US3623878A - Silver halide emulsion containing copolymer of glycidyl methacrylate and vinyl monomer as hardener - Google Patents

Silver halide emulsion containing copolymer of glycidyl methacrylate and vinyl monomer as hardener Download PDF

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Publication number
US3623878A
US3623878A US811627A US3623878DA US3623878A US 3623878 A US3623878 A US 3623878A US 811627 A US811627 A US 811627A US 3623878D A US3623878D A US 3623878DA US 3623878 A US3623878 A US 3623878A
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Prior art keywords
layer
gelatin
copolymer
glycidyl methacrylate
aqueous dispersion
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US811627A
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English (en)
Inventor
Fumihiko Nishio
Nobuo Tsuji
Kotaro Yamasue
Kinji Ohkubo
Tatsuya Tajima
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • 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
    • G03C1/30—Hardeners
    • G03C1/307—Macromolecular substances

Definitions

  • a photographic light-sensitive element comprising at least one gelatin layer wherein the gelatin layer contains an aqueous solution or dispersion of a copolymer of glycidyl methacrylate or glycidyl acrylate, and a vinyl monomer.
  • the copolymer lends enhanced hardening properties to the gelatin.
  • the present invention relates to a photographic lightsensitive element, and more particularly to a hardening agent, that is, an agent for hardening gelatin, to be incorporated in a gelatin layer useful in photographic light-sensitive element.
  • gelatin is widely used as a binder component (a vehicle) for photographic layers such as a light-sensitive silver halide emulsion layer, an under-coating layer, a backing layer, a protective layer for silver halide emulsion layers, an antihalation layer, and the like.
  • a binder component a vehicle
  • photographic layers such as a light-sensitive silver halide emulsion layer, an under-coating layer, a backing layer, a protective layer for silver halide emulsion layers, an antihalation layer, and the like.
  • a layer composed of gelatin is mechanically weak, the layer formed tends to be easily scratched by rubbing.
  • the .gelatin layer is swollen or weakened during photographic processings such as developing, fixing and water washing, the tendency for scratching, etc., is
  • a photographic light-sensitive element in which paper is employed as the support is, after processing (such as exposure, developing, fixing, and water washing), dried and glazed, often by means of a ferrotype glazing machine.
  • a ferrotype glazing machine when the melting point of the gelatin which is used as the binder is much lower than the surface temperature of the glazing plate, the emulsion layer or protective layer composed of gelatin is melted off at the glazing plate, causing the phenomenon called ferrotype melting (the melting of the emulsion layer due to the heat of glazing machine).
  • ferrotype melting the melting of the emulsion layer due to the heat of glazing machine.
  • a printing paper is subjected to drying by a glazer while a gelatin layer faces the cloth-covered side of the glazing machine, the layer frequently becomes partially attached to the cloth.
  • the amount of hardening agent in the gelatin layers has been increased, but in this case, the viscosity of the gelatin solution containing the silver halide to which the hardening agent has been added is increased considerably during the coating operation, and the coating thickness becomes thicker when the coating operation occurs after increasing lapses of time. This makes the coating operation frequently very ditficult.
  • the present invention does provide an answer to the problems which have heretofore plagued the prior art in that an improved hardening agent and a photographic light-sensitive material utilizing an improved hardening agent is provided.
  • the present invention provides an improved hardening agent and an improved photographic light-sensitive material utilizing the hardening agent.
  • the hardening agent comprises a copolymer of glycidyl methacrylate or glycidyl acrylate and a vinyl monomer, and is in the form of an aqueous dispersion or solution in at least one gelatin layer occurring in the photographic light-sensitive element.
  • the gelatin layer may be, inter alia, a gelatino silver halide emulsion layer, a protective layer, an antihalation layer, or a backing layer.
  • an object of the present invention is to provide a photographic light-sensitive element having at least one gelatin layer containing an improved hardening agent which is not accompanied by the aforesaid faults.
  • Another oobject of this invention is to provide an improved hardening agent for use in photographic lightsensitive elements.
  • a gelatino silver halide photographic light-sensitive element having a gelatin layer containing as a hardening agent an aqueous dispersion of a copolymer of glycidyl methacrylate or glycidyl acrylate and a vinyl compound.
  • Glycidyl methacrylate or glycidyl acrylate, used as a ingredient of the copolymer of this invention are represented by the following chemical formulae:
  • the vinyl compound which is copolymerized with glycidyl methacrylate or glycidyl acrylate is a monomer capable of being substantially copolymerized with glycidyl methacrylate or glycidyl acrylate, causing no reaction with the glycidyl group during emulsion polymerization, thereby making emulsion polymerization possible.
  • vinyl monomers there are alkyl acrylates, alkyl methacrylates, tit-substituted alkyl acrylates, acrylamide derivatives, methacrylamide derivatives, a-substituted acrylamide derivatives, vinyl esters, vinyl halides, vinylidene halides, vinyl oxazolidinone, vinylpyrrolidone, other N-vinylamides, vinylpyridine, styrene, styrene derivatives, butadiene, isoprene, acrylonitrile, methacrylonitrile, and the like.
  • the copolymer used as a hardening agent in the present invention can be obtained by the copolymerization of the aforesaid glycidyl methacrylate or glycidyl acrylate and the aforesaid vinyl compound.
  • the monomers i.e., glycidyl methacrylate or glycidyl acrylate and the vinyl compound abovementioned
  • degassed distilled water in an amount of -60% by weight of the total system
  • suitable amounts of anionic surface active agents and water soluble polymerization initiators such as potassium persulfate are added to the system, and after adding, if necessary, additives for polymerization, the mixture is stirred vigorously for several hours at -90 C.
  • the desired aqueous emulsified dispersion of the copolymer is obtained.
  • the proportion of glycidyl methacrylate or glycidyl acrylate is less than 10 mole percent, the hardening agent thus prepared shows an insufficient hardening action.
  • the proportion thereof is higher than 90 mole percent, the copolymer tends to form aggregates with itself when the copolymer is added to a solution of gelatin, whereby the layer thus formed tends to become opaque. Therefore, it is desirable that the copolymerization ratio of glycidyl methacrylate or glycidyl acrylate to the vinyl compound comonomer be from 1/9 to 9/1 (mole ratio).
  • the aqueous dispersion of the copolymer in this invention may be prepared, as mentioned above, by subjecting the monomeric ingredients to emulsion polymerization onic surface active agents, there are lauryl sulfate alcohol, sodium alkylbenzene sulfonate, sodium l3-(p-nonylphe'noxy-5,8,l1-trioxatridecane-l-sulfate), and the like.
  • the particle size of the copolymer in the aqueous dispersion thereof used in this invention is too large, the compatibility thereof with gelatin is poor.
  • the particle size is controlled by the conditions for emulsion polymerization. That is, the particle size can be controlled by adjusting the reaction conditions such as the amount of a surface active agent as the dispersion agent, the stirring conditions, the reaction time, the reaction temperature, and the like.
  • the particle size employed in this invention is usually from 0.01 to 1 micron preferably from 0.05 to 0.3 micron.
  • PREPARATION 1 A glass-lined close-type reaction vessel having temperature control means, a stirrer, a reflux condenser, heating means, and a gas inlet was purged with nitrogen gas.
  • Into the reaction vessel were charged 800 parts by weight of degassed distilled water, 120 parts by weight of glycidyl methacrylate which had been purified by distillation to remove any polymerization inhibitor and parts by weight of butyl methacrylate (the mole ratio of glycidyl methacrylate to butyl methacrylate was 60/40).
  • the reaction mixture was stirred vigorously by means of a stirrer at 500- 800 rpm. to be emulsified. Thereafter, 0.15 part of ammonium persulfate and 0.05 part by weight of sodium bisulfite as a polymerization initiator were added, and the system was maintained at l00 C. with stirring. The reaction was continued for 6 hours, the polymerization being finished completely.
  • the particle size of the solid polymer in the aqueous dispersion of the glycidyl methacrylate copolymer thus prepared was confirmed to be about 0.1-0.3 micron by electron microscope measurements.
  • PREPARATION 2 The same procedure as in Example 1 was repeated using the same reaction vessel as in the example but 754 parts by weight of distilled water, 80 parts by weight of glycidyl methacrylate, parts of butyl acrylate, (mole ratio of glycidyl methacylate to butyl acrylate being 40/60), 9.3 parts by weight of as a dispersing agent, and 0.5 part of potassium persulfate as a polymerization initiator were added. The particle size of the solid polymer in the aqueous dispersion of the glycidyl methacrylate/butyl acrylate copolymer thus obtained was confirmed to be 0.10.3 micron.
  • PREPARATION 3 The same procedure as in Example 1 was repeated using the same reaction vessel as in the example but parts by weight of glycidyl acrylate and 70 parts by weight of ethyl acrylate instead of glycidyl methacrylate and butyl methacrylate were added (the other components being the same) to provide an aqueous emulsified dispersion of a copolymer of substantially the same size.
  • PREPARATION 4 The same procedure as in Example 1 was repeated using the same reaction vessel as in the example and 80 parts by weight of glycidyl acrylate and 120 parts by weight of styrene were used to replace the monomers (other conditions being equal) to provide an aqueous emulsified dispersion of a copolymer of substantially the same size.
  • PREPARATION 5 The same procedure as in Example 1 was repeated by using the same reaction vessel, etc. as in the example, but 120 parts by weight of glycidyl methacrylate and 80 parts by weight of vinyl acetate were used as the monomers to provide an aqueous emulsified dispersion of a copolymer of substantially the same size.
  • the aqueous dispersion of copolymers prepared above may be used alone or as a mixture of two or more kinds thereof in this invention. Moreover, the dispersion may be used together with other aqueous emulsified dispersion of polymers having no glycidyl group, and this case is sometimes more effective for some purposes.
  • the weight ratio of the copolymer of the aqueous dispersion thereof (the weight of monomer used for preparing the copolymer) to the gelatin is desirably from 0.05/1 to 1/ 1. If the ratio is less than 0.05/1, the effect of the aqueous dispersion of copolymer is too weak, and if it is higher than l/l, the layer is hardened too much, which delays the developing procedure.
  • aqueous dispersion of copolymer of this invention may be incorporated in a gelatino silver halide emulsion layer as well as into other gelatin-containing layers such as a protective layer, an antihalation layer, a backing layer and the like.
  • a gelatin-containing solution or dispersion having incorporated therein the aqueous dispersion of the copolymer of glycidyl methacrylate or glycidyl acrylate and the vinyl compound is applied to a support, a layer having a sufiiciently high transparency as well as a very high hardness and excellent wear resistance can be obtained in a short period of time after coating and drying.
  • the gelatin-containing solution or dispersion can be utilized for preparing photographic printing paper, ferrotype melting of printing paper during glazing by a glazer can be prevented.
  • aqueous dispersions of copolymers in accordance with the present invention provide many advantages, such as that when the dispersion is incorporated in a gelatin solution in an amount sufficient to show an adequate hardening effect, the viscosity change when the solution is stored for a long period of time is lessened.
  • Example 1 To 1 kg. of a gelatino silver chlorobromide emulsion containing 7.5% by weight gelatin and 2.5% by weight silver chlorobromide was added ml. (no addition; control example), 50 ml., 100 ml., 150 ml. or 200 ml. of the aqueous dispersion of the copolymer of glycidyl methacrylate and butyl methacrylate prepared by the procedure as in Preparation 1 described above to provide five kinds of photographic light-sensitive emulsions. Each of the emulsions thus prepared was applied to a photographic baryta-coated paper so that the amount of silver per unit area of the emulsion layer was the same in each case. The layer was then dried.
  • the melting point of the formaldehyde-containing layer was suddenly increased when the layer was allowed to stand for 24 hours at a temperature of 50 C. and a relative humidity of 90%
  • 150 ml. of the aqueous dispersion of the copolymer of glycidyl methacrylate and butyl methacrylate was added to 1 kg. of the photographic emulsion mentioned above to provide a sample in accordance with this invention.
  • 40 ml. of an aqueous 6% Formalin solution was also added to 1 kg. of the photographic emulsion to provide a comparative sample.
  • the viscosity change of each of the samples was observed by measuring the viscosity of the emulsion after 0 hours, 2 hours, and 4 hours, while maintaining the sample at 35 C. (The viscosity was shown by the specific viscosity at 35 C.) The results are shown in the following table.
  • Example 2 Into '1 kg. of a coating composition for use as an antihalation layer consisting of an aqueous 6% by weight gelatin solution containing a standard antihalation dye, there was incorporated (separate 1 kg. base for each):
  • the resulting mixtures were applied to a cellulose triacetate film having a gelatin under coating so that the dry thickness of the layer was 9.0105 micron. After drying the four kinds of samples thus prepared, they were allowed to stand for days at room temperature, and the melting point of the layers was measured as in Example 1. To test the strength of the layer of the samples during development, each sample was developed for three minutes in a commercial developer, and the surface of the layer of the sample immersed in the developer was scratched with a loaded metallic stylus. The minimum weight of the loaded metallic stylus capable of scratching the surface (scratch hardness) was measured.
  • the sample was processed for two minutes in a conventional fixing solution and the scratch hardness of the surface of the layer was again measured by means of a loaded metallic stylus. Further, after fixing, the sample was washed with flowing water for minutes and the scratch hardness of the surface of the film was again measured. After mixing and water-washing, the permeability of the layer was also measured. The results are shown in the following table.
  • Preparation 3 (6:4 mole ratio). After stirring thoroughly, the resulting mixture was applied to a photographic baryta-coated paper having a weight of 150 g./m. so that the same amount of silver was applied to the paper throughout this series of tests. After drying, the samples were allowed to stand at room temperature for four days, 15 days, days, and days, respectively. Other samples (same composition) were allowed to stand for 24 hours at a temperature of C. and a relative humidity of Each of these samples thus stored was subjected to the following processings: development, stopping, fixing, water washing and then drying by a glazer at C.
  • One kg. of the aforesaid gelatino silver halide emulsion was also mixed with: (2) 10 ml. of an aqueous 5% chromium alum solution and 30 ml. of an aqueous 6% Formalin solution; (3) 15 ml. of an aqueous 5% chromium alum solution and 65 ml. of an aqueous 6% Formalin solution; or (4) 150 ml. of an aqueous dispersion of a homopolymer of ethylacrylate.
  • Each of the resulting mixtures was applied to a support and dried, and thereafter each of the samples thus prepared was subjected to the above-described processings and drying by a glazer.
  • the scratch hardness of the former layer was higher than those of the gelatin layers containing the aqueous dispersion of the homopolymers of glycidyl methacrylate or butyl acrylate, or an aqueous solution of mucochloric acid.
  • Example 3 To 1 kg. of a gelatino silver halide emulsion containing 10.2% by weight gelatin and 3.5% by weight silver chloroiodobromide consisting of 48 mole percent silver chloride, 50 mole percent silver bromide and 2 mole percent silver iodide, there was added ml. of the aqueous dispersion of the copolymer of glycidyl acrylate and ethyl acrylate prepared by the procedure as in 24 hrs. at 90% Forum- R.H. and Develop Water tion of 10 days 50 0. ing, Fixing washing haze 72 82 50 65 60 None. 42 72 38 52 46 Hazy. 40 58 45 6O 50 None. 46 78 40 55 47 None.
  • the layer prepared using the aqueous dispersion of the copolymer of glycidyl methacrylate and ethyl acrylate gave no ferrotype melting even within a short period of time after coating and drying. Such a result could not be obtained by the layers prepared by using chromium alum and increased amounts of Formalin respectively.
  • the layers prepared by using chromium alum and increased amounts of Formalin were not be obtained by the layers prepared by using chromium alum and increased amounts of Formalin respectively.
  • Example 4 A gelatine silver halide emulsion containing 8.2 percent by weight of gelatin and 2.7 percent by weight of silver chlorobromide (70 mole percent silver bromide and 30 mole percent silver chloride) was applied to a photographic baryta-coated paper of 240 g./sq. In. at a dry thickness of 12 microns. On the layer thus prepared there was applied as a protective layer a mixture of one liter of a solution containing 2.2 percent by weight gelatin and: (l) 200 ml. of an aqueous dispersion of the copolymer of glycidyl acrylate and styrene (4:6 mole ratio) prepared by Preparation 4 described above; (2) 30 ml. of an aqueous 6 percent Formalin solution; or (3) 70 ml. of an aqueous 6 percent Formalin solution all at a dry thickness of about 0.8 microns. The layers were dried.
  • Example 2 The melting point of thus formed layer was measured as in Example 1. Also each of the samples was developed, stopped, fixed, water Washed and subjected to drying by a glazer at a temperature of 95 C. With respect to the samples dried, the extent of the attaching of naps to the emulsion layer was designated by the symbols A, B, C, and D, wherein the symbol A represents the smallest amount of nap. The value in the parenthesis is the melting point of the emulsion layer.
  • Sample 1 2 3 4 5 Amount of the copolymer, (ml.) O 50 100 150 200 MR after 3 days 0.). 58 68 76 82 M.P. after 24 hours at 90% RH. and 50 0.
  • Example 1 the viscosity increase of the emulsion containing the aqueous dispersion was comparatively low.
  • Example 6 Into 1 kg. of a coating composition for use as an antihalation layer consisting of an aqueous 6 percent by weight gelatin solution containing a standard antihalation dye as in Example 2, there was incorporated each of (1) 100 ml. of the aqueous dispersion of the copolymer of glycidyl methacrylate and acrylonitrile (4:6 mole ratio) prepared in Preparation 6.
  • Example 2 The resulting mixture was applied to a cellulose triacetate film having a gelatin under coating as in Example 2.
  • the gelatin film prepared by the aqueous dispersion of the copolymer of glycidyl methacrylate and acrylonitrile had a higher melting point than the other gelatin layer, and the scratch hardness of the former layer was higher than the gelatin layer prepared with the aqueous dispersion of each of the aforesaid homopolymer.
  • Example 7 The procedure of Example 1 was repeated except that the aqueous dispersion of the copolymer of glycidyl methacrylate and vinylidene chloride was employed instead of the aqueous dispersion of the copolymer of glycidyl methacrylate and butyl methacrylate.
  • the emulsion layer having incorporated therein the aqueous dispersion of the copolymer had a very high melting point even after being allowed to stand for three days after drying.
  • the other chemical structures are the same as those for the acrylamide derivatives; vinylesters useful are vinyl acetate, vinyl propionate, vinyl butylate; a useful vinyl halide is one as vinyl chloride; a useful vinylidene halide is one such as vinylidene chloride; other N-vinylamide utilizable are those such as N-methyl-N-vinyl acetoamide, N-methyl-N-vinyl formamide, N-vinyl caprolactam; styrene derivatives utilized are those such as alphamethyl styrene.
  • the surface activation utilized is much preferably in the range 01-20 percent by weight, based on the total weight of monomer.
  • this is most preferably utilized within the range 0.01-l percent by weight based on the total weight of monomer.
  • reaction time is substantially not critical with reference to the present invention, a most preferred reaction time is within the range 38 hours.
  • the size of the particles will become smaller as the amount of surface active agent utilized is increased. However, the size of the particles is generally not affected by the initiator material utilized, or the reaction time.
  • the developer referred to in the prior part of the specification comprises 500 cc. hot water, 30 grams anhydrous sodium sulfite, 7.5 grams p-formaldehyde, 22 grams sodium bisulfite, 7.5 grams boric acid, 22.5 grams hydroquinone, 1.6 grams potassium bromide, and water to make 1 liter.
  • the fixer utilized in the heretofore provided portion of the specification comprises: first solution-hot water at 50 C. (600 cc.), 300 grams of hypo; second solutionhot water at 50 C. (200 cc.), grams of anhydrous sodium sulfite, 12 cc. of glacial acetic acid, grams of potassium alum and 12 grams of sodium metaborate. Generally, the first and second solutions are mixed together and water is added to make one liter. This results in a final fixer.
  • the other polymer can comprise 10- 90 percent by weight of the total polymer mixture. Obviously, this will depend upon the exact contemplated final use for the photographic light-sensitive element.
  • a photographic silver halide light-sensitive element comprising a support and at least one gelatin layer containing an aqueous solution of a copolymer of glycidyl methacrylate or glycidyl acrylate, and a vinyl monomer, capable of being substantially copolymerized with glycidyl methacrylate or glycidyl acrylate, causing no reaction with the glycidyl group during emulsion polymerization.
  • said vinyl monomer is selected from the group consisting of alkyl acrylate, alkyl methacrylate, alpha-chloro or alpha-cyano alkyl acrylate, the alkyl groups of said monomers each having from 1 to 8 carbon atoms, acrylamide, N,N-dimethyl acrylamide, N,N-diethyl acrylamide, N-methyl acrylamide, N-ethyl acrylamide, acryloyl morpholine, methacrylamide, N,N-dimethyl methacrylamide, N,N-diethyl methacrylamide, N- methyl methacrylamide, N-ethyl methacrylamide, methacryloyl morpholine, alpha-chloro or alpha-cyano acrylamide, vinyl acetate, vinyl propionate, vinyl butylate, vinyl halide, vinylidene halide, N-vinylamide, vinyl pyri- 12 dine
  • a photographic light-sensitive element wherein the ratio of the weight of the polymer in an aqueous dispersion to the weight of gelatin in an aqueous dispersion of from about 0.05:1 to about 1:1.
  • a photographic light-sensitive element wherein the aqueous dispersion of a copolymer is prepared by the emulsion polymerization of monomers dispersed in water by an anionic surface active agent.
  • a photographic light-sensitive element according to claim 1, wherein said copolymers are particulate and have a diameter of from about 0.01 micron to about 1 micron.
  • gelatin layer is a gelatino silver halide emulsion layer 7.
  • gelatin layer is a protective layer.
  • gelatin layer is an antlhalation layer.
  • gelatin layer is a backing layer.
  • aqueous dispersion contains a copolymer consisting of from about 10-90 mole percent of a member from the group consisting of glycidyl methacrylate and glycidyl acrylate and from about 10 mole percent of a vinyl monomer.
  • a photographic light-sensitive element wherein said vinyl monomer is selected from the group consisting of alkyl acrylate, alkyl methacrylate, alpha-chloro or alpha-cyano alkyl acrylate, the alkyl groups of said monomers each having 1 to 8 carbon atoms, acrylamide, N,N-dimethyl acrylamide, N,N-diethyl acrylamide, N-methyl acrylamide, N-ethyl acrylamide, acryloyl morpholine, methacrylamide, N,N-dimethyl methacrylamide, N,N-diethyl methacrylamide, N- methyl methacrylamide, N-ethyl methacrylamide, methacryloyl morpholine, alpha-chloro or alpha-cyano acryl amide, vinyl acetate, vinyl propionate, vinyl butylate vinyl halide, vinylidene halide, N-vinylamide, vinyl pyridine, styrene
  • a photographic light-sensitive element wherein the ratio of the weight of the polymer in an aqueous dispersion to the weight of gelatin in an aqueous dispersion of from about 0.05:1 to about 1:1.
  • a photographic light-sensitive element according to claim 1, wherein said aqueous solution is an aqueous dispersion.
  • a photographic light-sensitive element wherein said anionic surface active agent is a member selected from the group consisting of lauryl sulfate alcohol, sodium alkylbenzene sulfonate, and sodium 13 (p nonylphenoxy 5,8,11 trioxatridecane 1- sulfate).

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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US811627A 1968-03-28 1969-03-28 Silver halide emulsion containing copolymer of glycidyl methacrylate and vinyl monomer as hardener Expired - Lifetime US3623878A (en)

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BE (1) BE730647A (enrdf_load_stackoverflow)
DE (1) DE1916148A1 (enrdf_load_stackoverflow)
GB (1) GB1230354A (enrdf_load_stackoverflow)
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4145221A (en) * 1977-11-08 1979-03-20 Gaf Corporation Synthetic polymer latices in photographic silver halide emulsions containing multivalent metal salts
EP0204530A2 (en) 1985-05-31 1986-12-10 Konica Corporation Method for forming direct positive color image
US4647528A (en) * 1983-09-16 1987-03-03 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5252446A (en) * 1991-09-25 1993-10-12 Konica Corporation Silver halide color photographic light-sensitive material comprising a 1-pentachlorinated phenyl-5-pyrazolone coupler and specific red sensitizing dyes
US5275926A (en) * 1991-09-25 1994-01-04 Konica Corporation Silver halide color photographic light-sensitive material
US5302506A (en) * 1991-06-26 1994-04-12 Konica Corporation Silver halide photographic materials
EP0772082A1 (en) 1995-10-23 1997-05-07 Konica Corporation Plastic film with antistatic layer and silver halide light-sensitive photographic element using the same
EP1750173A1 (en) 2005-08-04 2007-02-07 Fuji Photo Film Co., Ltd. Silver halide photosensitive material and packaged body containing the same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4510238A (en) * 1982-03-11 1985-04-09 Ciba Geigy Ag Photographic material and a process for its manufacture

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4145221A (en) * 1977-11-08 1979-03-20 Gaf Corporation Synthetic polymer latices in photographic silver halide emulsions containing multivalent metal salts
US4647528A (en) * 1983-09-16 1987-03-03 Fuji Photo Film Co., Ltd. Silver halide photographic material
EP0204530A2 (en) 1985-05-31 1986-12-10 Konica Corporation Method for forming direct positive color image
US5302506A (en) * 1991-06-26 1994-04-12 Konica Corporation Silver halide photographic materials
US5252446A (en) * 1991-09-25 1993-10-12 Konica Corporation Silver halide color photographic light-sensitive material comprising a 1-pentachlorinated phenyl-5-pyrazolone coupler and specific red sensitizing dyes
US5275926A (en) * 1991-09-25 1994-01-04 Konica Corporation Silver halide color photographic light-sensitive material
EP0772082A1 (en) 1995-10-23 1997-05-07 Konica Corporation Plastic film with antistatic layer and silver halide light-sensitive photographic element using the same
EP1750173A1 (en) 2005-08-04 2007-02-07 Fuji Photo Film Co., Ltd. Silver halide photosensitive material and packaged body containing the same

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NL6904691A (enrdf_load_stackoverflow) 1969-09-30
BE730647A (enrdf_load_stackoverflow) 1969-09-01
GB1230354A (enrdf_load_stackoverflow) 1971-04-28

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