US3926869A - Process for hardening gelatin in photographic layers which contain a thickener and hardener by utilizing acrylic acid-acrylamide copolymers - Google Patents

Process for hardening gelatin in photographic layers which contain a thickener and hardener by utilizing acrylic acid-acrylamide copolymers Download PDF

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US3926869A
US3926869A US477236A US47723674A US3926869A US 3926869 A US3926869 A US 3926869A US 477236 A US477236 A US 477236A US 47723674 A US47723674 A US 47723674A US 3926869 A US3926869 A US 3926869A
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gelatin
hardener
thickener
mol
acrylic acid
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Ikutaro Horie
Taksuhi Miyazako
Takeo Shimada
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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
    • 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
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • Gelatin is used in the production of photographic light-sensitive materials as a binder for photographic layers such as a silver halide emulsion layer, a protective layer, a filter layer, an intermediate layer, an undercoating layer and an antihalation layer or a backing layer.
  • a light-sensitive material having some of these layers containing gelatin is processed, after exposure, under various conditions with processing solutions having different compositions.
  • the layers containing gelatin in the photographic material are not treated with a hardener, the layers swell excessively and tend to be injured because of their poor water resistance. The gelatin sometimes even dissolves when processed at higher temperatures. The performance of the light-sensitive material is thus deteriorated.
  • Various hardeners for gelatin have been used for eliminating these defects of gelatin.
  • anionic sites such as carboxy or sulfo groups in the molecule
  • cationic sites such as amino groups in the gelatin molecule to :hinder the hardening effect of the hardener thus requiring use of the hardener in a large amount.
  • Such a large amount of hardener is not i only wasteful but also tends to adversely affectthe photographic properties.
  • hardened gelatin "layers.
  • R and R are each a hydrogen atom'or a methyl group
  • R and R are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which can contain oxo, hydroxy or alkoxy groups or can combine to form a non-metal atom (e.g., carbon, oxygen and/or nitrogen) containing 5 to 7 membered ring
  • X is a hydrogen atom, a sodium atom, a potassium atom, a lithiumatom or an ammonium group.
  • alkyl groups having 1 to 6 carbon atoms which may include oxo, hydroxy or alkoxy groups for R and R are groups such as methyl, ethyl, butyl, tert-butyl, hexyl, cyclohexyl, benzyl, 1,1-dimethyl-3-oxobutyl, l 1 -dimethyl-3-hydroxybutyl, hydroxyethyl, methojxyethyl, hydroxyethoxyethyl, morpholinoethyl, etc groups.
  • rings formed by the combination of R and R are rings such as morpholino, N-methylpiperazino, piperidino, pyrrolidino, hexamethyleneimino, etc., rings.
  • Suitable examples of ammonium groups are those of triethanolamine, diethanolamine, ethanolamine, ammonia, etc.
  • copolymers used in this invention have too low a molecular weight, they improve the swelling of photographic layers during processing to a lesser extent,
  • copolymers having a limiting viscosity in the range of about 0.3 to about 6.0 measured at 30C using a l by weight aqueous solution of sodium chloride are usually desired.
  • Copolymers containing 30 to mol of the aforesaid repeating unit (A) and 20 to 70 mol of the aforesaid repeating unit (B) are particularly useful.
  • the copolymers used in this invention can be easily synthesized by reacting one or more compounds selected from acrylic acid and derivatives thereof with one or more compounds selected from acrylamide and derivatives thereof in a desired ratio in a solvent such as water, water-methanol or water-ethanol with heating to about 70 to C using a polymerization catalyst such as potassium persulfate, ammonium persulfate or po- 3 tassium perphosphate.
  • a polymerization catalyst such as potassium persulfate, ammonium persulfate or po- 3 tassium perphosphate.
  • isopropanol can be used as a chain transfer agent.
  • acrylic acid and derivatives thereof are acrylic acid or methacrylic acid
  • examples of acrylamide or derivatives thereof are acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-methylolacrylamide, N-hydroxyethylacrylamide, N-tert-butylacrylamide, N,N-dibutylacrylamide, N-cyclohexylacrylamide, diacetone acrylamide, N- l l -dimethyl-3-hydroxybutyl)acrylamide, N-(B-morpholino)ethylacrylamide, N-benzylacrylamide, N- acryloylmorpholine, N-methacryloylmorpholine, N- methyl-N'-acryloylpiperazine, N-acryloylpiperidine, N-acryloylpyrrolidine, N-acryloylhexamethyleneimine, etc.
  • the preparation of the copolymers which can be used in this invention is shown below.
  • the limiting viscosity in the following preparation examples is represented as a value measured at 30C using a l aqueous solution of sodium chloride.
  • PREPARATION EXAMPLE 3 Preparation of Polymer (3) Into a one-liter flask provided with a stirrer were placed 43 g (0.5 mol) of methacrylic acid, 35.5 g (0.5 mol) of acrylamide, 500 ml of water, 2 ml of isopropanol and 350 mg of potassium persulfate as a polymerization catalyst. After purging with nitrogen, stirring was effected for 2 hours while keeping the temperature at 70 90C. The reaction product was cooled to room temperature, neutralized with an aqueous solution of sodium hydroxide and then put into a cellophane membrane, which was then dialyzed in running water overnight and then freeze-dried.
  • the copolymers used in this invention can be prepared by copolymerizing acrylic acid or derivatives thereof, acrylamide or derivatives thereof and, if desired, one or more other monomers capable of forming addition polymers therewith such as alkyl esters of acrylic acid or methacrylic acid, styrene and derivatives thereof, vinyl esters, vinyl ethers, acrylonitriles, maleic acid anhydride, vinylpyrrolidone, vinyloxazolidone, vinylmethylimidazole or vinylpyridine in an amount of up to about 5 mol
  • the photographic layers according to this invention include gelatin, a thickener, a hardener and the polymer of this invention. Modified gelatin as well as conventional unmodified gelatin can be used. All of gelatins and derivatives thereof generally used for photography can be preferably employed in this invention.
  • gelatin and gelatin derivatives which include gelatin which is treated with a reagent having one group capable of reacting with the amino groups, imino groups, hydroxy groups or carboxy groups, which are contained in the gelatin molecule as a functional group, and a gelatin graft polymer wherein the molecular chain of another high molecular weight substance is grafted onto the gelatin molecule, can be employed.
  • reagents for preparing the gelatin derivative there are illustrated, e.g., isocyanates as described in U.S. Pat. No. 2,614,928; acid chlorides; acid anhydrides; acid anhydrides as described in US. Pat. No. 3,118,766; phenyl glycidyl ethers as described in Japanese Pat. Publication No. 26845/67; vinylsulfone compounds as described in US. Pat. No. 3,132,945; N- allylvinylsulfonamides as described in British Pat. No. 861,414; maleimides as described in U.S. Pat. No. 3,186,846; acrylonitriles as described in U.S. Pat. No.
  • Vinyl monomers such as acrylic acid, methacrylic acid or the ester, amide or nitrile derivatives thereof can widely be used.
  • Hydrophilic vinyl polymers having some compatibility with gelatin such as the polymers or copolymers of acrylic acid, acrylarnide, methacrylarnide, hydroxyalkyl acrylate, hydroxyalkyl methacrylate or the like are particularly preferred.
  • Thickeners are high molecular weight compounds which increase the viscosity of a coating composition of gelatin and are quite compatible with gelatin.
  • the term thickener as used herein designates those high molecular weight compounds which function to increase the viscosity of a gelatin containing coating composition and any such material which has the function of increasing the viscosity of such a coating solution to a viscosity of about 30 to about 100 centipoises at 40C can be employed.
  • Suitable thickeners are hydroxyethyl cellulose, hydroxypropyl cellulose, a copolymer of methylvinyl ether and maleic acid anhydride, a copolymer containing semiamide of maleic acid as disclosed in British Pat. No.
  • Z is a sulfonic acid group or the salts thereof with, for example, the sodium, potassium, ammonium and like salts.
  • the amount of the thickener is suitably in the range of about 0.001 to about 0.5 parts by weight per part by weight of gelatin.
  • the thickener is usually added so that a viscosity of about 30 to about 100 centipoises, preferably 30 to centipoises, is obtained at 40C with a gelatin coating composition.
  • hardeners compounds generally used for hardening photographic layers can be advantageously employed. Suitable hardeners are, for example, those as described in C.E.K. Mees & T. H. James, The Theory of the Photographic Process, 3rd Ed., pp. 55 60,
  • aldehyde compounds such as mucochloric acid, mucobromic acid, mucophenoxychloric acid, mucophenoxybromic acid, formaldehyde, dirnethlolurea, trimethylolmelamine, 1 ,3-bis( diallylamino )methylurea, 1 ,3-bis(- piperidinomethyl)urea, glyoxal, monomethylglyoxal, 2,3-dihydroxy-1 ,4-dioxane, 2,3-dihydroxy-5-methyl- 1,4-dioxane, succinaldehyde, 2,5-dimethoxytetrahydrofuran or glutaraldehyde; acitve vinyl compounds such as divinyl sulfone, methylenebismaleimide, 5- acetyl- 1 ,3 -diacryloyl-hexahydro-s-triazine, 1 ,3 ,S-triacryloyl-he
  • the amount of a hardener significantly varies depending upon its hardening ability. Generally, a suitable amount is on the order of about 0.0001 to about 0.1 parts, preferably 0.001 to 0.05 parts by weight per part by weight of gelatin.
  • the amount of a polymer used in this invention depends upon the types and amounts of thickener and hardener used therewith. Generally, a suitable amount is on the order of about 0.001 to about 0.1 parts, preferably 0.01 to 0.05 parts by weight per part by weight of gelatin.
  • the photographic layers according to this invention can contain the aforesaid gelatin, thickener, hardener, the polymer of this invention and, if desired, substances which are conventionally added to photographic layers.
  • matting agents such as silica, strontium barium sulfate or a polymethyl methacrylate latex
  • lubricants such as liquid parafiin, polyfluorohydrocarbons or polyalkyl (or aryl) polysiloxane
  • surface active agents such as saponin, polyethyleneglycol monolauryl ether, etc., for example, as described in US. Pat. Nos.
  • the photographic layers of this invention can be light-sensitive silver halide emulsion layers containing light-sensitive silver halide particles.
  • the photographic light-sensitive materials according to this invention have at least one silver halide emulsion layer on a support and are characterized by the presence of at least one photographic layer of this invention.
  • Cellulose ester films such as cellulose nitrate or cellulose acetate
  • polyester films such as polyethylene terephthalate, polyvinyl acetal films, polyvinyl chloride films, polystyrene films, polycarbonate films, baryta papers, polyethylene-coated papers, etc.
  • acetate cellulose nitrate or cellulose acetate
  • polyester films such as polyethylene terephthalate, polyvinyl acetal films, polyvinyl chloride films, polystyrene films, polycarbonate films, baryta papers, polyethylene-coated papers, etc.
  • Silver halide emulsions which are preferably used are those having silver halide particles dispersed in a hydrophilic high molecular weight binder.
  • Suitable silver halides are silver bromide, silver bromoiodide, silver bromoiodchloride, silver bromochloride, silver chloride, silver iodide, etc.
  • suitable hydrophilic high molecular weight binders are gelatin or gelatin derivatives as described above with up to about 20 by weight of the gelatin or gelatin derivative being replaced by hydrophilic high molecular weight substances which are generally used as binders'for photographic layers.
  • Such hydrophilic high molecular weight substances arenatural high molecular weight substances and derivatives thereof such as albumin or agar, cellulose derivatives such as carboxy cellulose alkyl ester, hydroxyethyl cellulose or carboxymethylhydroxyethyl cellulose, synthetic high molecular weight substances such as polyvinyl alcohol, polyacrylamide, polyvinyl pyrrolidone, polyacrylic acid, polyacrylic acid ester or a copolymer of maleic acid anhydride with another vinyl compound.
  • The'silver' halide emulsions can contain silver halide particles of the so-called modified halide type was described in US. Pat. No. 3,622,318, British Pat. No. 635,841, etc.
  • the silver halide emulsions can be sensitized with active gelatin or sulfur compounds as described in US. Pat. Nos. 1,574,944; 1,623,499; and 2,410,689. Also, they can be sensitized with noble metal salts such as palladium or gold as described in US. Pat. Nos. 2,448,060; 2,399,083 and 2,642,361, reducing agents such as stannous salts as described in US. Pat. No. 2,487,850, as well as polyalkylene oxide derivatives. Moreover, they can be spectrally sensitized with cyanine or merocyanine dyes as described in U.SI Pat. Nos. 2,519,001; 2,666,761; 2,734,900; 2,739,964 and 3,481,742.
  • the silver halide emulsions can contain antifogging agents or stabilizing agents such as mercury compounds and azaindenes. Furthermore, the emulsions can contain plasticizers such as glycerine or coating adjuvants as described above, as well as antistatic agents, ultraviolet absorbing agents, fluorescent brighteners, antioxidants, dyes, etc.
  • two-equivalent or four-equivalent color forming couplers canbe present in the emulsion.
  • yellow forming couplers of the open chain type ketomethylene type such as the benzoylacetoanilide or pivaloylacetoanilide compounds
  • magenta forming couplers such as the pyrazolone orindazolone compounds
  • cyan forming couplers such as the phenol or naphthol compounds
  • suitable examples of color forming couplers which canbe employed are disclosed in US. Pats.
  • the silver halide emulsions include various photographic silver halide emulsions, for example, orthochromatic emulsions, panchromatic emulsions, infrared-sensitive emulsions, emulsions for use in recording X-rays and other invisible rays, color photographic emulsions such as emulsions containing color forming couplers, emulsions containing a dye developing agent, emulsions containing a dye which can be bleached, etc.
  • photographic silver halide emulsions for example, orthochromatic emulsions, panchromatic emulsions, infrared-sensitive emulsions, emulsions for use in recording X-rays and other invisible rays, color photographic emulsions such as emulsions containing color forming couplers, emulsions containing a dye developing agent, emulsions containing a dye which can be bleached, etc.
  • the photographic light-sensitive material according to this invention can contain non-light-sensitive auxiliary layers such as filter layers, intermediate layers, antihalation layers, undercoating layers 'or backing layers.
  • auxiliary layers cancontain hydrophilic high molecular weight binder and, if desired, various additives such as colorants or antioxidants.
  • hydrophilic high molecular weight substances used in the silver halide emulsion layers and auxiliary layers in a photographic light-sensitive material are hardened with the aforesaid hardeners.
  • the photographic light-sensitive material according to this invention can be processed by conventional methods. Temperatures in the range of 20C or lower 9 to60C or higher are applicable for processing.
  • the photographic layers in the photographic light-sensitive material of this invention are particularly suitable for rapid processing at high temperature which is effected at temperatures above 30C, since they possess both a high melting temperature and a high swelling rate.
  • Processing solutions are used without particular limitation in this invention, and all of the conventional processing solutions can be employed.
  • gelatin layers containing a thickener which have a high melting temperature and high swelling are obtained. These layers are very useful as photographic layers, and a photographic material having such photographic layers can be used to rapidly provide a photographic image with high sensitivity.
  • EXAMPLE 1 A preparation was made for photographic light-sensitive materials used for a reversal color film to be processed in coupler-containing developer which were provided with a red-sensitive silver halide emulsion layer with a 3 p. thickness, a green-sensitive silver halide emulsion layer with a 2.5 1. thickness, a yellow filter layer with a l p. thickness and a blue-sensitive silver halide emulsion layer with a 3 p. thickness on an undercoated polyethylene terephthalate film (thickness: 84 u).
  • a silver halide emulsion used in the red-sensitive layer was a silver bromoiodide emulsion containing 2.0 mol of iodide, which contained 4.5 of silver halide and 5.4 of gelatin.
  • the silver halide emulsion used in the green-sensitive layer and the blue-sensitive layer was a silver bromoiodide emulsion containing 3.3 mol of iodide, which contained 4.5 of silver halide and 5.4 of gelatin.
  • the yellow filter layer comprised gelatin containing a yellow dye.
  • each of the red-sensitive layer, the green-sensitive layer, the yellow filter layer and the blue-sensitive layer in each light-sensitive material contained poly-p-vinylbenzenesulfonic acid" potassium salt as a thickener and 2,4-dichloro-6- hydroxy-s-triazine'sodium salt as a hardener and Polymer (1) of this invention in the amounts shown in Table l per g of gelatin contained in each layer.
  • EXAMPLE 3 a green-sensitive silver halide emulsion layer with a 4 u thickness and a gelatin protective layer with a 0.7 1. thickness on an undercoated cellulose triacetate film (thickness: 130 u).
  • the silver halide emulsion used for the blue-sensitive layer was a silver bromoiodochloride emulsion containing 6.8 mol of chloride and 1.2 mol of iodide, which contained 9 of silver halide and 10 of gelatin.
  • the silver halide emulsion used for the red-sensitive layer and the green-sensitive layer was a silver bromochloride emulsion containing 30 mol of bromide, which contained 10 of silver halide and 12 of gelatin.
  • the blue-sensitive layer, the red-sensitive layer and the green-sensitive layer contained 2'-chloro- 5'-2-(2,4 -di-tert-amylphenoxy)butylamido-4-methoxybenzoylacetoanilide as a yellow forming coupler, 1- hydroxy-4-chloro-N-dodecyl-2-naphthoamide as a cyan forming coupler and l-( 2,4,6-trichlorophenyl)-3- 3-(2,4-di-tert-amylphenoxy)acetoamidobenzamido S-pyrazolone as a magenta forming coupler, respectively.
  • Each of the intermediate layer (I), the red-sensitive layer, the intermediate layer (II), the green-sensitive layer and the protective layer in each light-sensitive material contained 1.2 mg of 2,4-dichloro-6- hydroxy-s-triazine-sodium salt as a hardener and 25 mg of poly-p-vinylbenzenesulfonic acid'potassium salt as a thickener per g of gelatin contained in each layer, but contained no polymers of this invention.
  • the blue-sensitive layer in each light-sensitive material contained 1 mg of 2,4-dichloro-6-hydroxy-s-triazinesodium salt as a hardener (1), 1 mg of N,N',N"-trisacryloyl-1,3,5- hexahydrotriazine as a hardener (2), mg of poly-pvinylbenzenesulfonic acid-potassium salt as a thickener and the polymer of this invention shown in Table 5 per g of gelatin contained in the layer.
  • the light-sensitive materials were kept under the conditions of a temperature of C and a relative humidity of 60 for 7 days. Thereafter, the photographic layers were measured as to the melting temperature in a 0.2 N aqueous solution of sodium hydroxide and the swelling rate in water at27C. The results obtained are shown in Table 5.
  • EXAMPLE 4 Light-sensitive materials used for indirect X-ray photography were prepared by applying a light-sensitive emulsion layer with a 4 p. thickness on an undercoated cellulose triacetate film (thickness: 175 u).
  • the use of the polymer of this invention can increase the swelling rate of photographic layers.
  • the results obtained in this example confirm that the melting temperature of photographic layers is raised by the use of such a polymer.
  • a process for hardening gelatin which comprises incorporating an acrylic acid-acrylamide copolymer into the system containing gelatin, a thickener and a hardener; said acrylic acid-acrylamide copolymer being a copolymer containing about 5 to mol of the following repeating unit (A):
  • R, and R are each a hydrogen atom or a methyl group, R and R are each a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms, or wherein R and R; can combine to form a non-metal atom containing 5-, 6- or 7 -membered ring, and X is a hydrogen atom, a sodium atom, a potassium atom, a lithium atom, or an ammonium group, said acrylic acid-acrylamide copolymer being present in said sys-v tem at about 0.001 to about 0.1 parts by weight per part by weight of gelatin, and having a limiting viscosity ranging from about 0.3 to about 6.0 measured at 30C using a l by weight aqueous solution of sodium chlo- '13 ride; and said thickener being a high molecular weight polymer comprising the following repeating unit:
  • said hardener is an aldehyde compound, an active vinyl compound, an active halogen containing compound, an epoxy compound, an ethyleneimine compound, a methane sulfonic acid ester compound, a carbodiimide compound, an isoxazole compound, or an inorganic hardener.

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US477236A 1973-06-07 1974-06-07 Process for hardening gelatin in photographic layers which contain a thickener and hardener by utilizing acrylic acid-acrylamide copolymers Expired - Lifetime US3926869A (en)

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US4152161A (en) * 1975-02-26 1979-05-01 Agfa-Gevaert, A.G. Photographic silver halide emulsion with hetero-N containing polymeric binder
US4166050A (en) * 1975-12-01 1979-08-28 Fuji Photo Film Co., Ltd. Method of increasing the viscosity of photographic coating solutions
US4193795A (en) * 1977-10-06 1980-03-18 Eastman Kodak Company Photographic film units containing a polymeric mordant which covalently bonds with certain dyes
US4201840A (en) * 1977-10-06 1980-05-06 Eastman Kodak Company Photographic film units containing a polymeric mordant which covalently bonds with certain dyes
US4294921A (en) * 1979-06-22 1981-10-13 Fuji Photo Film Co., Ltd. Method of hardening gelatin
US4444926A (en) * 1980-11-10 1984-04-24 Fuji Photo Film Co., Ltd. Method of hardening gelatin and photographic materials produced thereby
US4590151A (en) * 1982-11-29 1986-05-20 Eastman Kodak Company Reduction of reticulation in gelatin-containing elements
US5104914A (en) * 1989-05-23 1992-04-14 Ilford Limited Preparation of polymer dispersions and photographic elements containing polymer particles
US5312725A (en) * 1992-04-20 1994-05-17 Konica Corporation Silver halide color photographic light-sensitive material in roll form
EP0597289A1 (en) * 1992-11-12 1994-05-18 Eastman Kodak Company Photographic composition containing a thickening agent
US5547832A (en) * 1992-07-07 1996-08-20 Eastman Kodak Company Method for hardening photographic materials
US5610002A (en) * 1992-11-12 1997-03-11 Eastman Kodak Company Photographic composition containing a thickening agent
US5972591A (en) * 1990-12-20 1999-10-26 Eastman Kodak Company Thickener for delivery of photographic emulsions
US6833488B2 (en) 2001-03-30 2004-12-21 Exotech Bio Solution Ltd. Biocompatible, biodegradable, water-absorbent material and methods for its preparation
US20090306290A1 (en) * 2004-03-02 2009-12-10 Mircea Dan Bucevschi Biocompatible, Biodegradable, Water-Absorbent Hybrid Material
US20090324537A1 (en) * 2006-03-30 2009-12-31 Mircea Dan Bucevschi Polymeric Materials as Stomach Filler and Their Preparation
US11552297B2 (en) * 2014-06-04 2023-01-10 Zeon Corporation Binder composition for lithium ion secondary battery electrode-use, slurry composition for lithium ion secondary battery electrode-use, electrode for lithium ion secondary battery-use, and lithium ion secondary battery

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JPS54147414A (en) * 1978-05-10 1979-11-17 Sanyo Electric Co Ltd Rotation controller for motor
JPS56121590A (en) * 1980-02-27 1981-09-24 Matsushita Electric Ind Co Ltd Controller for revolution of motor of washing machine
GB2090991A (en) * 1981-01-02 1982-07-21 Eastman Kodak Co A Method of Retarding Microspot-defect Formation in a Silver image
JPS6169061A (ja) * 1984-09-12 1986-04-09 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JPH0782218B2 (ja) * 1985-04-01 1995-09-06 富士写真フイルム株式会社 ハロゲン化銀写真感光材料及びそれを用いた超硬調ネガ画像形成方法
JPH0648351B2 (ja) * 1986-03-19 1994-06-22 富士写真フイルム株式会社 ハロゲン化銀写真感光材料の製造方法
JPH0766160B2 (ja) * 1986-03-25 1995-07-19 富士写真フイルム株式会社 超硬調ネガ型写真感光材料
JP2640236B2 (ja) * 1987-12-11 1997-08-13 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料

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US3284207A (en) * 1962-03-29 1966-11-08 Ilford Ltd Photographic light-sensitive materials
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Cited By (18)

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DE2427297A1 (de) 1975-01-02
JPS5013447A (enrdf_load_stackoverflow) 1975-02-12
GB1431245A (en) 1976-04-07

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