EP0767400A1 - Herstellungsverfahren für chloridreiche (100)-Tafelkörner mit Kieselsäuresol als Bindemittel - Google Patents
Herstellungsverfahren für chloridreiche (100)-Tafelkörner mit Kieselsäuresol als Bindemittel Download PDFInfo
- Publication number
- EP0767400A1 EP0767400A1 EP95202639A EP95202639A EP0767400A1 EP 0767400 A1 EP0767400 A1 EP 0767400A1 EP 95202639 A EP95202639 A EP 95202639A EP 95202639 A EP95202639 A EP 95202639A EP 0767400 A1 EP0767400 A1 EP 0767400A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silica sol
- tabular
- added
- chloride
- silver
- 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.)
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- -1 silver halide Chemical class 0.000 title claims abstract description 53
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 39
- 239000004332 silver Substances 0.000 title claims abstract description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 32
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011230 binding agent Substances 0.000 title claims abstract description 10
- 239000000839 emulsion Substances 0.000 claims abstract description 76
- 150000004010 onium ions Chemical class 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 52
- 230000005070 ripening Effects 0.000 claims description 19
- 239000008119 colloidal silica Substances 0.000 claims description 13
- 150000004820 halides Chemical class 0.000 claims description 11
- 230000006911 nucleation Effects 0.000 claims description 11
- 238000010899 nucleation Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical class [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 2
- 229940006461 iodide ion Drugs 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 abstract description 12
- 239000000084 colloidal system Substances 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 description 50
- 239000000243 solution Substances 0.000 description 34
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 30
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 30
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 28
- 239000000975 dye Substances 0.000 description 19
- 238000001556 precipitation Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- 239000000377 silicon dioxide Substances 0.000 description 17
- 239000001103 potassium chloride Substances 0.000 description 15
- 235000011164 potassium chloride Nutrition 0.000 description 15
- 229910001961 silver nitrate Inorganic materials 0.000 description 14
- 229920000159 gelatin Polymers 0.000 description 13
- 235000019322 gelatine Nutrition 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 108010010803 Gelatin Proteins 0.000 description 11
- 206010070834 Sensitisation Diseases 0.000 description 11
- 239000008273 gelatin Substances 0.000 description 11
- 235000011852 gelatine desserts Nutrition 0.000 description 11
- 230000008313 sensitization Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000003607 modifier Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- 230000003595 spectral effect Effects 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 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 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 3
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 2
- 229930024421 Adenine Natural products 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 239000001828 Gelatine Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229960000643 adenine Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- FDGQSTZJBFJUBT-UHFFFAOYSA-N hypoxanthine Chemical compound O=C1NC=NC2=C1NC=N2 FDGQSTZJBFJUBT-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000013518 transcription Methods 0.000 description 2
- 230000035897 transcription Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- IHWDSEPNZDYMNF-UHFFFAOYSA-N 1H-indol-2-amine Chemical compound C1=CC=C2NC(N)=CC2=C1 IHWDSEPNZDYMNF-UHFFFAOYSA-N 0.000 description 1
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical class O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UGQMRVRMYYASKQ-UHFFFAOYSA-N Hypoxanthine nucleoside Natural products OC1C(O)C(CO)OC1N1C(NC=NC2=O)=C2N=C1 UGQMRVRMYYASKQ-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- XEIPQVVAVOUIOP-UHFFFAOYSA-N [Au]=S Chemical compound [Au]=S XEIPQVVAVOUIOP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000002180 anti-stress Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229940083747 low-ceiling diuretics xanthine derivative Drugs 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000005324 oxide salts Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- LETVJWLLIMJADE-UHFFFAOYSA-N pyridazin-3-amine Chemical compound NC1=CC=CN=N1 LETVJWLLIMJADE-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000000837 restrainer Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000004354 sulfur functional group Chemical group 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
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
- G03C1/0051—Tabular grain emulsions
- G03C1/0053—Tabular grain emulsions with high content of silver chloride
-
- 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
-
- 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
- G03C2200/00—Details
- G03C2200/01—100 crystal face
Definitions
- the present invention relates to the preparation of a new type of tabular grain silver halide emulsions rich in chloride.
- High aspect ratio tabular grains exhibit several pronounced photographic advantages. Thanks to their particular morphology greater amounts of spectral sensitizers can be adsorbed per mole silver halide compared to classical globular grains. As a consequence such spectrally sensitized tabular grains show an improved speed-granularity relationship and a wide separation between their blue speed and minus blue speed. Sharpness of photographic images can be improved using tabular grains thanks to their lower light scattering properties again compared to conventional globular emulsion grains. In color negative materials the conventional sequence of the light sensitive layers can be altered and the yellow filter layer can be omitted.
- An emulsion is generally understood to be a "tabular grain emulsion" when tabular grains account for at least 50 percent of total grain projected area.
- a grain is generally considered to be a tabular grain when the ratio of its equivalent circular diameter (ECD) to its thickness (t) is at least 2.
- the equivalent circular diameter of a grain is the diameter of a circle having an area equal to the projected area of the grain.
- intermediate aspect ratio tabular grain emulsion refers to an emulsion which has an average tabular grain aspect ratio in the range of from 5 to 8.
- thin tabular grain is generally understood to be a tabular grain having a thickness of less than 0.2 ⁇ m.
- chloride rich emulsion grains show a cubic morphology with (100) crystal faces. It is known that to alter this crystallographic habit into a (111) habit so-called “growth modifiers” or “crystal habit modifiers” are required (see Klein and Moisar, in Berichte der Bunsengesellschaft Vol. 67 (4), p. 349-355, and Claes et al., J. Photogr. Sci. Vol. 21 (1973), p. 39-50).
- Typical examples of these modifiers include adenine, thiourea, hypoxanthine, benzimidazole and benzothiazole derivatives. The mechanism of the growth modifying action of adenine was studied in detail by Szucs in J. Signal AM Vol. 6 (1978) No 5 p. 381-405.
- EP 0 481 133 describes the presence of adenine-like compounds in the preparation of chloride rich tabular grains using conventional gelatin, and Maskasky US 5,183,732 discloses similar compounds. Maskasky further describes triaminopyrimidines in US 5,185,239, xanthine derivatives in US 5,178,998, and other heterocyclic compounds in US 5,178,997, all as growth modifiers in the preparation of chloride rich tabular emulsions.
- Mignot U.S. Pat. No. 4,386,156 represents an improvement over Bogg in that the disadvantages of ammoniacal ripening were avoided in preparing a silver bromide emulsion containing tabular grains with square and rectangular major faces.
- Mignot specifically requires ripening in the absence of silver halide ripening agents other than bromide ion (e.g., thiocyanate, thioether or ammonia).
- the present invention extends the teachings on tabular silver halide grains rich in chloride and prepared in a silica sol medium.
- the objects of the present invention are realized by providing a process for the preparation of a radiation sensitive silver halide emulsion comprising colloidal silica sol as the substantially sole binder, and containing at least 50 mole % of chloride, based on total amount of silver halide, in which more than 50 % of the total projected area of the grain population is accounted for by tabular grains bounded by parallel major faces lying in (100) crystallographic planes and having an adjacent edge ratio of less than 10, and wherein the average aspect ratio of the (100) tabular grain poulation is at least 2, said process comprising the following steps :
- the amount of silica sol added during physical ripening step (b) ranges from 40 to 60 % of the total amount of silica sol added, and the ratio of the total amount of onium compound added to the total amount of silica sol added ranges from 0.07 to 0.15.
- Silica sols used as a protective colloid in the preparation of silver halide emulsions comprising tabular grains according to this invention are commercially available such as the "Syton” silica sols ( trademarked products of Monsanto Inorganic Chemicals Div.), the “Ludex” silica sols (trademarked products of du Pont de Nemours & Co., Inc.), the "Nalco” and “Nalcoag” silica sols (trademarked products of Nalco Chemical Co), the "Snowtex” silica sols of Nissan Kagaku K.K. and the "Kieselsol, Types 100, 200, 300, 500 and 600" (trademarked products of Bayer AG).
- Particle sizes of the silica sol particles are in the range from 3 nm to 30 ⁇ m. Smaller particles in the range from 3 nm to 0.3 ⁇ m are preferred as the coverage degree per gram of silica sol that can be achieved will be higher and as the protective action of the colloidal silica will be more effective.
- a preferred onium compound is (phenyl) 3 -P + -CH 2 -CH 2 OH.Cl - .
- onium compounds are disclosed in U.S. Patent 3,017,270.
- trialkyl sulfonium salts polysulfonium salts, tetraalkyl quaternary ammonium salts, quaternary ammonium salts in which the quaternary nitrogen atom is a part of a ring system, cationic polyalkylene oxide salts including e.g. quaternary ammonium and phosphonium and bis-quaternary salts.
- onium salt polymers wherein the onium group may be, e.g., an ammonium, excluding inorganic ammonium compounds, phosphonium or sulphonium group, are disclosed in U.S. Patent 4,525,446. Said onium compounds act as effective stabilisers of the colloidal stability of silver halide tabular crystals covered with silica, provided that, according to this invention, an appropriate amount is added to the reaction vessel versus the amount of silica present.
- an ammonium excluding inorganic ammonium compounds, phosphonium or sulphonium group
- steps (a) and (b) of the amounts of silica sol added is of great importance for the successful practice of the present invention.
- the physical ripening step 10 to 100 % of the final amount must be added.
- the amount of silica sol is about equally divided : 40 to 60 % in step (a) and 60 to 40 % in step (b).
- the silica sol For each partition ratio of the silica sol added there is also an optimal ratio for the amount of costabilizing onium compound to silica sol.
- the ratio of the total amount of onium compound added to the total amount of silica added is preferably comprised between 0.07 and 0.15.
- the nucleation step which consists preferably of an addition by means of the double-jet method of silver nitrate and halide salts at a constant flow rate.
- the pCl of the medium must be established and maintained at a value between 0.5 and 3.0.
- the growth step is performed by adding simultaneously silver salt and halide solutions at increasing flow rates. Linearly increasing flow rates are preferred. During said growth step the pCl must be maintained between 0.5 and 3.0. In principle more than one growth step can be performed. It is important to avoid renucleation during the growth step by controlling the preferred increasing rate of addition of the silver nitrate and the halide salts to make the distribution predictable of the emulsion crystals comprising tabular silica silver halide.
- the photographic emulsions comprising silver halide tabular crystals covered with silica particles may have a homogeneous or a heterogeneous halide distribution within the crystal volume.
- a heterogeneous halide distribution may be obtained by application of growth steps having a different halide composition or by conversion steps, e.g. by addition of halide ions that provide less soluble silver salts, onto existing tabular cores.
- a heterogenous distribution of halide ions a multilayered grain structure is obtained.
- the tabular form has to be maintained in this case, in order to get silica tabular emulsion crystals in accordance with this invention.
- the crystals may further be doped with whatever a dope, as e.g. with Rh 3+ , Ir 4+ , Cd 2+ , Zn 2+ , Pb 2+ .
- grain growth restrainers or accelerators may be added to obtain crystals with a preferred average crystal size between 0.05 and 5 ⁇ m.
- grain growth accelerators are compounds carrying e.g. a thioether function.
- the light-sensitive emulsion comprising silver halide tabular crystals with silica as protective colloid, prepared in accordance with the present invention is, after redispersion, a so-called primitive emulsion.
- said emulsion can be chemically sensitized as described i.a. "Chimie et Physique Photographique” by P. Glafkides, in “Photographic Emulsion Chemistry” by G.F. Duffin, in “Making and Coating Photographic Emulsion” by V.L. Zelikman et al, and in "Die Grundlagen der Photographischen mit Silberhalogeniden” edited by H. Frieser and published by Akademische Verlagsgesellschaft (1968).
- chemical sensitization can be carried out by effecting the ripening in the presence of small amounts of compounds containing sulphur e.g. thiosulphate, thiocyanate, thioureas, sulphites, mercapto compounds, and rhodanines.
- sulphur e.g. thiosulphate, thiocyanate, thioureas, sulphites, mercapto compounds, and rhodanines.
- the emulsions can be sensitized also by means of gold-sulphur ripeners or by means of reductors e.g. tin compounds as described in GB-A 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds.
- Chemical sensitization can also be performed with small amounts of Ir, Rh, Ru, Pb, Cd, Hg, Tl, Pd, Pt, or Au.
- One of these chemical sensitization methods or a combination thereof can be used.
- a mixture can also be made of two or more separately precipitated emulsions being chemically sensitized before mixing them.
- the light-sensitive emulsion comprising silver halide tabular crystals with silica as a protective colloid, prepared in accordance with the present invention may be spectrally sensitized with methine dyes such as those described by F.M. Hamer in "The Cyanine Dyes and Related Compounds", 1964, John Wiley & Sons.
- Dyes that can be used for the purpose of spectral sensitization include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
- Particularly valuable dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.
- a survey of useful chemical classes of spectral sensitizing dyes and specific useful examples in connection with tabular grains is given in the already cited Research Disclosure Item 22534.
- spectral sensitization traditionally follows the completion of chemical sensitization.
- spectral sensitization may occur simultaneously with or may even precede completely the chemical sensitization step: the chemical sensitization after spectral sensitization is believed to occur at one or more ordered discrete sites of tabular grains. This may also be done with the emulsions of the present invention.
- silica sol Before chemical sensitizaton and or before coating extra silica sol can be added to the tabular (100) emulsions as protective colloid. Also the conventional binder gelatin can be added.
- the final ratio of the amount of total binder (silica + gelatin) to silver, expressed as silver nitrate, is then preferably comprised between 0.2 and 1.0, most preferably between 0.3 and 0.6.
- the finished photographic can further contain the well-known conventional ingredients such as antifoggants, stabilizers, wetting agents, UV absorbers, antistatics, plasticizers, development accelerators antihalation dyes, colour couplers, filter dyes, spacing agents, hardeners, etc..
- well-known conventional ingredients such as antifoggants, stabilizers, wetting agents, UV absorbers, antistatics, plasticizers, development accelerators antihalation dyes, colour couplers, filter dyes, spacing agents, hardeners, etc.
- the photographic material can contain several non-light sensitive layers, e.g. a protective antistress topcoat layer, one or more backing layers, and one or more intermediate layers optionally containing filter- or antihalation dyes that absorb scattering light and thus promote the image sharpness.
- a protective antistress topcoat layer e.g. a protective antistress topcoat layer
- one or more backing layers e.g. a protective antistress topcoat layer
- one or more intermediate layers optionally containing filter- or antihalation dyes that absorb scattering light and thus promote the image sharpness.
- the photographic silica tabular silver halide emulsions can be used in various types of photographic elements such as i.a. in photographic elements for so-called amateur and professional photography, for graphic arts, diffusion transfer reversal photographic elements, low-speed and high-speed photographic elements, X-ray materials, micrografic materials etc..
- the support of the photographic material may be opaque or transparent, e.g. a paper support or resin support.
- a paper support preference is given to one coated at one or both sides with an Alpha-olefin polymer, e.g. a polyethylene layer which optionally contains an anti-halation dye or pigment.
- an organic resin support e.g. cellulose nitrate film, cellulose acetate film, poly(vinyl acetal) film, polystyrene film, poly(ethylene terephthalate) film, polycarbonate film, polyvinylchloride film or poly-Alpha-olefin films such as polyethylene or polypropylene film.
- the thickness of such organic resin film is preferably comprised between 0.07 and 0.35 mm.
- These organic resin supports are preferably coated with a subbing layer which can contain water insoluble particles such as silica or titanium dioxide.
- the photographic material containing tabular grains prepared according to the present invention can be image-wise exposed by any convenient radiation source in accordance with its specific application.
- processing conditions and composition of processing solutions are dependent from the specific type of photographic material in which the tabular grains prepared according to the present invention are applied.
- Emulsion layers in accordance with the present invention, and more particularly thin emulsion layers, are showing remarkable improvements concerning both resistance to stress and rapid processability compared to conventional emulsions prepared in gelatinous medium. As the ratio by weight of gelatin to silver halide decreases more pronounced pressure marks can be expected.
- a decreased pressure sensitivity for the materials coated from silver halide emulsions according to this invention is attained in various processing conditions and should be recognized as an exceptional advantage offered by the tabular (100) silver halide emulsion crystals rich in chloride and prepared in silica sol as protective colloid binder.
- This example was designed to illustrate the influence of the concentration of the colloidal silica and the concentration of the onium compound during the precipitation on the final crystal structure of the precipitated silver halide.
- a silver iodochloride emulsion was precipitated as follows: a 2280 mL solution containing x1 g of 'Kieselsol 500' (Bayer AG) and y1 g of the co-stabilizing phosphonium compound (Phenyl) 3 -P + -CH 2 -CH 2 OH.Cl - was provided in a stirred reaction vessel. The pCl was adjusted with KCl to a value of 1.0, the pH was adjusted to 3.0 and the reaction vessel was maintained at 45 o C.
- the resulting emulsions contained 0.5 mole percent iodide, based on silver.
- the emulsions were statistically analysed towards their crystal structures using the transmission electron micrographs of the shadowed replicas.
- the results for emulsions A to N are shown in table I, where
- This example illustrates an optimization of the results of example 1 towards more [100] tabular crystals with a higher aspect ratio.
- Emulsion O (Invention).
- a tabular silver iodochloride emulsion was precipitated as follows: a 2280 mL solution containing 18 g of 'Kieselsol 500' and 1.8 g of the co-stabilizing phosphonium compound (Phenyl) 3 -P + -CH 2 -CH 2 OH.Cl - was provided in a stirred reaction vessel. The pCl was adjusted with KCl to a value of 2.0, the pH was adjusted to 6.0 and the reaction vessel was maintained at 45 o C.
- tabular grain emulsion tabular grains accounted for 50 percent of the total grain projected area with an average aspect ratio of about 4.
- Figure 3 shows a transmission electron micrograph of the resulting emulsion.
- Emulsion P (Comparative emulsion in gelatine)
- a silver iodochloride emulsion was precipitated according to the formula of Emulsion O with the modification that silica sol was replaced by gelatin as binder and that no onium compound was present:
- a 2280 mL solution containing 20 g of gelatin was provided in a stirred reaction vessel.
- the pCl was adjusted with KCl to a value of 2.0, the pH was adjusted to 6.0 and the reaction vessel was maintained at 45 o C.
- the mixture was then held 20 minutes while raising the temperature to 70 o C. Then the pH was adjusted to 3.0 and a 2.94 M silver nitrate solution and a 2.925 M potassium chloride and 0.015 M potassium iodide solution were added simultaneously at a rate during 77 minutes and 36 seconds starting at a flow rate of 4 mL/min and linearly increasing the flow rate to an end value of 16 mL/min with the pCl being maintained at 1.4.
- Emulsion Q Emulsion Q.
- a 1600 mL solution containing 10 g of gelatin was provided in a stirred reaction vessel.
- the pCl was adjusted with KCl to a value of 1.0, the pH was adjusted to 6.0 and the reaction vessel was maintained at 50 o C.
- the mixture was then held 20 minutes while raising the temperature to 70 o C. Then a 2.94 M silver nitrate solution and a 2.925 M potassium chloride and 0.015 M potassium iodide solution were added simultaneously at a rate during 77 minutes and 36 seconds starting at a flow rate of 4 mL/min and linearly increasing the flow rate to an end value of 16 mL/min with the pCl being maintained at 1.4.
- a 1600 mL solution containing 10 g of "Kiezelsol 500" and 1 g of the co-stabilizing phosphonium compound (Phenyl) 3 -P + -CH 2 -CH 2 OH.Cl - was provided in a stirred reaction vessel.
- the pCl was adjusted with KCl to a value of 1.0, the pH was adjusted to 6.0 and the reaction vessel was maintained at 50 o C.
- the mixture was then held 20 minutes while raising the temperature to 70 o C. Then a 2.94 M silver nitrate solution and a 2.925 M potassium chloride and 0.015 M potassium iodide solution were added simultaneously at a rate during 77 minutes and 36 seconds starting at a flow rate of 4 mL/min and linearly increasing the flow rate to an end value of 16 mL/min with the pCl being maintained at 1.4.
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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)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP95202639A EP0767400A1 (de) | 1995-10-02 | 1995-10-02 | Herstellungsverfahren für chloridreiche (100)-Tafelkörner mit Kieselsäuresol als Bindemittel |
| US08/715,499 US5840474A (en) | 1995-10-02 | 1996-09-18 | Preparation method for (100) tabular silver halide grains rich in chloride in silica sol as binder |
| JP8275413A JP2835714B2 (ja) | 1995-10-02 | 1996-09-25 | 保護コロイドとしてのシリカゾル中で塩化銀を多く含む平板状ハロゲン化銀粒子の製造法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP95202639A EP0767400A1 (de) | 1995-10-02 | 1995-10-02 | Herstellungsverfahren für chloridreiche (100)-Tafelkörner mit Kieselsäuresol als Bindemittel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0767400A1 true EP0767400A1 (de) | 1997-04-09 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP95202639A Withdrawn EP0767400A1 (de) | 1995-10-02 | 1995-10-02 | Herstellungsverfahren für chloridreiche (100)-Tafelkörner mit Kieselsäuresol als Bindemittel |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0767400A1 (de) |
| JP (1) | JP2835714B2 (de) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5840474A (en) * | 1995-10-02 | 1998-11-24 | Agfa-Gevaert, N.V. | Preparation method for (100) tabular silver halide grains rich in chloride in silica sol as binder |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5632339B2 (ja) * | 2011-08-05 | 2014-11-26 | 株式会社ジャパンディスプレイ | 液晶表示装置 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0392092A1 (de) * | 1989-04-11 | 1990-10-17 | Agfa-Gevaert N.V. | Verfahren zur Herstellung von lichtempfindlichen Silberhalogenid Emulsionen |
| JPH0772578A (ja) * | 1993-09-02 | 1995-03-17 | Konica Corp | ハロゲン化銀写真感光材料 |
| EP0653669A1 (de) * | 1993-11-16 | 1995-05-17 | Agfa-Gevaert N.V. | Chloridreiche Tafelkornemulsion mit (100)-Hauptflächen |
| JPH07225439A (ja) * | 1994-02-10 | 1995-08-22 | Konica Corp | ハロゲン化銀写真感光材料 |
| EP0677773A1 (de) * | 1994-04-06 | 1995-10-18 | Agfa-Gevaert N.V. | Tafelförmige Kristalle enthaltende Silberhalogenidemulsionen und Verfahren zu deren Verarbeitung |
-
1995
- 1995-10-02 EP EP95202639A patent/EP0767400A1/de not_active Withdrawn
-
1996
- 1996-09-25 JP JP8275413A patent/JP2835714B2/ja not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0392092A1 (de) * | 1989-04-11 | 1990-10-17 | Agfa-Gevaert N.V. | Verfahren zur Herstellung von lichtempfindlichen Silberhalogenid Emulsionen |
| JPH0772578A (ja) * | 1993-09-02 | 1995-03-17 | Konica Corp | ハロゲン化銀写真感光材料 |
| EP0653669A1 (de) * | 1993-11-16 | 1995-05-17 | Agfa-Gevaert N.V. | Chloridreiche Tafelkornemulsion mit (100)-Hauptflächen |
| JPH07225439A (ja) * | 1994-02-10 | 1995-08-22 | Konica Corp | ハロゲン化銀写真感光材料 |
| EP0677773A1 (de) * | 1994-04-06 | 1995-10-18 | Agfa-Gevaert N.V. | Tafelförmige Kristalle enthaltende Silberhalogenidemulsionen und Verfahren zu deren Verarbeitung |
Non-Patent Citations (2)
| Title |
|---|
| DATABASE WPI Week 9520, Derwent World Patents Index; AN 95-149871, XP002004505 * |
| DATABASE WPI Week 9542, Derwent World Patents Index; AN 95-326111, XP002004506 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5840474A (en) * | 1995-10-02 | 1998-11-24 | Agfa-Gevaert, N.V. | Preparation method for (100) tabular silver halide grains rich in chloride in silica sol as binder |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2835714B2 (ja) | 1998-12-14 |
| JPH09203981A (ja) | 1997-08-05 |
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