US3305362A - Process for developing silver halide and compositions therefor - Google Patents

Process for developing silver halide and compositions therefor Download PDF

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US3305362A
US3305362A US260998A US26099863A US3305362A US 3305362 A US3305362 A US 3305362A US 260998 A US260998 A US 260998A US 26099863 A US26099863 A US 26099863A US 3305362 A US3305362 A US 3305362A
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stabilizer
formula
emulsion
fogging
plus
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US260998A
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Riester Oskar
Stracke Werner
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Agfa Gevaert NV
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Agfa AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/60—Naphthoxazoles; Hydrogenated naphthoxazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
    • C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D277/70—Sulfur atoms
    • C07D277/72—2-Mercaptobenzothiazole
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/84—Naphthothiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D293/00—Heterocyclic compounds containing rings having nitrogen and selenium or nitrogen and tellurium, with or without oxygen or sulfur atoms, as the ring hetero atoms
    • C07D293/10—Heterocyclic compounds containing rings having nitrogen and selenium or nitrogen and tellurium, with or without oxygen or sulfur atoms, as the ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D293/12—Selenazoles; Hydrogenated selenazoles
    • 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
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium

Definitions

  • This invention relates to photographic emulsions, respectively to light-sensitive layers produced of the said emulsions which are improved with respect to their stability by the use of novel stabilizers.
  • Another object is to provide new stabilizers having excellent stabilizing properties without concomitant decreases in sensitivity or displacement of the colour tone of the developed silver image or without deleterious influence on the gradation.
  • Z represents an oxygen, sulphur or selenium atom and Y represents the carbon atom necessary for completing a S-membered or 6-membered ring
  • the said atoms at the same time constituting ring members of an aromatic system which consists of one or two condensed benzene rings having an acid substituent, such as a carboxyl group, a sulpho group or sulphonamide group.
  • the organic system for example, a benzene or naphthalene ring, can in its turn contain other substituents, but these generally have no influence on the activity of the class of compounds according to the invention.
  • substituents include for example halogen atoms and alkyl, ether and ester groups, containing preferably up to carbon atoms.
  • the sulphonamide group can in its turn also be substituted by alkyl, aralkyl or aryl radicals.
  • the compounds according to the invention can be used with all usual silver halide emulsions. Their eifect is particularly advantageous with silver chlorobromide emulsions, such as described by way of example in the Bios-Final-Report 3,305,302 Patented Feb. 21, 1967 "ice 252, under the names Brovira-braun, Portriga kralftig, Lupex normalbraun, etc.
  • the silver chlorobromide emulsions may contain silver iodide up to 10 mol percent. The optimal concentration for use may -be determined in each particular case without difficulties.
  • the quantities set out below may in general be used:
  • the superiority of the stabilizer according to the invention is particularly apparent under extreme conditions such as prolonged development periods or raising of the temperature of the developer.
  • the substances according to the invention can be used in the form of the free acids or as salts, for example, of sodium, potassium or barium, or of an organic base.
  • the substances are dissolved in a solvent which is compatible with the emulsion, such as water or methanol.
  • the stabilizers can also be added to another layer.
  • the stabilizers can also be used in the development baths or in a preliminary bath, in order to achieve the same effect and in order to develop already slightly fogged photographic layers with a substantially smaller degree of fogging.
  • the activity of the stabilizers according to the invention is generally not influenced by other emulsion additives such as sensitizers, wetting agents of natural or synthetic origin, hardeners, etc.
  • the stabilizers according to the invention can be used in black and white and-colour photographic materials, containing colour couplers capable of reacting with the oxidation product of a primary aromatic amine developer to form a dye.
  • Example 1 To a silver chlorobromide emulsion, which has, for example, been prepared ac-cording to Bios-Berichte, Final Report 252, Item No. 9, Brovira Normal Braun, the sodium salt of 2'mercapto-[naphtho-l,2:4,5-oxazole]-sulphonic acid-(4) (Formula 1) is added before casting in the form of an aqueous methanolic solution and in a dilution of 121000. The reduction in the fogging obtained is apparent from the following table:
  • a developer of the following composition is used:
  • Example 2 80 mg. of the sodium salt of Z-mercapto-(naphtho- 2,3;4,5-oxazole-(7)-sulphonic acid-(6') in the form of a 1% solution in water (Formula II) are added to 1 litre of a silver chlorobromide emulsion ready for casting. A photographic paper coated therewith shows a reduction in fogging, even with considerably extended development times.
  • FIG- URES 1 and 2 The results of the measurements are evaluated in FIG- URES 1 and 2.
  • the development time is plotted as abscissae against the density of the fogging as ordinates.
  • FIGURE 1 relates to experiments which are carried out at room temperature
  • FIGURE 2 illustrates the behaviour of an emulsion which has been stored for 2 days at 60 C. in a heating chamber.
  • Curve 1 applies to the emulsion without stabilizer, curve 2 to an emulsion with a standard stabilizer and curve 3 to an emulsion which contains the aforementioned stabilizer according to the invention.
  • the oxazole of Formula II was prepared in the manner described in Example 1, starting from 2-amino-3-0xynaphthalene-6-sulphonic acid, the sodium salt being obtained as colourless needle-shaped crystals.
  • Example 3 30 mg. of the sodium salt of 2-mercapto-6,7-benzobenzoxazole-S-sulphonic acid as a 1% aqueous solution (Formula III are added) to 1 litre of the emulsion ready for casting.
  • the Formula III compound is prepared by reacting 1- oxy-2-aminonaphthalene-4-sulphonic acid with carbon disulphide in the manner previously described.
  • the sodium salt is obtained as colourless crystals containing 1 mol of water of crystallization.
  • 1-amino-2-oxynaphthalene-6-sulphonic acid is used for the preparation of the stabilizer, of Formula IV and the preparation is carried out as indicated in Example 1.
  • the sodium salt+1 mol of water of crystallisation is obtained.
  • Example 5 An aqueous solution of the sodium salt of 2-mercapto- (perioxazinsulfonic acid-(8)) (Formula V) used as a stabilizer gives the following results with specimens subjected to the heating chamber test referred to above.
  • the stabilizer is prepared according to the method indicated in Example 4 from 1-amino-8-oxynaphthalene-o-sulphonic acid. Colourless crystals are obtained.
  • Example 6 The addition of the sodium salt of 2-mercapto(naphtho- 2',3',:4,5-oxazole)-disulphonic acid (6',8) (Formula VII) reduces the fogging in the following manner when the development time is extended to 10 minutes:
  • the stabilizer is prepared from 2-oxy-3-aminonaphthalene 5,7-disulphonic acid in the manner described.
  • the disodium salt which crystallizes with 3 mols of water, is obtained as colourless crystals.
  • Example 8 30 mg. of the sodium salt of Z-mercapto-S-chlorobenzoxazole-7-sulphonic acid per litre of a gelatine-silver chlorobromide emulsion produces a reduction in fogging with a development time of 10 minutes from 0.095 to 0.051.
  • the stabilizer (Formula VIII) is prepared in the manner indicated from 2-amino-4-chlorophenol-6-sulphonic acid. Colourless crystals of the sodium salt are obtained which are readily soluble in water.
  • Example 9 45 mg. of sodium salt of Z-mercaptobenzoxazole-S- sulphonic acid per litre of a normal silver bromide emulsion produced a reduction in the fogging from 0.095 to 0.064 when a development time of 10 minutes was employed.
  • the stabilizer (Formula IX) is prepared from 2-aminophenol-4-sulphonic acid in the manner described. Colourless crystals of the sodium salt, containing /2 mol of water are obtained.
  • Example Fogging after 7 l0 development Emulsion without additive Emulsion with 30 mg. of standard stabilizer Example Fogging after 7 l0 development Emulsion without additive Emulsion with 30 mg. of standard stabilizer.
  • Stabilizer X was prepared as follows:
  • Example 11 Example 12 2 mercaptobenzoxazole 5 carboxylic acid (Formula XII) produces the following fogging values in a silver chlorobromide emulsion which has been heated for 7 days in an oven at 40 C.
  • Emulsion +45 mg. of stabilizer according to Formula XII The stabilizer according to Formula XII is prepared from 3-amino-4-hydroxybenzoic acid in the manner described.
  • Example 13 45 mg. of Z-mercaptobenzoxazole-7-carboxylic acid (XIII) per litre of emulsion produce a fogging of 0.052 and a gradation in the experiments indicated in Example 12. It is prepared from 2-hydroxy-3-aminobenzoic acid, the sodium salt containing /2 mol of water crystallisation being obtained.
  • the stabilizer is prepared from l-hydroxy-Z-aminobenzene-4-sulphonic acid amide in the manner described and the sodium salt is obtained in the form of colourless crystals.
  • Example 15 60 mg. of the sodium salt of 2-merca-pto-6-sulphonamidobenzoxazole produce a fogging of 0.044 in the series of experiments described in Example 14.
  • the stabilizer is prepared from 1-hydroxy-2-aminobenzene-S-sulphonamide and the sodium salt is obtained.
  • Example 16 45 mg. of the sodium salt of 2-mercapto-S-methyl-benzoxazole-7-sulphonic acid produce the following fogging values after 10 minutes development:
  • Emulsion without additive 0.074 Emulsion plus standard stabilizer 0.057 Emulsion plus stabilizer according to Formula XVI 0.047
  • the stabilizer is prepared from 1-oxy-2-amino-4-methylbe-nzene-6-sulphonic acid in the manner described and the sodium salt containing /z mol of Water is obtained.
  • Example 17 The stabilizers can be applied in admixture with other stabilizers according to the invention or with other known stabilizers.
  • the following tables show the results of tests with mixtures of stabilizers.
  • the stabilizers were added in the form of an aqueous solution to a silver chlorobromide emulsion.
  • Emulsion development Without stabilizer 0.273 Plus 40 mg./l. stabilizer II 0.133 Plus 20 mg./l. stabilizer II and IV each 0.138 Plus 20 mg./l. stabilizer II and I each 0.122 Plus 20 g. standard stabilizer (compare Example 2) 0.160
  • Emulsion development Without stabilizer 0.287 Plus 10 mg./l. standard stabilizer (compare Example 2) 0.193 Plus 20 mg./l.- standard stabilizer (comp-are Example 2) 0.168 Plus 10 mg./l. standard stabilizer plus 20 m'g./l.
  • stabilizer II 0.159 Plus 15 mg./l. standard stabilizer plus 20 mg./l. stabilizer II 0.136 Plus 5 mg./l. standard stabilizer plus 40 mg./l.
  • Compound X VII .--2 mercapto 5 (methylaminosulphor1)-benzthiazole is prepared from l-chloro-2-nitro-4- (methylaminosulph-on)-benzene with Na S in water and carbondisulp-hide, as described in Example 10.
  • Compound XX .-t-2-mercapto-su1phonicacid-6,7benz0- benzthiozol is prepared by sulfonating 2n1ercapto-6,7 benzobenzthiazol with 20% oleurn at a temperature of 20. The reaction mixture is poured onto ice and precipitated with a saturated solution of sodium chloride.
  • Compound X XI .--2-rnercapto-su1phonicacid-benzothiazin is prepared as described in Example XX from Z-mercapto-benzothiazin.
  • Compound XXII .2-mercapto-5 -suiphonieacid benzselenazol is prepared from 1-chloro-2-nitro-4-benzenesulphonic acid with potassiumselenide and cyclisation with carbondisulphide, as described in Example X.
  • Compound XXlII.2-mercapto-5 carboxybenzselenazole is prepared as described for Compound XXII from 4-ch1oro-3-nitr0benzoicacid.
  • Z stands for a bivalent atom selected from the group consisting of oxygen, sulfur and selenium and Y stands for the carbon atoms necessary for completing a ring selected from the group consisting of a -membered ring and a 6-membered ring, said rings being fused to an aryl ring selected from the group consisting of benzene and naphthalene, said aryl ring being substituted by a substituent selected from the group consisting of carboxyl, sulfonic acid and sulphonamide.
  • a light-sensitive material having at least one supported silver halide emulsion layer, containing a stabilizing compound of the formula:
  • Z stands for a bivalent atom selected from the group consisting of oxygen, sulfur and selenium and Y stands for the carbon atoms necessary for completing a ring selected from the group consisting of a 5-membered ring and a 6-membered ring, said rings being fused to an aryl ring selected from the group consisting of benzene and naphthalene, said aryl ring being substituted by a substituent selected from the group consisting of carboxyl, sulfonic acid and sulphonamide.
  • An aqueous alkaline developing composition containing a developing amount of a silver halide developer and a stabilizing amount of a stabilizing compound of the formula:
  • Z stands for a bivalent atom selected from the group consisting of oxygen, sulfur and selenium and Y stands for the carbon atoms necessary for completing a ring selected from the group consisting of a 5-membered ring and a 6-membered ring, said rings being fused to an aryl ring selected from the group consisting of benzene and naphthalene, said aryl ring being substituted by a substituent selected from the group consisting of carboxyl, sulfonic acid and sulphonamide.
  • Y stands for the ring members necessary to complete a heterocyclic ring selected from the group consisting of benzoxazole, naphthoxazole, benzthiazole, naphthothiazole, benzselenazole, benzsthiazine and naphthoxazine, said rings being substituted by substituents selected from the group consisting of carboxyl, sulfonic acid and sulfonamide.
  • Y stands for the ring members necessary to complete a heterocyclic ring selected from the group consisting of benzoxazole, naphthoxazole, benzthiazole,
  • Y stands for the ring members necessary to complete a heterocyclic ring selected from the group consisting of benzoxazole, naphthoxazole, benzthiazole, naphthothiazole, benzselenazole, benzthiazine and naphthoxazine, said rings being substituted by substituents selected from the group consisting of carboxyl, sulfonic acid and sulfonamide.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
US260998A 1962-03-08 1963-02-26 Process for developing silver halide and compositions therefor Expired - Lifetime US3305362A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA39654A DE1151731B (de) 1962-03-08 1962-03-08 Verfahren zur Verhinderung der Schleierbildung in Halogensilber-emulsionsschichten

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BE (1) BE629343A (en, 2012)
CH (1) CH446884A (en, 2012)
DE (1) DE1151731B (en, 2012)
GB (1) GB1007020A (en, 2012)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3457078A (en) * 1964-03-11 1969-07-22 Agfa Ag Supersensitized silver halide emulsions
DE2112728A1 (de) * 1970-03-20 1971-09-30 Eastman Kodak Co Photographisches Aufzeichnungsmaterial
US3645738A (en) * 1967-05-18 1972-02-29 Agfa Gevaert Nv Stabilizing silver image in presence of heterocyclic thioxo compound containing sulphogroup
US3655380A (en) * 1970-01-14 1972-04-11 Eastman Kodak Co Diffusion transfer product and process containing 5-seleno-1,2,3,4-tetrazole
US3808005A (en) * 1968-02-22 1974-04-30 Agfa Gevaert Nv Silver halide emulsion stabilized with a bidentate heterocyclic compound containing a sulpho or a carboxyl group
US4021248A (en) * 1974-09-03 1977-05-03 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material
US4245033A (en) * 1974-12-28 1981-01-13 Canon Kabushiki Kaisha Heat developable photosensitive composition and a heat developable photosensitive member having a layer comprising the composition
US4657847A (en) * 1984-08-16 1987-04-14 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
US4683189A (en) * 1985-04-19 1987-07-28 Fuji Photo Film Co., Ltd. Toners for silver halide diffusion transfer image with sulfo or carboxyl groups
EP0234392A3 (en) * 1986-02-22 1989-02-01 Agfa-Gevaert Ag Photographic-recording material and process for making photographic images
US4839263A (en) * 1986-07-31 1989-06-13 Konishiroku Photo Industry Co., Ltd. Method of forming dye image having superior rapid processing performance
EP0189840A3 (en) * 1985-01-25 1989-09-27 Fuji Photo Film Co., Ltd. Silver halide photographic material
EP0317886A3 (en) * 1987-11-24 1990-12-27 Agfa-Gevaert Ag Gradation-variable black and white paper
DE4214196A1 (de) * 1992-04-30 1993-11-04 Agfa Gevaert Ag Farbfotografisches silberhalogenidmaterial
US5919612A (en) * 1996-01-26 1999-07-06 Agfa-Gevaert Ag Color photographic silver halide material
US20040124149A1 (en) * 2002-09-13 2004-07-01 Ciphergen Biosystems, Inc. Preparation and use of mixed mode solid substrates for chromatography adsorbents and biochip arrays

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3605713A1 (de) * 1986-02-22 1987-08-27 Agfa Gevaert Ag Farbfotografisches aufzeichnungsmaterial
EP0754971A1 (en) 1995-07-18 1997-01-22 Agfa-Gevaert N.V. Material for industrial radiography and development method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2453346A (en) * 1945-10-25 1948-11-09 Eastman Kodak Co Stabilization of processed photographic emulsions to high temperatures and humidities
US2657136A (en) * 1951-03-30 1953-10-27 Eastman Kodak Co Photographic antiplumming agents and compositions containing them
US3113026A (en) * 1959-01-19 1963-12-03 Gen Aniline & Film Corp Polyvinyl alcohol photographic silver halide emulsions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2453346A (en) * 1945-10-25 1948-11-09 Eastman Kodak Co Stabilization of processed photographic emulsions to high temperatures and humidities
US2657136A (en) * 1951-03-30 1953-10-27 Eastman Kodak Co Photographic antiplumming agents and compositions containing them
US3113026A (en) * 1959-01-19 1963-12-03 Gen Aniline & Film Corp Polyvinyl alcohol photographic silver halide emulsions

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3457078A (en) * 1964-03-11 1969-07-22 Agfa Ag Supersensitized silver halide emulsions
US3645738A (en) * 1967-05-18 1972-02-29 Agfa Gevaert Nv Stabilizing silver image in presence of heterocyclic thioxo compound containing sulphogroup
US3808005A (en) * 1968-02-22 1974-04-30 Agfa Gevaert Nv Silver halide emulsion stabilized with a bidentate heterocyclic compound containing a sulpho or a carboxyl group
US3655380A (en) * 1970-01-14 1972-04-11 Eastman Kodak Co Diffusion transfer product and process containing 5-seleno-1,2,3,4-tetrazole
DE2112728A1 (de) * 1970-03-20 1971-09-30 Eastman Kodak Co Photographisches Aufzeichnungsmaterial
US4021248A (en) * 1974-09-03 1977-05-03 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material
US4245033A (en) * 1974-12-28 1981-01-13 Canon Kabushiki Kaisha Heat developable photosensitive composition and a heat developable photosensitive member having a layer comprising the composition
US4657847A (en) * 1984-08-16 1987-04-14 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
EP0175148A3 (en) * 1984-08-16 1988-10-05 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
EP0189840A3 (en) * 1985-01-25 1989-09-27 Fuji Photo Film Co., Ltd. Silver halide photographic material
US4683189A (en) * 1985-04-19 1987-07-28 Fuji Photo Film Co., Ltd. Toners for silver halide diffusion transfer image with sulfo or carboxyl groups
EP0234392A3 (en) * 1986-02-22 1989-02-01 Agfa-Gevaert Ag Photographic-recording material and process for making photographic images
US4839263A (en) * 1986-07-31 1989-06-13 Konishiroku Photo Industry Co., Ltd. Method of forming dye image having superior rapid processing performance
EP0317886A3 (en) * 1987-11-24 1990-12-27 Agfa-Gevaert Ag Gradation-variable black and white paper
JP2622407B2 (ja) 1987-11-24 1997-06-18 アグフア―ゲヴエルト・アクチエンゲゼルシヤフト 階調可変黒白紙
DE4214196A1 (de) * 1992-04-30 1993-11-04 Agfa Gevaert Ag Farbfotografisches silberhalogenidmaterial
US5385813A (en) * 1992-04-30 1995-01-31 Agfa-Gevaert Ag Color photographic silver halide material
DE4214196C2 (de) * 1992-04-30 2003-08-28 Agfa Gevaert Ag Farbfotografisches Silberhalogenidmaterial
US5919612A (en) * 1996-01-26 1999-07-06 Agfa-Gevaert Ag Color photographic silver halide material
US20040124149A1 (en) * 2002-09-13 2004-07-01 Ciphergen Biosystems, Inc. Preparation and use of mixed mode solid substrates for chromatography adsorbents and biochip arrays
US7144743B2 (en) * 2002-09-13 2006-12-05 Pall Corporation Preparation and use of mixed mode solid substrates for chromatography adsorbents and biochip arrays
US20070015143A1 (en) * 2002-09-13 2007-01-18 Pall Corporation Preparation and use of mixed mode solid substrates for chromatography adsorbents and biochip arrays
US7326776B2 (en) 2002-09-13 2008-02-05 Pall Corporation Preparation and use of mixed mode solid substrates for chromatography adsorbents and biochip arrays

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CH446884A (de) 1967-11-15
BE629343A (en, 2012)
DE1151731B (de) 1963-07-18
GB1007020A (en) 1965-10-13

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