US3704130A - Photographic fine grain silver halide emulsions - Google Patents

Photographic fine grain silver halide emulsions Download PDF

Info

Publication number
US3704130A
US3704130A US77695A US3704130DA US3704130A US 3704130 A US3704130 A US 3704130A US 77695 A US77695 A US 77695A US 3704130D A US3704130D A US 3704130DA US 3704130 A US3704130 A US 3704130A
Authority
US
United States
Prior art keywords
silver halide
alkylene
emulsions
silver
photographic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US77695A
Other languages
English (en)
Inventor
Robert Joseph Pollet
Herman Adelbert Philippaerts
Jozef Frans Willems
Frans Henri Claes
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
Original Assignee
Agfa Gevaert NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
Application granted granted Critical
Publication of US3704130A publication Critical patent/US3704130A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • 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
    • 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
    • G03C1/07—Substances influencing grain growth during silver salt formation
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances

Definitions

  • the average silver halide grain size can be reduced to less than 50 nm.
  • the emulsions show a high diffraction efiiciency and a high signal to noise ratio.
  • the present invention relates to the preparation of lightsensitive silver halide emulsions; more particularly to the preparation of fine-grain silver halide emulsions of the Lippmann type; to the fine-grain silver halide emulsions prepared according to this method, and to photographic elements having at least one layer of the aforesaid finegrain silver halide emulsion.
  • Lippmann-emulsions normally having an average grainsize of about 50100 nm., are of particular importance for the preparation of photographic plates or films with high resolution; for use in microphotography and in astrophotography; for recording nucleo-physical phenomenons; for the preparation of masks in the production of microelectronic integrated circuits; for use in holography, etc.
  • Lippman-emulsions with an average grain size smaller than usual i.e. smaller than 50 nm. by varying the working conditions during the precipitation of the silver halide, have not been successful and therefore, it has been tried to use compounds restraining the growth of the silver halide crystals during precipitation.
  • silver halide emulsions with very fine grain can be prepared by efiecting the precipitation of the silver halide in an aqueous hydrophilic colloid medium in the presence of compounds corresponding to the following general formula:
  • the compounds corresponding to the above general formula are bidentate ligands which form complexes or salts with silver, thus restraining growth of the silver halide crystals so that very fine silver halide grains are formed.
  • homogeneous Lippmann-emulsions can be prepared with an average grain size markedly smaller than in the absence of said compounds so that emulsions are obtained practically without scattering.
  • the compounds or solutions of these compounds of use according to the present invention are generally added into the aqueous hydrophilic colloid composition, more particularly aqueous gelatin, into which the silver halide is precipitated. They can be used in amounts varying between very wide limits, preferably between 2 g. and 20 g. per mole of silver halide.
  • the ratio of hydrophilic colloid binder to silver halide in the fine-grain emulsions according to the present invention is preferably comprised between 0.2 and 6.0.
  • the hydrophilic colloid used as the vehicle for the silver halide may be any of the common hydrophilic colloids employed in photographic light-sensitive emulsions, for example gelatin, albumin, zein, casein, algininc acid, collodion, a cellulose derivative such as carboxymethyl cellulose, a synthetic hydrophilic colloid such as polyvinyl alcohol and poly-N-vinyl pyrrolidone, etc. gelatin being however preferred. If desired compatible mixtures of two or more colloids may be employed for dispersing the silver halide.
  • Various silver salts may be used as the light-sensitive salt such as silver bromide, silver chloride or mixed silver halides such as silver chlorobrmide, silver bromoiodide and silver chlorobromoiodide.
  • Emulsions containing silver bromide or silver chloride or a mixture of silver chloride and silver bromide and such emulsions containing small amount of silver iodide up to 8% are favoured.
  • the emulsion After precipitation of the silver halide grains in the presesce of the compounds of use according to the present invention the emulsion is washed in order to remove the water-soluble salts whereupon the emulsions may be chemically as well as spectrally sensitized.
  • emulsions according to the invention may also comprise compounds which sensitize the emulsion by development acceleration for example quaternary ammonium compounds and compounds of the polyoxyalkylene type.
  • the emulsions may comprise antifoggants and stabilizers for example heterocyclic nitrogen-containing thioxo compounds such as benzothiazoline-Z-thione and 1- phenyl2-tetrazoline-5-thione, compounds of the hydroxytriazolopyrimidine type such as 5-methyl-7-hydroxy-striazolo[1,5-a1pyrimidine and mercury compounds.
  • antifoggants and stabilizers for example heterocyclic nitrogen-containing thioxo compounds such as benzothiazoline-Z-thione and 1- phenyl2-tetrazoline-5-thione, compounds of the hydroxytriazolopyrimidine type such as 5-methyl-7-hydroxy-striazolo[1,5-a1pyrimidine and mercury compounds.
  • any of the hardening agents for hydrophilic colloids may be used in the emulsions according to the present invention for example formaldehyde, dialdehydes, diketones, halogen substituted aldehyde acids such as mucochloric acid and mucobromic acid, etc.
  • the emulsions may be coated on a wide variety of 1958, Fountain Press, London. i photographic emulsion supports. Typical supports include Um'ier completely analogous wofkmg Condlfions other cellulose ester film, polyvinyl acetal film, polystyrene fil emulsions were prepared wlth the d fference that the IQ% Polyethylene terephthalate fil and l d fil f i aqueous solution of gelatin into WhlCh the silver bromlde ous m t rial a ell as paper nd l 10 was precipitated now contained one of the compounds
  • the following example illustrates the present invention. listed in the table below in an amount of P 111016 of silver nitrate used.
  • EXAMPLE The average silver bromide grain size was determined A silver bromide emulsion comprising 25 g. of silver by turbimetry. bromide and 65 g. of gelatin was prepared by simultaneous 15 The results attained are listed in the table below and addition of an aqueous silver nitrate solution and an show that the compounds corresponding to the above aqueous potassium bromide solution to a 10% aqueous general formula restrain growth of the silver halide grains.
  • Nona 67 l N C I 46.5 HOaS-(CHzh-S-T Ts-wum-soazr 1' N--- OHz-CHz- -N 1 (I:H3 1 HaCC-CHr-(
  • Preparation 3 Compound 3 To a solution of 11.4 g. of 1,2-bis(5-mercapto-1H-1,2,- 4-triazol-3-yl) ethane and 12 g. of sodium methylate in 150 ml. of methanol, g. of 1,1,3-trimethylpropanesultone were added. The mixture was refluxed for 3 hours and filtered over decolourizing carbon. The filtrate was concentrated by evaporation and the residue dissolved in ethanol. The product was precipitated by means of acetone.
  • Preparation 6zcompound 6 24.6 g. (0.2 mole) of a-picolinic acid and 21.6 g. (0.2 mole) of o-phenylenediamine were heated to 250 C. in 20 minutes and kept at this temperature for 20 minutes, the water formed being removed by distillation. The residue was dissolved by heating in m1. of hydrochloric acid 5 N whereupon it was precipitated again by means of ammonium hydroxide. The precipitate was filtered by suction and recrystallised from a mixture of 200 ml. of ethanol and 100 ml. of water.
  • Preparation 7 compound 7 To a solution of 27.5 g. (0.1 mole) of the disodium salt of 2-mercapto-5(6) sulphobenzimidazole in 200 ml. of dimethylformamide 8.7 g. (0.05 mole) of dibromomethane were added dropwise with stirring at room-temperature. The solution was heated for 3 hours at 100 C. whereupon it was concentrated by evaporation and the residue recrystallized from a mixture of 300 ml. ethanol and 40 ml. of water.
  • Preparation 8zcompound 8 43 g. (0.4 mole) of o-phenylenediamine and 33.5 g. (0.2 mole) of 2,6-pyridinedicarboxylic acid were heated in 40 g. of polyphosphoric acid for 6 hours at C. After having been cooled the reaction mixture was poured into 400 ml. of water and the precipitate formed was filtered by suction and washed till neutral. The product was recrystallized from a mixture of water and ethanol.
  • Method of preparing a photographic fine-grain silver halide emulsion which comprises the step of precipitating the silver halide in an aqueous hydrophilic colloid medium in the presence of a compound corresponding to the following general formula:
  • each of Z and X stands for imidazole, benzoimidazole, naphthoimidazole, pyridine, quinoline, pyrazole, tetrazole, triazole, thiazole, or benzothiazole.
  • the emulsion is a silver bromide, silver chloride or a silver chloro- 8 bromide emulsion which may comprise a minor amount of silver iodide.
  • a photographic fine-grain silver halide emulsion wherein said emulsion is prepared by precipitating the silver halide in an aqueous hydrophilic colloid medium in the presence of a compound corresponding to the following general formula:
  • Photographic material according to claim 5 wherein Z and X stand for imidazole, benzoimidazole, naphthoimidazole, pyridine, quinoline, pyrazole, tetrazole, triazole, thiazole, or benzothiazole.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
US77695A 1969-10-29 1970-10-02 Photographic fine grain silver halide emulsions Expired - Lifetime US3704130A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB5302569 1969-10-29

Publications (1)

Publication Number Publication Date
US3704130A true US3704130A (en) 1972-11-28

Family

ID=10466324

Family Applications (1)

Application Number Title Priority Date Filing Date
US77695A Expired - Lifetime US3704130A (en) 1969-10-29 1970-10-02 Photographic fine grain silver halide emulsions

Country Status (7)

Country Link
US (1) US3704130A (en, 2012)
JP (1) JPS4946928B1 (en, 2012)
BE (1) BE758103A (en, 2012)
CH (1) CH564790A5 (en, 2012)
DE (1) DE2053023C3 (en, 2012)
FR (1) FR2066207A5 (en, 2012)
GB (1) GB1320138A (en, 2012)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3847617A (en) * 1971-12-09 1974-11-12 Agfa Gevaert Process of preparing fine-grain silverhalide emulsions
US4298683A (en) * 1977-12-29 1981-11-03 Agfa-Gevaert Aktiengesellschaft Light-sensitive photographic material
US4379837A (en) * 1980-05-23 1983-04-12 Agfa-Gevaert Aktiengesellschaft Process for the preparation of silver halide emulsions, photographic materials, and a process for the production of photographic images
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
WO1986004694A1 (en) 1985-02-06 1986-08-14 Fuji Photo Film Co., Ltd. Silver halide photographic photo-sensitive material
EP0239363A2 (en) 1986-03-25 1987-09-30 Konica Corporation Light-sensitive silver halide photographic material feasible for high speed processing
EP0313051A1 (en) 1987-10-20 1989-04-26 Fuji Photo Film Co., Ltd. Silver halide photographic material
US4871658A (en) * 1986-01-24 1989-10-03 Konishiroku Photo Industry Co., Ltd. Silver halide photographic material that is resistant to fogging during storage
US5196300A (en) * 1989-12-05 1993-03-23 Fuji Photo Film Co., Ltd. Method for making silver halide emulsion, photosensitive materials using the same, and methods of recording images using the photosensitive materials
EP0562476A1 (en) 1992-03-19 1993-09-29 Fuji Photo Film Co., Ltd. A silver halide photographic emulsion and a photographic light-sensitive material
EP0563708A1 (en) 1992-03-19 1993-10-06 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion and light-sensitive material using the same
US5318887A (en) * 1991-06-06 1994-06-07 Konica Corporation Method for production of silver halide emulsion, and silver halide photographic light-sensitive material
US5409809A (en) * 1992-10-01 1995-04-25 E. I. Du Pont De Nemours And Company Silver halide emulsions stabilized with improved antifoggants
WO1996013755A1 (en) 1994-10-26 1996-05-09 Eastman Kodak Company Photographic emulsions of enhanced sensitivity
EP0777153A1 (en) 1995-11-30 1997-06-04 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US5962493A (en) * 1994-02-04 1999-10-05 Fuji Photo Film Co., Ltd. 2-mercaptobenzimidazole derivatives and antihyperlipemic agent or antiarteriosclerotic agent containing the same
US6143484A (en) * 1999-05-06 2000-11-07 Eastman Kodak Company Method for stabilizing photographic dispersions in melts containing fine grain silver halide
US6780576B1 (en) * 2003-06-06 2004-08-24 Agfa-Gevaert Surfactants
US20050053871A1 (en) * 2003-06-06 2005-03-10 Agfa-Gevaert N.V. Novel surfactants for use in substantially light-insensitive thermographic recording materials
US10073416B2 (en) * 2015-04-24 2018-09-11 Lg Display Co., Ltd. Method for producing a holographic optical element

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58160948A (ja) * 1982-03-18 1983-09-24 Konishiroku Photo Ind Co Ltd リツプマン型ハロゲン化銀写真感光材料
JPS58189628A (ja) * 1982-04-28 1983-11-05 Konishiroku Photo Ind Co Ltd 熱現像画像記録材料
JPS58193541A (ja) * 1982-05-07 1983-11-11 Konishiroku Photo Ind Co Ltd 熱現像画像記録材料
WO2005100340A2 (en) * 2004-04-13 2005-10-27 Icagen, Inc. Polycyclic pyridines as potassium ion channel modulators

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3847617A (en) * 1971-12-09 1974-11-12 Agfa Gevaert Process of preparing fine-grain silverhalide emulsions
US4298683A (en) * 1977-12-29 1981-11-03 Agfa-Gevaert Aktiengesellschaft Light-sensitive photographic material
US4379837A (en) * 1980-05-23 1983-04-12 Agfa-Gevaert Aktiengesellschaft Process for the preparation of silver halide emulsions, photographic materials, and a process for the production of photographic images
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
WO1986004694A1 (en) 1985-02-06 1986-08-14 Fuji Photo Film Co., Ltd. Silver halide photographic photo-sensitive material
US4871658A (en) * 1986-01-24 1989-10-03 Konishiroku Photo Industry Co., Ltd. Silver halide photographic material that is resistant to fogging during storage
EP0239363A2 (en) 1986-03-25 1987-09-30 Konica Corporation Light-sensitive silver halide photographic material feasible for high speed processing
EP0313051A1 (en) 1987-10-20 1989-04-26 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5196300A (en) * 1989-12-05 1993-03-23 Fuji Photo Film Co., Ltd. Method for making silver halide emulsion, photosensitive materials using the same, and methods of recording images using the photosensitive materials
US5318887A (en) * 1991-06-06 1994-06-07 Konica Corporation Method for production of silver halide emulsion, and silver halide photographic light-sensitive material
EP0562476A1 (en) 1992-03-19 1993-09-29 Fuji Photo Film Co., Ltd. A silver halide photographic emulsion and a photographic light-sensitive material
EP0563708A1 (en) 1992-03-19 1993-10-06 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion and light-sensitive material using the same
US5409809A (en) * 1992-10-01 1995-04-25 E. I. Du Pont De Nemours And Company Silver halide emulsions stabilized with improved antifoggants
US5962493A (en) * 1994-02-04 1999-10-05 Fuji Photo Film Co., Ltd. 2-mercaptobenzimidazole derivatives and antihyperlipemic agent or antiarteriosclerotic agent containing the same
WO1996013755A1 (en) 1994-10-26 1996-05-09 Eastman Kodak Company Photographic emulsions of enhanced sensitivity
EP0777153A1 (en) 1995-11-30 1997-06-04 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US6143484A (en) * 1999-05-06 2000-11-07 Eastman Kodak Company Method for stabilizing photographic dispersions in melts containing fine grain silver halide
US6780576B1 (en) * 2003-06-06 2004-08-24 Agfa-Gevaert Surfactants
US20040249166A1 (en) * 2003-06-06 2004-12-09 Agfa-Gevaert Novel surfactants
US20050053871A1 (en) * 2003-06-06 2005-03-10 Agfa-Gevaert N.V. Novel surfactants for use in substantially light-insensitive thermographic recording materials
US7015332B2 (en) 2003-06-06 2006-03-21 Agfa Gevaert 2-thioalkyl-benzimidazole-5 or 6 sulphonic acids
US7040929B2 (en) 2003-06-06 2006-05-09 Agfa-Gevaert Surfactants for use in substantially light-insensitive thermographic recording materials
US10073416B2 (en) * 2015-04-24 2018-09-11 Lg Display Co., Ltd. Method for producing a holographic optical element
US10921751B2 (en) 2015-04-24 2021-02-16 Lg Display Co., Ltd. Method for producing a holographic optical element

Also Published As

Publication number Publication date
JPS4946928B1 (en, 2012) 1974-12-12
FR2066207A5 (en, 2012) 1971-08-06
DE2053023C3 (de) 1979-08-23
BE758103A (nl) 1971-04-28
DE2053023B2 (en, 2012) 1978-12-14
CH564790A5 (en, 2012) 1975-07-31
GB1320138A (en) 1973-06-13
DE2053023A1 (de) 1971-05-06

Similar Documents

Publication Publication Date Title
US3704130A (en) Photographic fine grain silver halide emulsions
JP3323525B2 (ja) 写真ハロゲン化銀乳剤及び金（ｉ）化合物
US2819965A (en) Carboxymethylmercapto compounds as stabilizers for photographic emulsions
US5229248A (en) Silver halide photographic light sensitive material
US3137578A (en) Photographic emulsions containing 2-heterocyclic benzimidazole antifoggants
JP2638347B2 (ja) アリールヒドラジドを含有する写真用ハロゲン化銀材料
US4420554A (en) Silver halide photosensitive materials
US3909268A (en) Tetrazolium C-oxy-betaine compounds as antifog agents for silver halide photographic emulsions
US3765901A (en) Spectral sensitization of light-sensitive silver halide emulsions
US3661592A (en) Photographic fine grain silver halide materials
US4920043A (en) Method for processing silver halide photographic light-sensitive material
US3765900A (en) Spectrally sensitized silver halide emulsions
JPS63314534A (ja) 写真ハロゲン化銀乳剤
JPS63172266A (ja) ハロゲン化銀写真乳剤
US2944900A (en) Sensitization of photographic emulsions with ionic polyalkyene oxide salts
US4281059A (en) Photographic material
GB2059613A (en) Photographic silver halide emulsion material containing an anti-foggant precursor
US3705038A (en) Spectral sensitization of silver halide lippmann emulsions
US3869290A (en) Photographic silver halide elements of the Lippmann-type
US3847617A (en) Process of preparing fine-grain silverhalide emulsions
US3656958A (en) Silver halide emulsions containing carboxy-alkyl thiazole or selenazole rhodanine merocyanine sensitizing dyes
US3825426A (en) Development of exposed photographic silver halide elements
US5219724A (en) Method for producing a silver halide photographic light-sensitive material
JPH0225494B2 (en, 2012)
US3752673A (en) Silver halide emulsion containing a merocyanine dye