EP0689091A1 - Procédé de préparation d'une émulsion photographique à l'halogénure d'argent sensibilisée en présence de dérivés d'hydroguinone - Google Patents
Procédé de préparation d'une émulsion photographique à l'halogénure d'argent sensibilisée en présence de dérivés d'hydroguinone Download PDFInfo
- Publication number
- EP0689091A1 EP0689091A1 EP95420137A EP95420137A EP0689091A1 EP 0689091 A1 EP0689091 A1 EP 0689091A1 EP 95420137 A EP95420137 A EP 95420137A EP 95420137 A EP95420137 A EP 95420137A EP 0689091 A1 EP0689091 A1 EP 0689091A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- emulsion
- silver halide
- hydroquinone derivative
- hydroquinone
- mol
- 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.)
- Withdrawn
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 80
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 37
- 239000004332 silver Substances 0.000 title claims abstract description 37
- -1 silver halide Chemical class 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005864 Sulphur Substances 0.000 claims abstract description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052737 gold Inorganic materials 0.000 claims abstract description 9
- 239000010931 gold Substances 0.000 claims abstract description 9
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 9
- 239000011669 selenium Substances 0.000 claims abstract description 9
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 claims description 30
- 239000000975 dye Substances 0.000 claims description 17
- 231100000489 sensitizer Toxicity 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 230000003595 spectral effect Effects 0.000 claims description 9
- CLDZVCMRASJQFO-UHFFFAOYSA-N 2,5-bis(2,4,4-trimethylpentan-2-yl)benzene-1,4-diol Chemical compound CC(C)(C)CC(C)(C)C1=CC(O)=C(C(C)(C)CC(C)(C)C)C=C1O CLDZVCMRASJQFO-UHFFFAOYSA-N 0.000 claims description 5
- CEZVGLHZVYEJBR-UHFFFAOYSA-N 2,5-didodecylbenzene-1,4-diol Chemical compound CCCCCCCCCCCCC1=CC(O)=C(CCCCCCCCCCCC)C=C1O CEZVGLHZVYEJBR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 20
- 230000001603 reducing effect Effects 0.000 abstract description 6
- 108010010803 Gelatin Proteins 0.000 description 12
- 239000008273 gelatin Substances 0.000 description 12
- 229920000159 gelatin Polymers 0.000 description 12
- 235000019322 gelatine Nutrition 0.000 description 12
- 235000011852 gelatine desserts Nutrition 0.000 description 12
- 206010070834 Sensitisation Diseases 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- IJHIIHORMWQZRQ-UHFFFAOYSA-N 1-(ethenylsulfonylmethylsulfonyl)ethene Chemical compound C=CS(=O)(=O)CS(=O)(=O)C=C IJHIIHORMWQZRQ-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- SGYIRNXZLWJMCR-UHFFFAOYSA-M 3-methyl-1,3-benzothiazol-3-ium;iodide Chemical compound [I-].C1=CC=C2[N+](C)=CSC2=C1 SGYIRNXZLWJMCR-UHFFFAOYSA-M 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000206672 Gelidium Species 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000004133 Sodium thiosulphate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229920002494 Zein Polymers 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- PGWMQVQLSMAHHO-UHFFFAOYSA-N sulfanylidenesilver Chemical compound [Ag]=S PGWMQVQLSMAHHO-UHFFFAOYSA-N 0.000 description 1
- BZWKPZBXAMTXNQ-UHFFFAOYSA-N sulfurocyanidic acid Chemical compound OS(=O)(=O)C#N BZWKPZBXAMTXNQ-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940071240 tetrachloroaurate Drugs 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
- 239000005019 zein Substances 0.000 description 1
- 229940093612 zein Drugs 0.000 description 1
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
- G03C1/10—Organic substances
-
- 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
- G03C1/015—Apparatus or processes for the preparation of emulsions
-
- 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
-
- 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
- G03C2001/091—Gold
-
- 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
- G03C2001/097—Selenium
-
- 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
- G03C2200/00—Details
- G03C2200/44—Details pH value
Definitions
- the present invention concerns a silver halide photographic emulsion, and particularly a silver halide emulsion sensitised by means of a novel combination of sensitising compounds, and the process for obtaining such an emulsion.
- the sensitisation of the emulsions is limited by the quantity of sensitising compounds which can be added to the emulsion without causing a significant increase in fogging.
- Hydroquinone and derivatives of hydroquinone are known for their silver halide reducing properties. They are usually used in photographic processing as photographic product developing substances. Derivatives of particular interest for this type of application are described in Chimie et Physique Photographiques, Glafkides, page 154, and in a large number of patents such as US patent 4 377 634.
- Hydroquinone derivatives can also be incorporated into a photographic product.
- US patent 4 614 707 describes a colour reversible photographic product which comprises several layers of silver halide emulsion, each of these layers containing a dye-forming coupler. These photosensitive layers are separated by intermediate layers comprising silver halides which do not participate in the formation of the image, and at least one of these intermediate layers contains a hydroquinone derivative substituted by a sulpho, carboxyl, sulphoalkyl or carboxyalkyl group.
- European patent 209 010 describes a high-contrast negative photographic product obtained using a monodisperse emulsion consisting of silver halide grains with a size of less than 0.7 ⁇ m and which are such that the latent image forms on the surface of these grains.
- This emulsion also comprises an arylhydrazide contrast amplifier and a quantity of a hydroquinone derivative for reducing sensitivity to pressure.
- US patent 3 192 146 describes a silver halide photographic emulsion sensitised by a novel combination of chemical sensitisers which comprises a thioether and a hydroquinone derivative associated with a compound capable of salting out or forming bisulphite ions. Such a combination enables the sensitivity of a silver halide photographic emulsion to be increased.
- the object of the present invention is to increase the sensitivity of a silver halide emulsion without changing the fogging level, by associating a conventional chemical sensitisation using sulphur, gold or selenium with a sensitisation by reduction by means of a polyhydroxybenzene under particular pH conditions.
- the present invention resolves the problem related to the increase in fogging level when sensitisation by reduction is used.
- the present invention concerns a silver halide photographic emulsion chemically sensitised by means of a sensitiser chosen from among sulphur, gold and selenium and at least one reduction sensitiser characterized in that the reduction sensitiser is a polyhydroxybenzene, and in that the pH of the emulsion after the addition of the different chemical sensitisers is between 7 and 10.
- a sensitiser chosen from among sulphur, gold and selenium
- at least one reduction sensitiser characterized in that the reduction sensitiser is a polyhydroxybenzene, and in that the pH of the emulsion after the addition of the different chemical sensitisers is between 7 and 10.
- the polyhydroxybenzene according to the present invention is preferably a hydroquinone derivative.
- hydroquinone derivatives are, for example, 2-(2'-octodecyl)-5-sulphohydroquinone, 2,5-didodecylhydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone or a salt of these compounds. These hydroquinone derivatives can be used alone or in combination.
- the quantities of hydroquinone derivatives may be between 0.05 and 1 mmole per mole of silver, and preferably between approximately 0.1 and 0.6 mmole per mole of silver.
- the hydroquinone derivative is 2-(2'-octodecyl)-5-sulphohydroquinone and the pH of the emulsion is between 7 and 9 and preferably 8 and 9.
- the compounds of sulphur and/or gold and/or selenium which are used for chemically sensitising the emulsion of the invention are conventional compounds such as thiosulphates, thioureas, aurous sulphocyanide, aurothiocyanates, selenoureas, etc. These compounds were described, for example, in Research Disclosure No 308119, December 1989, Section III.
- the quantities of chemical sensitisers containing sulphur, gold or selenium added to the emulsion are determined experimentally in order to obtain an optimally sensitised emulsion.
- the process for preparing such emulsions is comprised of precipitating silver halide grains in a colloid using a solution of silver nitrate and one or more halide salts, and then adding one or more spectral sensitising dyes in order to sensitise the emulsion by one or more chemical sensitising compounds containing sulphur and/or gold and/or selenium and at least one polyhydroxybenzene such as, for example, a hydroquinone derivative.
- the pH of the emulsion is adjusted to a value lying between 7 and 10.
- the spectral sensitising dye or dyes, the chemical sensitising dye or dyes containing sulphur and/or gold and/or selenium and the hydroquinone derivative or derivatives are added to the emulsion in that order.
- the pH is then adjusted by adding a strong base, for example sodium hydroxide.
- the temperature of the sensitised emulsion is raised to between 30 and 90°C and preferably above 50°C, in order to obtain a better adsorption of the different sensitisers.
- a level stage is maintained at a temperature of around 60°C.
- the photographic emulsion may consist of one or more silver halides chosen from amongst silver chloride, bromide and iodide.
- the silver halide grains may have different morphologies, for example tabular, octahedral (faces 111), cubo-octahedral or cubic (faces 100).
- the silver halide emulsion may be spectrally sensitised with conventional spectral sensitising dyes as described for example in Research Disclosure, December 1989, No 308119, Section IV (hereinafter referred to as Research Disclosure).
- These dyes are, for example, cyanine, merocyanine or hemioxodol dyes.
- the quantity of each of the spectral sensitisers differs greatly according to the conditions of use, the quantity of spectral sensitisers is preferably between 0 and 1.4 mmole per mole of silver.
- the emulsions of the present invention may be used in black and white or colour photographic products of different types, such as negative, positive or reversal photographic products.
- these photographic products are colour photographic products, they comprise, in a conventional manner, at least three components which are respective blue, green and red sensitive, providing respectively the yellow, magenta and cyan components of the subtractive synthesis of the colour image.
- Colour photographic products generally comprise a support carrying at least one layer of blue-sensitive silver halide emulsion with which a yellow dye forming coupler is associated, at least one layer of green-sensitive silver halide emulsion with which a magenta dye forming coupler is associated, and at least one red-sensitive silver halide emulsion with which a cyan dye forming coupler is associated.
- the support may be any suitable support used in photographic products.
- Conventional supports comprise polymer films, paper (including polymer-coated paper), glass and metal. Research Disclosure, Section XVII, provides details about supports and ancillary layers in photographic products.
- the silver halide emulsions of the invention, and other layers on the photographic products of this invention may contain, as a carrier, hydrophilic colloids, used alone or in combination with other polymer substances (for example latexes).
- Suitable hydrophilic substances comprise natural substances such as proteins, protein derivatives, cellulose derivatives (for example cellulose esters), gelatin (for example gelatin such as cattle bone or tanned gelatin treated by means of a base or gelatin such as pigskin gelatin treated with an acid), gelatin derivatives (for example acetylated gelatin, phthalylated gelatin, etc), polysaccharides such as dextran, gum arabic, zein, casein, pectin, collagen derivatives, collodion, agar-agar and albumin.
- Surfactants can be incorporated in a layer of photographic emulsion or in another hydrophilic colloidal layer of the photographic product as a coating adjuvant, for example in order to prevent the accumulation of static charges, to improve lubrication properties, to improve the dispersion of the emulsion, to prevent adhesion, and/or to improve the sensitometric properties such as an increase in contrast or the sensitisation or acceleration of development.
- the photographic emulsion of the present invention may contain dye image forming couplers, that is to say compounds capable of reacting with an aromatic amine oxidation product (generally a primary amine) to form a dye.
- dye image forming couplers that is to say compounds capable of reacting with an aromatic amine oxidation product (generally a primary amine) to form a dye.
- Non-diffusible couplers containing a ballast group are desirable. It is possible to use either couplers with four equivalents or couplers with two equivalents.
- couplers enabling the colours to be corrected, or couplers releasing a development inhibiter during development referred to as DIR couplers).
- the photographic products of the invention may contain, amongst other things, optical brighteners, anti-fogging compounds, tanning agents, stabilising agents or absorption and/or diffusion agents as described in Sections V, VI, VIII, XI, XII and XVI of the above-mentioned Research Disclosure.
- the products of the invention after being exposed, undergo photographic processing for developing the silver latent image and a colour image, in the presence of a coupler, which, in certain cases, may be incorporated in the photographic product.
- Development takes place by means of a reducing compound which, by oxydo-reduction reaction, transforms the exposed silver halide grains into metallic silver grains.
- the oxidised form of the reducing compound then reacts with the coupler to form a dye.
- reducing compounds are chosen from amongst the aromatic primary amines such as paraphenylene diamines, aminophenols, etc. These compounds may be used alone or in a mixture, or with ancillary developers.
- This bath may, in addition, contain a stabiliser such as sulphites, a buffer such as carbonates, boric acid, borates or alkanolamines.
- an AgBr tabular grain emulsion was prepared as follows:
- a step consisting of the nucleation of the grains was carried out at 45°C and with a pH of 1.8 and pAg of 9, by introducing, over 15 seconds by the double-jet method, a 0.6 M solution of AgNO3 and a 0.6 M solution of NaBr.
- the emulsion was then cooled to 40°C. After washing of the emulsion, the pH was adjusted to 6.0 and the pAg to 8.
- a pure tabular grain bromide emulsion was obtained, having an equivalent circular diameter of 2.0 ⁇ m and a thickness of 0.11 ⁇ m.
- the emulsion thus obtained was separated into four equal parts and each of the parts was treated in accordance with Table 1.
- the hydroquinone derivative used in this example was the sodium salt of [2-(2'-octadecyl)-5-sulphohydroquinone (D8N).
- the temperature was increased to 65°C. This temperature was maintained for 15 min, and then the emulsions were cooled to 40°C.
- the emulsions obtained were coated on a cellulose triacetate support with a silver content of 0.807 g/m2, a gelatin content of 3.23 g/m2 and a coupler (C1) in a proportion of 1.05 g/m2. This layer of emulsion was covered with a top coating of gelatin (2.15 g/m2).
- the layer of emulsion was hardened using 1.75% bis(vinylsulphonyl)methane by weight of total gelatin.
- the samples thus obtained were exposed by means of a Kodak® sensitometer fitted with a lamp with a colour temperature of 5500°K for 1/100 seconds.
- the sensitometer was fitted with a "Wratten 9®” filter which transmits light of a wavelength shorter than 460 nm.
- Sensitivity 100(1-log E) where E represents the photographic exposure measured at the point of intersection between the tangent at maximum contrast and a straight line passing through the maximum density.
- the minimum density (Dmin) is equal to the optical density of the support and of the fogging obtained without exposure. Although the value of the minimum density varies according to the use of the photographic product, it must in every case be less than or equal to 0.2.
- Examples 1A to 1E show that, when the pH of the emulsion is increased, an increase in sensitivity is observed which is inevitably accompanied by a not insignificant increase in the fogging level.
- Example 1-C and the examples of the invention 1-I, 1-II, 1-V and 1-VI are compared, it is seen that the addition of the hydroquinone derivative results in an increase in sensitivity compared with Examples 1-A to 1-E and a fogging level which remains lower than that obtained in Example 1-D, where the highest sensitivity was obtained.
- Examples 1-III and 1-IV show that, for a pH of around 8.5, when the quantity of hydroquinone derivative is greater than or equal to 0.32 mmol/mol Ag, the increase in sensitivity of the emulsion is accompanied by an increase in the fogging level greater than that of Example 1-D but which remains acceptable.
- the comparative examples 1-VII and 1-VIII show that, for a pH of 10.5, the advantages of the present invention are no longer observed.
- the emulsion was treated as described in Example 1 except that the hydroquinone derivative was 2.5-didodecylhydroquinone (IDH).
- IDH 2.5-didodecylhydroquinone
- Example 2-I to 2-V the increase in sensitivity compared with the reference examples (without hydroquinone derivative) and a fogging level which always remains lower than that of Example 2-D, where the highest sensitivity was obtained, are observed as before.
- Example 2-VI shows that, when the pH is equal to 9, the quantity of hydroquinone derivative will preferably be less than 0.33 mmol/mol of Ag since, in this particular case, the fogging level is higher than in Example 2-D.
- Example 1 The emulsion of Example 1 treated as described in Example 2 except that the hydroquinone derivative was 2,5 bis(1,1,3,3-tetramethylbutyl)hydroquinone (DOH).
- DOH 2,5 bis(1,1,3,3-tetramethylbutyl)hydroquinone
- Examples 3-I to 3-V show that the addition of DOH at a pH of 8.5 or 9.0 enables the sensitivity of the emulsion to be increased compared with the reference emulsions without increasing the fogging level above that of Example 3-D, where the highest sensitivity was obtained.
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- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9407275 | 1994-06-09 | ||
| FR9407275A FR2721117B1 (fr) | 1994-06-09 | 1994-06-09 | Procédé de préparation d'une émulsion photographique aux halogénures d'argent sensibilisée en présence de dérivés de l'hydroquinone. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0689091A1 true EP0689091A1 (fr) | 1995-12-27 |
Family
ID=9464203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP95420137A Withdrawn EP0689091A1 (fr) | 1994-06-09 | 1995-05-26 | Procédé de préparation d'une émulsion photographique à l'halogénure d'argent sensibilisée en présence de dérivés d'hydroguinone |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0689091A1 (fr) |
| JP (1) | JPH086195A (fr) |
| FR (1) | FR2721117B1 (fr) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53144796U (fr) * | 1977-04-18 | 1978-11-15 |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3192146A (en) | 1959-06-17 | 1965-06-29 | Diffusion De Procedes Et Breve | Equipment for purification and sterilization of swimming pool waters |
| DE1207792B (de) * | 1962-08-04 | 1965-12-23 | Agfa Ag | Verfahren zur Stabilisierung der Lichtempfindlichkeit photographischer Materialien waehrend der Lagerung |
| DE2034064A1 (de) * | 1969-07-10 | 1971-05-13 | Konishiroku Photo Industry Co Ltd, Tokio | Lichtempfindliches, gelatinehaltiges farbfotografisches Aufzeichenmatenal |
| FR2208133A1 (en) * | 1972-11-22 | 1974-06-21 | Ilford Ltd | Monochromatic silver halide emulsion for automatic processing - contains 2-alkyl hydroquinone 5-sulphonic acid or salt for superior development, shoulder sensitivity and contrast |
| DE2632202A1 (de) * | 1975-07-17 | 1977-02-03 | Fuji Photo Film Co Ltd | Verfahren zur herstellung von photographischen silberhalogenidemulsionen |
| FR2414743A1 (fr) * | 1978-01-11 | 1979-08-10 | Kodak Pathe | Produit photographique a developpement non polluant pour la photographie en noir et blanc et procede de mise en oeuvre |
| GB2055221A (en) * | 1979-08-11 | 1981-02-25 | Du Pont | Process for the preparation of monodisperse photographic silver halide emulsions of sensitivity |
| US4377634A (en) | 1977-09-06 | 1983-03-22 | Fuji Photo Film Co., Ltd. | Method for forming high contrast photographic image |
| FR2538135A1 (fr) * | 1982-12-17 | 1984-06-22 | Wolfen Filmfab Veb | Procede pour la stabilisation et la prevention du voile dans les matieres pour photographie en couleurs a base d'halogenure d'argent |
| US4614707A (en) | 1984-02-17 | 1986-09-30 | Fuji Photo Film Co., Ltd. | Color reversal photographic light-sensitive materials |
| EP0209010A2 (fr) | 1985-07-18 | 1987-01-21 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Eléments photographiques à haut contraste qui présentent une sensibilité réduite à la pression |
-
1994
- 1994-06-09 FR FR9407275A patent/FR2721117B1/fr not_active Expired - Lifetime
-
1995
- 1995-05-26 EP EP95420137A patent/EP0689091A1/fr not_active Withdrawn
- 1995-06-08 JP JP7142221A patent/JPH086195A/ja active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3192146A (en) | 1959-06-17 | 1965-06-29 | Diffusion De Procedes Et Breve | Equipment for purification and sterilization of swimming pool waters |
| DE1207792B (de) * | 1962-08-04 | 1965-12-23 | Agfa Ag | Verfahren zur Stabilisierung der Lichtempfindlichkeit photographischer Materialien waehrend der Lagerung |
| DE2034064A1 (de) * | 1969-07-10 | 1971-05-13 | Konishiroku Photo Industry Co Ltd, Tokio | Lichtempfindliches, gelatinehaltiges farbfotografisches Aufzeichenmatenal |
| FR2208133A1 (en) * | 1972-11-22 | 1974-06-21 | Ilford Ltd | Monochromatic silver halide emulsion for automatic processing - contains 2-alkyl hydroquinone 5-sulphonic acid or salt for superior development, shoulder sensitivity and contrast |
| DE2632202A1 (de) * | 1975-07-17 | 1977-02-03 | Fuji Photo Film Co Ltd | Verfahren zur herstellung von photographischen silberhalogenidemulsionen |
| US4377634A (en) | 1977-09-06 | 1983-03-22 | Fuji Photo Film Co., Ltd. | Method for forming high contrast photographic image |
| FR2414743A1 (fr) * | 1978-01-11 | 1979-08-10 | Kodak Pathe | Produit photographique a developpement non polluant pour la photographie en noir et blanc et procede de mise en oeuvre |
| GB2055221A (en) * | 1979-08-11 | 1981-02-25 | Du Pont | Process for the preparation of monodisperse photographic silver halide emulsions of sensitivity |
| FR2538135A1 (fr) * | 1982-12-17 | 1984-06-22 | Wolfen Filmfab Veb | Procede pour la stabilisation et la prevention du voile dans les matieres pour photographie en couleurs a base d'halogenure d'argent |
| US4614707A (en) | 1984-02-17 | 1986-09-30 | Fuji Photo Film Co., Ltd. | Color reversal photographic light-sensitive materials |
| EP0209010A2 (fr) | 1985-07-18 | 1987-01-21 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Eléments photographiques à haut contraste qui présentent une sensibilité réduite à la pression |
Non-Patent Citations (2)
| Title |
|---|
| GUNTHER FISCHER: "STABILISATOREN UND ANTISCHLEIERMITTEL FÜR PHOTOGRAPHISCHE SILBERHALOGENIDMATERIALIEN TEIL II: AROMATISCHE, ALIPHATISHE UND ANORGANISHE VERBINDUNGEN", JOURNAL OF INFORMATION RECORDING MATERIALS, vol. 20, no. 3, YVERDON CH, pages 197 - 239 * |
| RESEARCH DISCLOSURE, vol. 308, no. 119, December 1989 (1989-12-01) |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2721117A1 (fr) | 1995-12-15 |
| JPH086195A (ja) | 1996-01-12 |
| FR2721117B1 (fr) | 1998-07-10 |
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