agent, a tackifier, a polycarboxylic chelating agent, an antioxidant, etc.
• the color photographic materials are usually bleached.
• the bleach process may be performed simultaneously with or separately from a fix process.
• the bleaching agent there are compounds of multivalent metals such as iron(III), cobalt(III), chromium(VI), copper(II), etc., peracids, quinones, nitroso compounds, etc.
• ferricyanides include bichromates; organic complex salts of iron(III) or cobalt(III), e.g., complex salts thereof and aminopolycarboxylic acids (e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid, and 1,3-diamino-2-propanoltetraacetic acid) or other organic- acids (e.g., citric acid, tartaric acid, and malic acid); persulfates; permanganates; and nitrosophenol.
• aminopolycarboxylic acids e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid, and 1,3-diamino-2-propanoltetraacetic acid
• other organic- acids e.g., citric acid, tartaric acid, and malic acid
• persulfates e.g., citric acid, tartaric acid, and malic acid
• additives causing reaction with the light-collecting dyes can be added to the processing solutions such as developer, blix solution, etc., for the purpose of decomposing and disclosing the light-collecting dyes existing in the light-sensitive materials.
• This invention can be applied to various kinds of color photographic materials and black and white photographic materials, such as general or cinne color negative films, color reversal films for slide or television, color photographic papers, color positive films, color reversal photographic papers, color diffusion transfer type photographic materials, heat development type color photographic material, etc.
• This invention can be also applied to radiographic black and white photographic materials utilizing a mixture of three color couplers described in Research Disclosure, No. 17123 (July, 1978) and utilizing black coloring couplers described in U.S. Patent 4,126,461 and British Patent 2,102,136.
• This invention can be further applied to process films such as lith films or scanner films, direct or indirect medical and industrial radiographic films, negative black and white photographic films for camera use, black and white photographic papers, computer output microfilms (COM), ordinary microfilms, silver salt diffusion transfer type photographic materials and printout type photographic materials.
• films such as lith films or scanner films, direct or indirect medical and industrial radiographic films, negative black and white photographic films for camera use, black and white photographic papers, computer output microfilms (COM), ordinary microfilms, silver salt diffusion transfer type photographic materials and printout type photographic materials.
• the most preferred utilization of this invention is as a matter of course in the point of further improving the spectrally sensitized sensitivity of a silver halide photographic material spectrally sensitized by dye(s) according to the use of the light-collecting dye(s) together with the aforesaid spectrally sensitizing dye(s) but among them, examples of the particularly preferred utilization method are, in the case of a black and white photographic material, the improvement of the sensitivity at the region having relatively low sensitized degree corresponding to the valley between the intrinsic sensitivity and the spectral.
• the blue region 450 to 520 n.m.
• the reinforcement of each spectral sensitivity of blue, green and red regions by the addition of the proper light-collecting dyes e.g., the blue region (450 to 520 n.m.) by the addition of the light-collecting dye and, in the case of a color photographic material, the reinforcement of each spectral sensitivity of blue, green and red regions by the addition of the proper light-collecting dyes.
• the technique of this invention is effective as a means for improving the spectrally sensitized sensitivity as well as is expected to improve the sharpness of images of the photographic light-sensitive materials in addition to the sensitization by an irradiation preventing effect or antihalation effect of the light-collecting dyes since the light-collecting dyes, which are sensitizers, in a dispersion medium are also light absorbers.
• the use of an irradiation preventing dye or an antihalation dye is generally accompanied by a desensitization by a light filter effect but the use of the light-collecting dyes in this invention can improve the sharpness of images formed without substantially reducing the sensitivity or rather with increasing the sensitivity.
• crossover light that is, the fluorescence from a fluorescent intensifying screen transmitting into the light-sensitive emulsion layer at the said opposite to the light incident side
• crossover light that is, the fluorescence from a fluorescent intensifying screen transmitting into the light-sensitive emulsion layer at the said opposite to the light incident side
• the sharpness can be greatly improved by greatly increasing the light absorption amount at the light incident side to increase the sensitivity and at the sale time intercept the crossover light.
• a multilayer color photographic material having the layers of the compositions shown below on a cellulose triacetate film support having subbing layer was prepared as a base sample. Also, a comparison sample was prepared by simply adding the light-collecting dye A-47 to the 1 st to 3rd green-sensitive emulsion layer of the base sample and furthermore, samples of this invention were also prepared by further adding various polymer mordants to these green-sensitive emulsion layers.
• the quantum yield of the luminescence of the light-collecting dye A-47 at a concentration of 10- 4 mole/dm 3 in dry gelatin was 0.74.
• the coating amounts were silver halide, shown by the g/m 2 unit of silver for silver halide, emulsions and colloid silver, the g/m 2 unit for coupers, additives and gelatin, and the mole number per mole of silver halide in the same layer for a sensitizing dye.
• Silver lodobromide Emuslion (Agl 2 mole%, inside high-Agl type, sphere-corresponding diameter 0.3 um, coeff. of variation of sphere-corresponding diameters 29%, normal crystal, twin-mixed grains, aspect ratio 2.5) 0.4
• Silver lodobromide Emuslion (Agl 5 mole%, inside high-Agl type, sphere-corresponding diameter 0.7 ⁇ m, coeff. of variation of sphere-corresponding diameters 25%, normal crystal, twin-mixed grains, aspect ratio
• Silver lodobromide Emuslion (Agl 10 mole%, inside high-Agl type, sphere-corresponding diameter 0.8 ⁇ m, coeff. of variation of sphere-corresponding diameters 16%, normal crystal, twin-mixed grains, aspect ratio)
• Silver lodobromide Emuslion (Agl 2 mole%, inside high-Agl type, sphere-corresponding diameter 0.3 ⁇ m, coeff. of variation of sphere-corresponding diameters 28%, normal crystal, twin-mixed grains, aspect ratio 2.5) 0.30
• Silver lodobromide Emuslion (Agl 4 mole%, inside high-Agl type, sphere-corresponding diameter 0.6 ⁇ m, coeff. of variation of sphere-corresponding diameters 38%, normal crystal, twin-mixed grains, aspect ratio
• Silver lodobromide Emuslion (Agl 6 mole%, inside high-Agl type, sphere-corresponding diameter 1.0 ⁇ m, coeff. of variation of sphere-corresponding diameters 80%, normal crystal, twin-mixed grains, aspect ratio 1.2) 0.85
• Silver lodobromide Emuslion (Agl 4 mole%, inside high-Agl type, sphere-corresponding diameter 0.5 ⁇ m, coeff. of variation of sphere-corresponding diameters 15%, octahedral grains) 0.4 Gelatin 1.0
• Silver lodobromide Emuslion (Agl 10 mole%, inside high-Agl type, sphere-corresponding diameter 1.3 ⁇ m, coeff. of variation of sphere-corresponding diameters 25%, normal crystal, twin-mixed grains, aspect ratio 4.5) 0.5
• each layer further contained a surface active agent as a coating aid in addition to the aforesaid components.
• the sample as obtained was used as the base sample.
• comparison sample 1-1 was prepared by adding light-collecting dye A-47 to the base sample and samples 1-2, 1-3, I-4 and I-5 of this invention were also prepared by further adding each polymer mordant to the sample I-1.
• each of polymer mordants B-1, B-2, B-3 and B-4 was added to the green-sensitive emulsion layers of the comparison sample I-1.
• the addition amount of each polymer mordant was shown by the ratio of the grain equivalent number as the cation thereof to the mole number of the dye A-47 and shown in Table 1 below. each addition amount was the amount necessary for having a mordanting power as each mordant.
• the polymer mordants B-1 to B-4 are shown below.
• Each of the samples was exposed to white light through a continuous wedge for 1/100 second using a light source of 4800 ° K in color temperature and processed by the following process.
• compositions of the processing solutions used in the aforesaid process are shown below.
• Example 1 using the light-collecting dye A-47 and the mordant B-1, each relative sensitivity of the G, G, and R sensitivities in the case of changing the addition amount of the mordant B-1 was determined. In this case, however, the mordant B-1 was used for the samples of this invention only. The results are shown in Table 3.
• the mordanting power is more intensified to inhibit the diffusion of the dye A-47 into other layers, whereby the desensitization of the emulsion layers, in particular, the green-sensitive emulsion layer is inhibited by a filter effect.
• the light-collecting dye was substantially removed and the deterioration of color images by residual color was not observed.
• a multilayer color photographic light-sensitive material having the following layers on a cellulose triacetate film support having subbing layer was prepared as the base sample. Then, a comparison sample containing light-collecting dye A-47 in the 1st and 2nd green-sensitive emulsion layers of the base sample was prepared. Also, the samples of this invention further containing the mordants B-1, B-2, and B-3, respectively, in the green-sensitive emulsion layers were prepared.
• compositions of the layers of the base sample were as follows.
• Each of the aforesaid layers contained a gelatin hardener H-3 and a surface active agent in addition to the aforesaid components.
• comparison sample III-1 was prepared by adding light-collecting dye A-47 to the 1st and 2nd green-sensitive emulsion layers of the base sample in a total amount of 28 moles per dm 2 of gelatin and samples 111-2, III-3, III-4 and III-5 of this invention were prepared by adding mordants B-1, B-2, B-3 and B-4, respectively to the green-sensitive emulsion layers of the comparison sample III-1.
• the amount of each mordant was shown by the ratio of the gram equivalent number as the cation to the mole number of the dye A-47 and shown in Table 4. The addition amount of the mordant was sufficient for giving a mordant power of each mordant.
• compositions of the processing solutions used in the aforesaid process were as follows.
• the pH was adjusted by hdyrochloric acid or potassium hydroxide.
• the pH was adjusted by hdyrochloric acid or potassium hydroxide.
• the pH was adjusted by hdyrochloric acid or potassium hydroxide.
• the pH was adjusted by hdyrochloric acid or potassium hydroxide.
• the pH was adjusted by hdyrochloric acid or potassium hydroxide.
• the pH was adjusted by hdyrochloric acid or potassium hydroxide.
• Comparison sample IV-1 was prepared by adding light-collecting dye A-56 to the 1st, 2nd, and 3rd red-sensitive emulsion layer of the comparison sample 1-1 in Example 1 in total amounts of 28 m moles per dm 3 of gelatin and also light-collecting dye A-3 to the 1 st and 2nd blue-sensitive emulsion layers of the same comparison sample in total amounts of 28 m moles per dm 3 of gelatin.
• the comparison sample IV-1 contained light-collecting dyes A-56, A-47 and A3 in the red-sensitive emulsion layers, green-sensitive emulsion layers, and blue-sensitive emulsion layers, respectively.
• sample IV-2 of this invention was prepared by adding polymer mordant B-1 to all the light-sensitive emulsion layers of the comparison sample IV-1 in 20 gram equivalent per mole of each light-collecting dye in each emulsion layer.
• sample IV-3 of this invention was also prepared by using light-collecting dye B-2 in place of B-1 used for the sample IV-2 of this invention in an amount of 30 g equivalent per mole of each light-collecting dye.
• sample IV-4 or IV-5 of this invention was similarly prepared respectively by adding 20 gram equivalent per mole of polymer mordant B-3 or 30 gram equivalent per mole of polumer mordant B-4 in place of B-1 in each light-collecting dye.
• Example 6 Each of these samples was exposed to white light through a continuous wedge for 1/100 second using a light source of 4800 ° K and processed as in Example 1. The results obtained are shown in Table 6, wherein the sensitivity was same as in Example 1, however, in this example the sensitivity of the comparison sample IV-1 being defined as 100.

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• 1987
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