US3764337A - Color photographic materials containing dihydroxyspirochroman compounds as stabilizers - Google Patents

Color photographic materials containing dihydroxyspirochroman compounds as stabilizers Download PDF

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US3764337A
US3764337A US00213540A US3764337DA US3764337A US 3764337 A US3764337 A US 3764337A US 00213540 A US00213540 A US 00213540A US 3764337D A US3764337D A US 3764337DA US 3764337 A US3764337 A US 3764337A
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group
color
compounds
coupler
dihydroxyspirochroman
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A Arai
Y Oishi
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP12145470A external-priority patent/JPS4920977B1/ja
Priority claimed from JP46034621A external-priority patent/JPS5112659B1/ja
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/10—Spiro-condensed systems
    • 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
    • G03C1/795—Photosensitive materials characterised by the base or auxiliary layers the base being of macromolecular substances
    • G03C1/7954—Polyesters
    • 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
    • G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
    • G03C1/8155—Organic compounds therefor
    • 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
    • G03C7/3928—Spiro-condensed

Definitions

  • the present invention relates to new dihydroxyspirochroman compounds as stabilizers.
  • An object of the invention is to obtain dihydroxyspirochroman compounds which are suitable as the color image stabilizer (often referred to as a dye stabilizer) of color photographic materials.
  • FIGS. l-S show spectrum data concerning Compounds I and XVI.
  • the dihydroxyspirochroman compounds of the present invention are represented by the following Formula I:
  • R is an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenoxy group, an aryloxy group, an acylamino group or an acylamino aralkyl group, each of which having one to 18 carbon atoms, R is a hydrogen atom, a halogen atom, an alkyl group an alkenyl group or an alkoxy group.
  • FIG. 1 The infrared absorption spectrum of the Compound I as measured by the KBr tablet method is shown in FIG. 1.
  • HO The nuclear magnetic resonance spectrum of this compound as measured in heavy-hydrogenated acetone using E TMS as an internal standard is shown in FIG. 2.
  • (XV) Cl Cm 1.28, l.54 p.p.m. (6H; of 4,4 gem. dimethyl groups, two
  • IM 4 kv. ua., IM 4 kv.
  • the fragment ion peaks at m/e 353 (M CH rn/e 204, m/e 189 (m/e 204CH and rn/e 165 (m/e 353-m/e 189+H) were observed.
  • the infrared absorption spectrum of the Compound XVI as measured by the KB'r tablet method is shown in FIG. 4.
  • the mass spectrum of this compound measured by the direct introduction method (130 C., 70 ev., 200 ua., IM 4 kv.) is shown in FIG. 5.
  • the fragment ion peaks at m/e 505 M+CH m/e 280, m/e 265 (m/e 280CH and m/e 241 (m/e 505-m/e 265+H) were observed.
  • the dihydroxyspirochroman compounds of the present invention are very effective as the color image stabilizer for color photographic materials.
  • the present invention relates to color photographic materials containing the dihydroxyspirochroman compounds represented by the above-mentioned Formula I as the color image stabilizer and particularly to color photographic materials that provide a color image which, even if exposed to light, is difficult of fading.
  • coupler tion in this instance is called a coupler.
  • the dyes formed belong to the classes of indophenols, indoanilines, azomethines, indamines and azines.
  • There are two methods of supplying couplers one is to supply from the developer solution a coupler which is capable of diffusing into the inside of the layer of emulsion and another method is to add a diffusion-fast coupler to the emulsion during the process of manufacture of the photographic material.
  • photographic material to be used for the former is called external type and that for the latter is called incorporated type.
  • the color photographic material to be used for color photography by the subtractive color process has usually those emulsion elements on the same support which sensitize themselves selectively to the lights of blue, green and red. These emulsion elements provide respective color images of yellow, magenta and cyan in the color development using a primary aromatic amine as a developing agent.
  • couplers providing a magenta color image are known S-pyrazolones, pyrazolobenzimidazoles, indazolones and 2-cyano-acetyl-cumarones. Of them S-pyrazolones are the most widely used.
  • magenta color image obtained from 5-pyrazolones fades, if exposed to a strong light over a prolonged period of time. This fading of the magenta color image due to light has been impedient to the use in case color photographs require to be preserved in a stable way without any change over a long period of time.
  • Some expedients have been so far tried with a view to making the magenta color image obtained from S-pyrazolones fast to lights. They are, for example, means of incorporating ultra-violet absorbents into color photographic materials to protect the color image from the ultra-violet rays, for making the dye itself fast to light by making a proper selection of the structure of the coupler or of using color dye stabilizers to prevent the decomposition of the dyes to be caused by light.
  • An object of the present invention is to provide color photographs of a small degree of fading and particularly of good light-fastness.
  • Another object of the present invention is to provide color photographic materials which are capable of giving stable color image of a small degree of fading.
  • the compounds of the present invention is to provide new dye stabilizers which make magenta color image obtained from the S-pyrazolone coupler fast to light.
  • Still another object of the present invention to provide color photographic materials containing new color image stabilizers which make the magenta color image fast to light.
  • the dihydroxyspirochroman compounds decrease greatly the degree to which the magenta color image obtained from a pyrazolone coupler is faded upon exposure to light. In comparison with the dye stabilizer known in the past, they can show an equivalent efiect in smaller quantities.
  • dihydroxyspirochroman compounds to be used in the present invention are very stable in themselves and do not lend themselves to the color forming reaction or do not give rise to coloring during the color development with use of aromatic primary amino compounds and also in a bleach bath containing a strong oxidizing agent such as ferricyamide or oichromate. They, even when left in the color photograph after processing, do not cause any taint.
  • the dihydroxyspirochroman compounds to be used in the present invention inhibit the undesirable change of the S-pyrazolone couplers to light or heat.
  • the dihydroxyspirochroman compounds to be used in the present invention are readily soluble in organic sol vents and can be incorporated readily and stably into the color photographic material.
  • magenta coupler to be used in the present invention can be selected from a Wide range of structures.
  • S-pyrazolone compounds that yield a particularly excellent result when used with the dihydroxyspirochroman compounds of the structural Formula I mentioned earlier belong to the groups represented by the following structural Formulas II and III.
  • R is an aryl group or a substituted aryl group.
  • substituent group for the aryl group there is useful an alkyl group, aryl group, alkoxyl group, aryloxy group, alkylthio group, arylthio group, halogen atom, trifiuoromethyl group, cyano group, acyl group, sulfonyl group, acylamino group, sulfonamino group, ureido group, amino group, carboxyl group, alkoxycarbonyl group or carbamyl group, and particularly a phenyl group substituted by these substituent groups is excellent as R R is an alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, aryl group, substituted aryl group, amino group, substituted amino group, acylamino group, substituted ureido group, sulfonamide group or alkoxy group, and
  • X represents those radicals which can be split ofi by the oxidation product of the primary aromatic amino developing agent, for instance, a hydrogen atom, halogen atom, cyano group, arylthio group, aryloxy group, arylazo group, heteroazo group and acyloxy group.
  • This hydrophobic radical tends to enhance the afiinity between the coupler molecules as well as between the coupler molecules and the coupler-solvent molecules and keeps the coupler in the interior and in the vicinity of the solvent particles keeping the close contact with each other.
  • This hydrophobic radical further affords aflinity for the coupler solvent to the dyes derived from it and also tends to strengthen the effect of the coupler solvent.
  • This hydrophobic radical is contained in R or R being linked with the coupler radical either directly or indirectly through a di-valent organic radical having an amino bond, ether bond, ester bond, urea bond or sulfonamide bond.
  • the useful hydrophobic radical for the present invention is selected from straight-chain or branched alkyl groups, alkenyl groups, alkoxyalkyl groups, alkoxyaryl groups, aryl groups, aryloxyalkyl groups, aryloxyaryl groups, and acylaminoalkyl groups.
  • Specific examples of the hydrophobic radical include:
  • a dispersion product in which a dihydroxyspirochroman compound has been emulsified may be added to 'a photographic emulsion of silver halide separated containing a diffusion-fast pyrazolone coupler, or the diffusion pyrazolone coupler and dihydroxyspirochroman compound are dissolved in one and the same solvent to form a mixed solution which is then dispersed in an aqueous medium, and the resultant dispersion is added to the photographic emulsion.
  • the amount of the dihydroxyspirochroman compound to be used in the present invention varies with the purpose for which the color photographic material is to be used, the type of the 5-pyrazolone coupler and also the structure of the dihydroxyspirochroman compound to be used, but the amount in the range of 0.05 mol-5.0 moles per mol of the 5-pyrazolone coupler is effective and particularly that of 0.1 mol2.0 mols is preferable.
  • dihydroxyspirochroman compounds to be used in the present invention sometimes exhibit the effect of improving the light-fastness also for the color images induced from the yellow color forming couplers consisting of acylacetoanilides and cyan forming couplers consisting of phenols or alpha naphthols.
  • the dihydroxyspirochroman compounds to be used in the present invention dissolve readily in many organic solvents. These comopunds are dispersed finely in an aque ous medium after being dissolved in an organic solvent. The emulsion so obtained is then added to the photographic emulsion.
  • One embodiment of the present invention is to mingle the dihydroxyspirochroman compounds With oil-soluble S-pyrazolone couplers and then to disperse the mixture in the said medium or to add the dye stabilizer and the coupler separately in the form of a solution or a dispersion to the emulsion.
  • a Wide range of organic solvents are used for the purpose of adding the coupler and the dye stabilizer to be used in the present invention to the photographic emulsion, but particularly suitable for this purpose are those described in the following:
  • Substantially Water-insoluble and non-volatile solvents having a boiling point of not lower than 200 C. at normal atmospheric pressure.
  • Solvents miscible with water This type of solvent is removed during the process of manufacture of the photographic material by means of rinsing or dialysis. For instance, methanol, ethanol, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, dimethyl sulfoxide, dimethylformamide, hexamethyl phosphoryl amide and methyl Cellosolve can be mentioned.
  • dihydroxyspirochroman compounds dispersed in an aqueous medium for photographic use are not soluble in water and further are not soluble either in other processing solutions including developing agents of a high pH value for use in the photoprocessing, and it never happens that they are lost by flow during the processing or that they are diffused into other layers of the photographic material.
  • alkyl hydroquinones disclosed in the specification of U.S. Patents No. 2,336,327, No. 2,403,721 and No. 2,728,659 are the compounds that are suitable to be used conjointly with dihydroxyspirochromans expressed by general Formula I.
  • the magenta color image formed from the pyrazolone coupler is rendered markedly fast to light, but also the pyrazolone coupler remaining in the color photographic material after processing can be effectively prevented from yellowing or staining upon exposure to heat or light.
  • magenta color image obtained from a diffusion-fast 5-pyrazolone is processed in a bleach bath containing a strong oxidizing agent such as a bichromate and ferricyanide, it becomes liable to fade upon exposure to light.
  • a strong oxidizing agent such as a bichromate and ferricyanide
  • the magenta color image processed in a bleach bath containing a weak oxidizing agent and a strong silver complex forming agent, for instance, thiosulphate and a mixture of ethylene diamine tetraacetic acid with a ferric salt is fast to light, and the use of such a bleach bath of weakly oxidizing nature is particularly useful for the practice of the present invention.
  • p-phenylenediarnine derivative to be used for the processing of the color photographic material of the present invention
  • many compounds that have been previously known can be used. Specific examples include N,N-diethyl-p-phenylenediamine,
  • the color photographic material of the present invention proves advantageous if it is processed with aldehydes like formaldehyde either during or after the color development processing. This not only serves to harden the hydrophilic film of the color photographic material, but improves the heat resistant property of the color image as well.
  • the color photographic material of the present invention processed in a stabilizing bath in the final stage of the color development processing.
  • This bath contains an acid substance, a substance soluble in water having the action to stabilize the color image, an ultra-violet absorbent and a fluorescent whitening agent.
  • the color image stabilizing agent to 'be added into the stabilization bath hydroquinone or its substituted derivatives, urea or its substituted derivatives and p-alkoxyphenol or its substituted derivatives are useful.
  • the color photographic material of the present invention should contain a substance which does not practically absorb visible rays, but strongly absorbs ultra-violet rays.
  • Such an ultra-violet ray absorbing material protects the color image and the residual coupler from the action of ultra-violet rays after the color development processing and further presents the color photograph from yellowing, staining or fading.
  • the dihydroxyspirochroman compound to 'be used in this invention particularly effectively prevents the color image protected by the ultra-violet absorbent from fading due to light.
  • the ultra-violet absorbent particularly suitable for use in the practice of the present invention in the specific form stilbene derivatives (see, for instance, pat. pub. No. 9,585-1970 or pat. pub. No.
  • the present invention applies to various types of color photographic materials. Namely, it is used for color negative films, color positive pictures, color photographic paper, color reversal and color films for enlargement display (for instance, Fuji Color G Print).
  • the support of the color photographic material of the present invention can be made from various materials and in various forms.
  • Plates made of glass or plastics, soft flexible sheets or paper of cellulose acetate, polyethylene terephthalate or poystyrene or resin-coated paper can be used.
  • the photographic emulsion to be used to put the present invention to practice is that in which silver halide is dispersed in fine grains in the hydrophilic colloid, and a suitable silver halide is silver chloride, silver bromochloride, silver bromide or silver iodobromide.
  • Suitable hydrophilic colloids include Water soluble polymers such as gelatin, polyvinyl alcohol, polyvinyl pyrolidone, polyacrylamide, polyacrylamide subjected to the Hofiman re action and co-polymers of acrylic acid, acrylamide and N-vinylimidazole.
  • EXAMPLE 1 17 grams of 1 (2,6 dichloro 4' methoxy)- phenyl 3 [3" (oz-(2 4"'-di-t-amylphenoxy)butylamide)benzamide] 5 pyrazolone (examplified compound O) as the magenta coupler, dye stabilizers (types and quantities shown in the following table) and the solution obtained by heating 34 grams of tricresylphosphate and 30 milliliters of ethyl acetate were mixed with an aqueous solution at 50 C. containing 1.0 gram of sodium dodecylbenzeuesulfonate and 25 grams of gelatin, and
  • EXAMPLE 2 On a paper support having a polyethylene layer on a surface, which was rendered hydrophilic, were coated in a first layer (with a dry film thickness of four microns) a blue-sensitive emulsion layer containing ot-(4-methoxybenzoyl)-[2'-chloro 5 (2",4" di-sec-amylphenoxyacetamide)] acetanilide as the yellow coupler and in a second layer (one micron) an intermediate layer consisting of gelatin.
  • Example 2 the following hydroquinone derivatives were further added in addition to the coupler, solvent and dye stabilizer. In all other points the example was practiced as it was and the results given in the following table were obtained.
  • a gelatin layer containing Z-benzotriazo-4-sec-butyl-6-tbutylphenol as an ultraviolet absorbent to a dry film thickness of two microns.
  • a red-sensitive emulsion layer containing 1-hydr0xy-4-chloro-2-dodecylnaphthamide as the cyan coupler to a dry film thickness of three microns and one micron thick gelatin layer as a protective layer were then applied to complete the color photographic paper.
  • the color photographic paper was exposed stepwise to green light and subjected to the color development processing in a way similar to that of Example 1 to obtain a magenta dye image which had a gradationally varying degree of color density.
  • the developed samples were directly exposed to light of a luminosity of 10,000 luxes from a fluorescent lamp of the day light type, and the results reported in the following table were obtained.
  • EXAMPLE 4 On a film base consisting of cellulose triacetate were placed as a first layer a red sensitive emulsion layer containing the sodium salt of l-hydroxy-4-sulfo-2-octadecylnaphthoamide as a cyan forming coupler to a dry film thickness of five microns and as a second layer a 1.5 micron thick gelatin intermediate layer, one after another.
  • the emulsified dispersion solution was added to one kilogram of a green sensitive emulsion containing 0.27 mol of silver iodobromide and 70 grams of gelatin. It was then added to an aqueous solution containing 21.8 grams of l-phenyl- 3[ (a oleylsuccinamide)benzamide] 5 pyrazolone exemplified compound A) and 1.5 grams of sodium hydroxide, and the pH value of the emulsion was adjusted to 6.0 with an aqueous solution of 5% acetic acid.
  • the comsolution of 4% sodium salt of l-hydroxy-3,5-dichloro-5- pounds of the present invention are both capable of strongly preventing the magenta dye image from fading and their improving effects are stronger than those of the conventionally known dye stabilizer. It was further ascertained that the compounds of the present invention efiiectively prevent the highlight area of the color print from yellowing upon exposure to light.
  • a gelatin layer containing a yellow colloid to a dry film thickness of two microns On the third layer of the film were further placed a gelatin layer containing a yellow colloid to a dry film thickness of two microns, a blue sensitive layer containing the 2Na salt of o:-(4-oleyl-succinamidobenzoyl)-2'-meth oxy-S-carboxy-acetoanilide as the yellow coupler as a fifth layer to a thickness of six microns and a gelatin to be added to the green sensitive emulsion in the manner containing a high molecular weight ultra-violet absorbent having the following structure to a thickness of 2.5 microns to complete the color film.
  • This film was exposed stepwise to green light and then processed in the color developing solution of the following composition at 20 C. for 18 minutes.
  • the color developed samples were exposed to light of a luminosity of 50,000 luxes from a xenon lamp (which was passed through a heat-absorbing filter) for three days. The results given in the following table were obtained.
  • Dispersion solutions of dye stabilizers The solutions obtained by dissolving the dye stabilizers described in Table 5 in a mixed solvent consisting of two milliliters of di-n-butyl phthalate and five milliliters of ethyl acetate were added to 30 milliliters of an aqueous solution containing 0.1 gram of sodium cetylsulphate and 2.0 grams of gelatin. They were dispersed by violent mechanical stirring in a homo-blender.
  • the dihydroxyspirochroman compounds to be used in the present invention make the azomethine dye image induced from 5- pyrazolone couplers having various substituent groups fast to light.
  • EXAMPLE 5 To 200 grams of an emulsion containing 0.27 mol of silver iodobromide and 70 grams of gelatin in one kilogram thereof were added the following magenta coupler dispersed solutions and dye stabilizer dispersed solutions. After the further addition of three milliliters of an acetone solution of 3% triethylene phosphamide thereto, they were coated on a polyethylene terephthalate film base to a dry film thickness of five microns. Coupler dispersed solutions: The couplers mentioned in Table 5 were dissolved by reflux in 10 milliliters of tri-n-hexylphosphate and 15 milliliters of ethyl acetate.
  • the solution obtained was added to 70 milliliters of an aqueous solution con- CH3 CH3 CH3 CH I l R1 R2 wherein R is an alkyl group, alkenyl group, aryl group, alkoxy group, alkenoxy group, aryloxy group, acylaminoalkyl group or acylaminoaral-kyl group having not more than 18 carbon atoms, and R is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group or an alkoxy group.
  • said color image stabilizing agent is selected from the group consisting of 6,6'-dihydroxy-7,7-dimethyl-4,4,4',4'-tetramethylbis-2,2'-spirochroman, 6,6'-dihydroxy-7,7'-di-t-butyl-4,4,4',4'-tetramethylbis-2,2-spirochroman, 6,6'-dihydroxy-7,7-di-t-amyl-4,4,4',4-tetramethylbis-2,2'-spirochroman, 6,6'-di-hydroxy-7,7'-di-n-0ctyl-4,4,4',4'-tetramethylbis-2,2'-spirochroman, 6,6'-dihydroxy-7,7-di-n-pentadecyl-4,4,4',4'-tetramethyl-bis-2,2'-spirochroman, 6,6-dihydroxy-7,7-di-n-penta
  • a color photographic material as in claim 1 wherein said silver halide is selected from silver chloride, silver bromochloride, silver bromide, and silver iodobromo chloride.

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US00213540A 1970-12-29 1971-12-29 Color photographic materials containing dihydroxyspirochroman compounds as stabilizers Expired - Lifetime US3764337A (en)

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Cited By (34)

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US3935016A (en) * 1973-04-13 1976-01-27 Fuji Photo Film Company, Ltd. Silver halide color photographic materials containing 3-anilino-5-pyrazolone couplers
DE2617826A1 (de) * 1975-04-24 1976-11-04 Fuji Photo Film Co Ltd Photographische farbmaterialien und verfahren zu ihrer behandlung
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EP0147854A2 (en) 1983-12-29 1985-07-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
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EP0218266A2 (en) 1984-05-02 1987-04-15 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
EP0239972A1 (en) * 1986-03-31 1987-10-07 Fuji Photo Film Co., Ltd. 3, 3'(2H,2'H)-spirobibenzofuran compounds and antioxidants comprising the same
EP0242013A2 (en) 1986-01-20 1987-10-21 Konica Corporation Silver halide color photographic light-sensitive material
EP0256537A2 (en) 1986-08-15 1988-02-24 Fuji Photo Film Co., Ltd. Color print and a method for producing the same
US4735893A (en) * 1984-06-08 1988-04-05 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US4741980A (en) * 1985-09-19 1988-05-03 Konishiroku Photo Industry Co., Ltd. Method for increasing color-fastness of organic coloring matter
US4767697A (en) * 1985-01-21 1988-08-30 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US4840870A (en) * 1983-12-19 1989-06-20 Konishiroku Photo Industry Co., Ltd. Heat-transfer image-receiving element
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US4895793A (en) * 1986-04-16 1990-01-23 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US5478721A (en) * 1995-01-31 1995-12-26 Eastman Kodak Company Photographic elements containing emulsion stabilizers
US5492805A (en) * 1994-06-30 1996-02-20 Minnesota Mining And Manufacturing Company Blocked leuco dyes for photothermographic elements
US5492804A (en) * 1994-06-30 1996-02-20 Minnesota Mining And Manufacturing Company Chromogenic leuco redox-dye-releasing compounds for photothermographic elements
US5492803A (en) * 1995-01-06 1996-02-20 Minnesota Mining And Manufacturing Company Hydrazide redox-dye-releasing compounds for photothermographic elements
US5576165A (en) * 1993-07-07 1996-11-19 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0800113A2 (en) 1996-04-05 1997-10-08 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US5928857A (en) * 1994-11-16 1999-07-27 Minnesota Mining And Manufacturing Company Photothermographic element with improved adherence between layers
US6117624A (en) * 1993-06-04 2000-09-12 Eastman Kodak Company Infrared sensitized, photothermographic article
US6171707B1 (en) 1994-01-18 2001-01-09 3M Innovative Properties Company Polymeric film base having a coating layer of organic solvent based polymer with a fluorinated antistatic agent

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JPS52152225A (en) * 1976-06-11 1977-12-17 Fuji Photo Film Co Ltd Color photographic light sensitive material
JPS5526590A (en) * 1979-05-25 1980-02-26 Fuji Photo Film Co Ltd Magenta density drop prevention method for color photographic material

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USRE29148E (en) * 1972-08-17 1977-03-08 Fuji Photo Film Co., Ltd. Color photographic diffusion transfer process
US3935016A (en) * 1973-04-13 1976-01-27 Fuji Photo Film Company, Ltd. Silver halide color photographic materials containing 3-anilino-5-pyrazolone couplers
US3926631A (en) * 1973-04-13 1975-12-16 Fuji Photo Film Co Ltd Silver halide photographic light-sensitive material
US3930866A (en) * 1973-04-25 1976-01-06 Fuji Photo Film Co., Ltd. Silver halide color photographic materials containing 3-anilino-5-pyrazolone couplers
DE2617826A1 (de) * 1975-04-24 1976-11-04 Fuji Photo Film Co Ltd Photographische farbmaterialien und verfahren zu ihrer behandlung
US4159910A (en) * 1976-08-09 1979-07-03 Konishiroku Photo Industry Co., Ltd. Color photographic materials containing color image fading inhibitor
US4178184A (en) * 1976-10-23 1979-12-11 Konishiroku Photo Industry Co., Ltd. Color photographic materials containing dye-fading inhibitors
US4138259A (en) * 1976-10-29 1979-02-06 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material
US4174220A (en) * 1976-10-30 1979-11-13 Konishiroku Photo Industry Co., Ltd. Color photographic materials containing dye fading inhibitors
US4148656A (en) * 1976-12-17 1979-04-10 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide color photographic materials
US4252893A (en) * 1978-04-11 1981-02-24 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic material
US4264720A (en) * 1978-12-28 1981-04-28 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material
US4360589A (en) * 1980-05-14 1982-11-23 Fuji Photo Film Co., Ltd. Color photographic light-sensitive materials
US4840870A (en) * 1983-12-19 1989-06-20 Konishiroku Photo Industry Co., Ltd. Heat-transfer image-receiving element
EP0147854A2 (en) 1983-12-29 1985-07-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
EP0218266A2 (en) 1984-05-02 1987-04-15 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US4931382A (en) * 1984-06-08 1990-06-05 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US4735893A (en) * 1984-06-08 1988-04-05 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US4767697A (en) * 1985-01-21 1988-08-30 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0209118A2 (en) 1985-07-17 1987-01-21 Konica Corporation Silver halide photographic material
US4741980A (en) * 1985-09-19 1988-05-03 Konishiroku Photo Industry Co., Ltd. Method for increasing color-fastness of organic coloring matter
EP0242013A2 (en) 1986-01-20 1987-10-21 Konica Corporation Silver halide color photographic light-sensitive material
EP0239972A1 (en) * 1986-03-31 1987-10-07 Fuji Photo Film Co., Ltd. 3, 3'(2H,2'H)-spirobibenzofuran compounds and antioxidants comprising the same
US4864039A (en) * 1986-03-31 1989-09-05 Fuji Photo Film Co., Ltd. 3,3'(2'H,2H-Spirobibenzofuran compounds
US4895793A (en) * 1986-04-16 1990-01-23 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US4868101A (en) * 1986-05-22 1989-09-19 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0256537A2 (en) 1986-08-15 1988-02-24 Fuji Photo Film Co., Ltd. Color print and a method for producing the same
US6117624A (en) * 1993-06-04 2000-09-12 Eastman Kodak Company Infrared sensitized, photothermographic article
US5576165A (en) * 1993-07-07 1996-11-19 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US6171707B1 (en) 1994-01-18 2001-01-09 3M Innovative Properties Company Polymeric film base having a coating layer of organic solvent based polymer with a fluorinated antistatic agent
US5492805A (en) * 1994-06-30 1996-02-20 Minnesota Mining And Manufacturing Company Blocked leuco dyes for photothermographic elements
US5492804A (en) * 1994-06-30 1996-02-20 Minnesota Mining And Manufacturing Company Chromogenic leuco redox-dye-releasing compounds for photothermographic elements
US5696289A (en) * 1994-06-30 1997-12-09 Minnesota Mining And Manufacturing Company Blocked leuco dyes for photothermographic elements
US5705676A (en) * 1994-06-30 1998-01-06 Minnesota Mining And Manufacturing Company Chromogenic leuco redox-dye-releasing compounds for photothermographic elements
US5928857A (en) * 1994-11-16 1999-07-27 Minnesota Mining And Manufacturing Company Photothermographic element with improved adherence between layers
US5492803A (en) * 1995-01-06 1996-02-20 Minnesota Mining And Manufacturing Company Hydrazide redox-dye-releasing compounds for photothermographic elements
US5478721A (en) * 1995-01-31 1995-12-26 Eastman Kodak Company Photographic elements containing emulsion stabilizers
EP0800113A2 (en) 1996-04-05 1997-10-08 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material

Also Published As

Publication number Publication date
DE2165371A1 (de) 1972-10-05
DE2166076A1 (de) 1973-07-19
CA998872A (en) 1976-10-26
GB1381499A (en) 1975-01-22
DE2165371C2 (de) 1983-06-23
BE777487A (fr) 1972-04-17
FR2121087A5 (enExample) 1972-08-18

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