US3850645A - Non-polymeric peptizers for silver halide suspensions - Google Patents
Non-polymeric peptizers for silver halide suspensions Download PDFInfo
- Publication number
- US3850645A US3850645A US00388316A US38831673A US3850645A US 3850645 A US3850645 A US 3850645A US 00388316 A US00388316 A US 00388316A US 38831673 A US38831673 A US 38831673A US 3850645 A US3850645 A US 3850645A
- Authority
- US
- United States
- Prior art keywords
- silver halide
- dye
- silver
- gelatin
- water
- 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
Links
- -1 silver halide Chemical class 0.000 title claims abstract description 113
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 79
- 239000004332 silver Substances 0.000 title claims abstract description 79
- 239000000725 suspension Substances 0.000 title description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims description 37
- 230000008569 process Effects 0.000 claims description 32
- 229920000159 gelatin Polymers 0.000 claims description 29
- 239000008273 gelatin Substances 0.000 claims description 28
- 235000019322 gelatine Nutrition 0.000 claims description 27
- 108010010803 Gelatin Proteins 0.000 claims description 26
- 235000011852 gelatine desserts Nutrition 0.000 claims description 26
- 239000000839 emulsion Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 16
- 108091005804 Peptidases Proteins 0.000 claims description 12
- 102000035195 Peptidases Human genes 0.000 claims description 12
- 150000004820 halides Chemical class 0.000 claims description 12
- 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 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 102000004190 Enzymes Human genes 0.000 claims description 8
- 108090000790 Enzymes Proteins 0.000 claims description 8
- UCTWMZQNUQWSLP-VIFPVBQESA-N (R)-adrenaline Chemical compound CNC[C@H](O)C1=CC=C(O)C(O)=C1 UCTWMZQNUQWSLP-VIFPVBQESA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000005588 protonation Effects 0.000 claims description 6
- 230000002797 proteolythic effect Effects 0.000 claims description 5
- 239000000975 dye Substances 0.000 abstract description 33
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 abstract 1
- 150000005840 aryl radicals Chemical class 0.000 description 15
- 239000000084 colloidal system Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 125000004429 atom Chemical group 0.000 description 12
- 125000000623 heterocyclic group Chemical group 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 230000005855 radiation Effects 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 229940088598 enzyme Drugs 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 150000001450 anions Chemical class 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QMHIMXFNBOYPND-UHFFFAOYSA-N 4-methylthiazole Chemical compound CC1=CSC=N1 QMHIMXFNBOYPND-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 238000001016 Ostwald ripening Methods 0.000 description 2
- 239000004365 Protease Substances 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000005670 electromagnetic radiation Effects 0.000 description 2
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- BGTVICKPWACXLR-UHFFFAOYSA-N 4,5-diphenyl-1,3-thiazole Chemical compound S1C=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 BGTVICKPWACXLR-UHFFFAOYSA-N 0.000 description 1
- KNDOFJFSHZCKGT-UHFFFAOYSA-N 4-chloroquinoline Chemical compound C1=CC=C2C(Cl)=CC=NC2=C1 KNDOFJFSHZCKGT-UHFFFAOYSA-N 0.000 description 1
- KXCQDIWJQBSUJF-UHFFFAOYSA-N 4-phenyl-1,3-thiazole Chemical compound S1C=NC(C=2C=CC=CC=2)=C1 KXCQDIWJQBSUJF-UHFFFAOYSA-N 0.000 description 1
- YXGBCQGWEUFUID-UHFFFAOYSA-N 4-thiophen-2-yl-1,3-thiazole Chemical compound C1=CSC(C=2N=CSC=2)=C1 YXGBCQGWEUFUID-UHFFFAOYSA-N 0.000 description 1
- ZLKGGEBOALGXJZ-UHFFFAOYSA-N 8-methoxyquinoline Chemical compound C1=CN=C2C(OC)=CC=CC2=C1 ZLKGGEBOALGXJZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- 108090000270 Ficain Proteins 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 108010019160 Pancreatin Proteins 0.000 description 1
- 108090000526 Papain Proteins 0.000 description 1
- 108090000284 Pepsin A Proteins 0.000 description 1
- 102000057297 Pepsin A Human genes 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 102000004142 Trypsin Human genes 0.000 description 1
- 108090000631 Trypsin Proteins 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- DHCATGATLDEXED-UHFFFAOYSA-N [ClH]1[ClH][ClH][ClH]C1 Chemical compound [ClH]1[ClH][ClH][ClH]C1 DHCATGATLDEXED-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- AQNQQHJNRPDOQV-UHFFFAOYSA-N bromocyclohexane Chemical compound BrC1CCCCC1 AQNQQHJNRPDOQV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- POTUGHMKJGOKRI-UHFFFAOYSA-N ficin Chemical compound FI=CI=N POTUGHMKJGOKRI-UHFFFAOYSA-N 0.000 description 1
- 235000019836 ficin Nutrition 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- ULAHIHHGQVIRTO-UHFFFAOYSA-N methanesulfonic acid;4-methylbenzenesulfonic acid Chemical compound CS(O)(=O)=O.CC1=CC=C(S(O)(=O)=O)C=C1 ULAHIHHGQVIRTO-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 1
- 230000004660 morphological change Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229940055695 pancreatin Drugs 0.000 description 1
- 229940055729 papain Drugs 0.000 description 1
- 235000019834 papain Nutrition 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229940111202 pepsin Drugs 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000837 restrainer Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000012588 trypsin Substances 0.000 description 1
- 229960001322 trypsin Drugs 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000008096 xylene Substances 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
- G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
- G03C1/496—Binder-free compositions, e.g. evaporated
Definitions
- Typical binder colloids absorb light of short wavelengths (e.g., ultraviolet rays); as such, the binder material can determine the short wavelength limit of usefulness for any given photographic element. The presence of such binder colloids operates to impede preparation of high quality, ultraviolet-sensitive photographic elements such as those used in astronomical studies.
- the present invention comprises the use of cyanine and azacyanine dyes as non-polymeric peptizers in dispersions of silver halides.
- the present invention comprises a process for preparing dispersions of silver halides comprising:
- A reacting a water-soluble silver salt with a watersoluble halide in aqueous solution in the presence of gelatin whereby a stable gelatinosilver halide photographic emulsion is formed;
- A is nitrogen or Cl o-c) v ⁇ il l n is 0, l or 2;
- An is an acid anion
- W, X and Y are independently selected from the group'consisting of hydrogen, alkyl radicals, aryl radicals, cycloalkyl radicals and alkaryl radicals; and R and R are independently selected from the group consisting of alkyl radicals, aryl radicals, cycloalkyl radicals and alkaryl radicals; and Z and Z each represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing five or six atoms in the heterocyclic ring;
- Another embodiment of the present invention comprises the silver halide products prepared by the fore- 60 going process.
- the present invention provides for the replacement of gelatin in preformed silver halide-gelatin dispersions by simple, monomeric organic compounds which are defined herein as being non-polymeric peptizers. These compounds are adsorbed to the silver halide surface and are not affected by the mild enzymatic hydrolysis conditions which are required for gelatin removal. It is a characteristic property of the present peptizers that they not only prevent the irreversible agglomeration of individual silver halide particles, but also interfere with recrystallization processes (Ostwald ripening) and thus help maintain the dispersity and crystal habit of the original silver halide dispersion.
- radiation-sensitive is descriptive of chemical species (silver salts) that are activated by exposure to electromagnetic radiation to typically provide latent images that can be intensified by various photographic development techniques to provide visible images.
- the subject silver salts are radiation-sensitive and include species that are lightsensitive.
- radiation-sensitive comprehends responsiveness to activating radiation both withinand without the visible portion of the spectrum.
- radiationsensitive refers to the responsiveness of an activatable silver salt species through a wide segment of electromagnetic radiation including, for example, x-radiation, ultraviolet radiation, infrared radiation and the like.
- the preformed, radiation-sensitive silver salt crystals prepared according to the practice of this invention include those of the silver halides typically employed in gelatino-silver halide photographic emulsions, such as silver bromide, silver chloride and silver iodide. Additionally, mixtures of these halides are advantageously utilized, as are co-crystals, such as, for example, silver bromoiodide, silver chlorobromide, silver chloroiodide, silver chlorobromoiodide, and the like.
- non-polymeric peptizers employed in the practice of this invention are cyanines, azacyanines and related compounds, all having the structure:
- A is nitrogen or wherein n is 0, l or 2 and W, X and Y are independently selected from the group consisting of hydrogen, alkyl radicals, aryl radicals, cycloalkyl radicals and alkaryl radicals.
- alkyl, aryl cycloalkyl
- alkaryl include the substituted derivatives thereof such as, for example, alkyl substituted derivatives, halogensubstituted derivatives, sulfonate-substituted derivatives, carboxyl-substituted derivatives, aryl-substituted derivatives and the like.
- alkyl radicals are employed, it is preferred that they have from 1 to 12 carbon atoms and most preferred that they have from one to four carbon atoms, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and isomers thereof.
- aryl radicals are employed, it is preferred that they be aryl radicals of from 6 to 12 carbon atoms, e.g., benzene, xylene,'toluene, ethyl benzene, butyl benzene, napthylene, chlorobenzene, chlorotoluene, bromonapthylene, and the like.
- cycloalkyl radicals that can be employed can be listed: cyclopentane, cyclohexane, chlorocyclohexane, bromocyclohexane, and the like.
- Benzyl radicals and phenethyl radicals are examples of the aryl radicals which can be employed in the dye structures used in this invention.
- R and R in the above dye structure are independently collected from the group consisting of alkyl radicals, aryl radicals, cycloalkyl radicals and alkaryl radicals, which radicals are as defined above for W, X and Y.
- An represents an acid anion such as hydroxide, chloride, bromide, p-toluenesulfonate methanesulfonate, methylsulfate, ethylsulfate, perchlorate, etc.
- Z and Z each represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing from five to six atoms in the heterocyclic ring, e.g., thiazole, 4- phenylthiazole, 4,5-diphenylthiazole, 4-( 2- thienyl)thiazole, 4-methylthiazole, benzothiazole, 4-
- chlorobenzothiazole 4-methylbenzothiazole, 4- methoxybenzothiazole, 4-ethoxybenzothiazole, 4- phenylbenzothiazole, 5-chlorobenzothiazole, 5- bromobenzothiazole, S-methylbenzothiazole, 5- methoxybenzothiazole, 5-ethoxybenzothiazole, 5- phenylbenzothiazole, 6-chlorobenzothiazole, 6- bromobenzothiazole, 6-methylbenzothiazole, 6- methoxybenzothiazole, -ethoxybenzothiazole, 4- phenyloxazole, benzoxazole, 5-chlorobenzoxazole, 5- methylbenzoxazole, 5-bromobenzoxazole, 5- methoxybenzoxazole, S-ethoxybenzoxazole, 5-
- phenylbenzoxazole l,3-dialkyl, l,3-diaryl or l-alkyl-3- aryl, imidazoles and benzimidazoles, such as 5-chlorol,3-dialkyl benzimidazoles, 5-chloro- -chloro-l,3- diaryl benzimidazoles, 5,6-dichloro-l,3-dialkyl benzimidazoles, 5,6-dichloro-1,3-diaryl benzimidazoles, 5- methoxy-l,3-dialkyl benzimidazoles, 5-methoxy-l,3- diaryl benzimidazoles, 5-methoxy-l,3-diaryl benzimidazoles, 5-cyano-l,3-dialkyl benzimidazoles, 5-cyanol,3-dialkyl benzimidazoles, 5-cyanol,3-dialkyl benzimidazoles, 5-cyanol,
- substantially complete removal of gelatin is effected by enzyme hydrolysis as described in Weiss, Ericson and Herz, J. Colloid and Interface Science, Vol. 23, p. 277 i967).
- Any enzymes suitable for the intended purpose can be employed, for example, pepsin, trypsin, papain, ficin, pancreatin, and the like.
- H. T. Proteolytic Takamine available from Miles Chemical Company, Elkhart, Indiana, has been found to be particularly effective, and is preferred.
- the non-polymeric peptizer be added to the silver halide prior to hydrolysis of the gelatin with the proteolytic enzyme. When this is done, the resulting silver halide particles, after purification, will be found to have retained their original size and morphology. If the nonpolymeric peptizer is added to the dispersion after completion of the gelatin hydrolysis, the dispersion will contain large agglomerates of silver halide particles whose morphology has changed drastically.
- the concentration of the non-polymeric peptizer will vary depending upon the size and morphology of the crystals being peptized and on the special characteristics of the particular peptizer. In general, however, levels of non-polymeric peptizer of about 0.05 to about grams per mole of silver halide have been found to be effective and such levels are preferred.
- the nonpolymeric peptizer may be desirable to remove the nonpolymeric peptizer from the silver halide surface.
- peptizing compounds which can be desorbed by acid are particularly useful. Since acidinduced desorption of these peptizers causes rapid agglomeration of the silver halide suspension which cannot be reversed by subsequent neutralization, it will be convenient to deposit the silver halide particles first on a suitable support and then to desorb the nonpolymeric peptizer by the acid wash. The resulting silver halide layers, which contain no organic peptizers, retain their original particle size and crystal habit.
- non-polymeric peptizers employed in the practice of this invention can be cationic, anionic or zwitterionic depending upon the identity of the groups chosen for R and R.
- R R' alkyl (e.g., --C H)
- the molecule will be a cationic compound, which upon adsorption to silver halide will increase its positive charge density.
- R R CH;
- CO Na acid residue
- the organic molecule will be anionic and, upon adsorption, will tend to increase the negative charge at the silver halide/solution interface.
- a similar increase in negative charge density will be observed when the molecule is zwitterionic (e.g., R C H R (CH SO seeWeiss et al., J. Colloid and Interface Science, 23, 277 (1967).
- cyanines are not only strongly adsorbed, but are also colored and efficient spectral sensitizers, their use as peptizers might be limited if they could not be decolorized or removed from the silver halide system. Both processes can be achieved by protonation. This reversible reaction, which is facilitated in cyanines with basic nuclei such as those derived from quinoline or benzimidazole, .decolorizes the dye so that it is no longer a spectral sensitizer. See Feldman et al., J. Phys. Chem., 72, 2008 (1968). Furthermore, as compared with the dye, the colorless protonation product is weakly bound to the silver halide substrate. Hence, as noted above, adsorbed dye can be readily and irreversibly removed from the silver halide surface by treatment with dilute acid.
- the paper was rinsed with distilled water to remove excess alumina and was dried at about 25C. This dry paper was then passed for a few seconds through the silver bromide suspension prepared in Part A. The coating was then rinsed again with distilled water in order to remove excess silver bromide and was allowed to dry at 25C. Part C A strip of the treated paper of Part B was exposed through a diffraction grating (360-720 nm) containing a superimposed neutral step tablet, developed for about 5 seconds in Kodak Developer D-l9, held briefly in an acetic acid stop bath, fixed and then washed in running water. The resulting silver image extended to about 600 nm.
- EXAMPLE 2 A second coating sample prepared as in Example 1 was rinsed consecutively in two 10" M KBr solutions for one minute, the first solution containing 0.1 M HNO;,. Upon exposing and developing as before, no spectral sensitization was observed and the image formed only in the intrinsic adsorption region of the silver bromide. Similar results were obtained when other acids, such as toluene sulfonic acid, were employed. The results indicated that the dye had been removed and electron micrographs gave no evidence of any morphological changes in the silver bromide substrate which was now free of organic surface impurities.
- EXAMPLE 3 was added to the dispersion. This provides a. 50 percent surface coverage of the silver bromide. Results similar to those of Example 1 were obtained.
- EXAMPLE 4 The same procedure as in Example I was repeated except that a solution of anhydro--chloro-l,l ,3- triethyl-3 3-sulfopropyl benzimidazolocarbocyanine hydroxide (0.01 l g.) in methanol (150 ml.) was added to the dispersion as the peptizer. Again, results equivalent to those of Example 1 were obtained.
- EXAMPLE 5 The same procedure as in Example 1 was repeated except that a solution of anhydro-3-methyl-3-( 3- sulfopropyl)-8-azathiacyanine hydroxide (0.008 g.) in methanol (50 ml.) was added to the dispersion as the peptizer. Again, results equivalent to those of Example 1 were obtained except that the resulting image did not extend past the intrinsic sensitivity of the silver bromide.
- a process for preparing dispersions of silver halides comprising:
- A reacting a water-soluble silver salt with a watersoluble halide in aqueous solution in the presence of gelatin whereby a stable gelatino-silver halide photographic emulsion is formed;
- A is nitrogen or l w ⁇ X Y n n is 0. l or 2;
- An is an acid anion
- W, X and Y are independently selected from the group consisting of hydrogen, alkyl radicals. aryl radicals, cycloalkyl radicals and alkaryl radicals; and R and R are independently selected from the group consisting of alkyl radicals, aryl radicals, cycloalkyl radicals and alkaryl radicals; and
- Z and 2' each represents the non-metallic atoms nec essary to complete a heterocyclic nucleus contain ing five or six atoms in the heterocyclic ring;
- a process for preparing dispersions of silver halides comprising:
- A is nitrogen or An is an acid anion
- W, X and Y are independently selected from the group consisting of hydrogen, alkyl radicals, aryl radicals, cycloalkyl radicals and alkaryl radicals; and R and R are independently selected from the group consisting of alkyl radicals, aryl radicals, cycloalkyl radicals and alkaryl radicals; and
- Z and Z each represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing five or six atoms in the heterocyclic ring;
- proteolytic enzyme is H. T. Proteolytic Takamine.
- a photographic silver halide emulsion prepared by process comprising:
- A reacting a water-soluble silver salt with a watersoluble halide in aqueous solution in the presence of gelatin whereby a stable gelatino silver halide photographic emulsion is formed;
- A is nitrogen or n is 0, l or 2;
- An is an acid anion
- W, X and Y are independently selected from the group consisting of hydrogen, alkyl radicals, aryl radicals, cycloalkyl radicals and alkaryl radicals; and R and R are independently selected from the group consisting of alkyl radicals, aryl radicals, cycloalkyl radicals and alkaryl radicals; and Z and Z each represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing five or six atoms in the heterocyclic ring;
- a photographic element comprising a support having deposited thereon a silver halide emulsion prepared by a process comprising:
- ' A is nitrogen or An is an acid anion
- W, X and Y are independently selected from the group consisting of hydrogen, alkyl radicals, aryl radicals, cycloalkyl radicals and alkaryl radicals; and R and R are independently selected from the group consisting of alkyl radicals, aryl radicals, cycloalkyl radicals and alkaryl radicals; and
- Z and Z each represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing five or six atoms in the heterocyclic ring;
Abstract
Cyanine and azacyanine dyes are used as non-polymeric peptizers in dispersions of silver halides.
Description
Wmted States Patent 1 1 [111 ,850,645
Herz et a1. 1 Nov. 26, 1974 [54] NON-POLYMERIC PEPTIZERS FOR SILVER 2,441,529 5/1948 Brookcr et a1 96/140 HALIDE SUSPENSIONS 2,573,178 12/1951 Derbyshire 61 a1. 96/139 3,130,197 4/1964 Seefelder et a1. 96/139 [751 Inventors: Arthur Herman Herz; David Frank 3,496,065 2/1970 Russell 96/94 R x OBrien, both of Rochester, NY. 3,620,737 11/1971 Etter et a] 96/363 g ee Eastman o ak Company, 3,697,282 10/1972 Rlester et a1 96/139 Rochester, NY. OTHER PUBLICATIONS Filed? 14, 1973 Harrow'et a1; Laboratory Manual of Biochem. 1960, [211 App}. NO; 388,316 W. B. Saunderg Co., Phi1a., pages 70-71.
Primary Examiner-David Klein [52] CL g 7 Assistant ExaminerAlfonso T. Suro Pico 511 lm. c1 G036 1/24, 603C 1/00 WW/13mm Thomas [58] Field of Search 96/139, 140, 94 R, 114.7,
96/67; 195/4 [57] ABSTRACT 56] References Ched Cyanine and azacyanipedyes are used as non- UNITED STATES PATENTS polymerlc peptlzers 1n dlsperslons 0f sllver halldes.
2,030,050 5/1937 Kendall 96/139 16 Claims, N0 Drawings NON-POLYMERIC PEPTIZERS FOR SILVER HALIDE SUSPENSIONS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to photography and more particularly to a process for preparing substantially binderfree silver halide crystals for use in light radiation sensitive photographic elements and to the products prepared thereby.
2. Description of the Prior Art Conventional photographic elements employ a support material coated with a photographic emulsion that typically includes photosensitive silver halide crystals dispersed in a hydrophilic colloid such as gelatin. In many instances, gelatin or another hydrophilic colloid is an advantageous constitutent of a photographic element. The use of a hydrophilic colloid binder to promote adequate adhesion between the photosensitive species and the support, however, can be attended by certain related disadvantages that pertain to various photographic situations. Typical binder colloids absorb light of short wavelengths (e.g., ultraviolet rays); as such, the binder material can determine the short wavelength limit of usefulness for any given photographic element. The presence of such binder colloids operates to impede preparation of high quality, ultraviolet-sensitive photographic elements such as those used in astronomical studies.
Moreover, developing agents are required to penetrate the colloid in order to develop a photographic image on the photosensitive material. Additionally, the hydrophilic colloid tends to attract moisture which can adversely affect the stability and image producing capability of the photographic element. Further, special 35 measures must be taken to insure adequate adhesion between the normally hydrophobic support and the hy drophilic colloid binder. To avoid the use of a colloid binder, it is known to prepare photographic elements having thin, binder-free layers of microcrystalline silver halide coated by vacuum deposition techniques wherein the silver halide crystals are formed in situ on the support. Such coating means. however, require spe-- cialized apparatus to carry out the coating operation in a sealed system under conditions of elevated tempera ture and reduced pressure. Additionally, the binderless, microcrystalline silver halilde layers so deposited are subject both to non-uniform photographic response and to deterioration upon storage, the deterioration generally resulting from such factors as pressurecaused abrasion fog.
It is possible to produce monodispersed and crystalographically defined silver halide dispersions in the absence of polymeric vehicles, but these dispersions are known to be both highly dilute and difficult to reproduce. See, for example, Journal of Colloid Science, Vol. 16, p. 581, (1961 and Journal of Colloid Science, Vol. 19, p. 606, (1964). It is also possible to remove gelatin by enzyme hydrolysis from conventionally prepared monodisperse silver halide-gelatin systems as described, for example, in Journal of Colloid and Interface Science, Vol. 23, p. 277, (1967); British Pat. No. 761,014 issued Nov. 7, 1956; British Pat. No. 811,907
issued Apr. 15, 1959; British Pat. No. 1,115,625 issued 65 SUMMARY OF THE INVENTION The present invention comprises the use of cyanine and azacyanine dyes as non-polymeric peptizers in dispersions of silver halides.
More particularly, the present invention comprises a process for preparing dispersions of silver halides comprising:
A. reacting a water-soluble silver salt with a watersoluble halide in aqueous solution in the presence of gelatin whereby a stable gelatinosilver halide photographic emulsion is formed;
25 B. adding to said silver halide emulsion at least one dye of the structure wherein:
A is nitrogen or Cl o-c) v \il l n is 0, l or 2;
An is an acid anion;
W, X and Y are independently selected from the group'consisting of hydrogen, alkyl radicals, aryl radicals, cycloalkyl radicals and alkaryl radicals; and R and R are independently selected from the group consisting of alkyl radicals, aryl radicals, cycloalkyl radicals and alkaryl radicals; and Z and Z each represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing five or six atoms in the heterocyclic ring;
C. hydrolyzing-said gelatin in the presence of said dye by means of at least one proteolytic enzyme;
D. separating the silver halide and said dye adsorbed thereto, and
E. redispersing said silver halide.
Another embodiment of the present invention comprises the silver halide products prepared by the fore- 60 going process. I
DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention provides for the replacement of gelatin in preformed silver halide-gelatin dispersions by simple, monomeric organic compounds which are defined herein as being non-polymeric peptizers. These compounds are adsorbed to the silver halide surface and are not affected by the mild enzymatic hydrolysis conditions which are required for gelatin removal. It is a characteristic property of the present peptizers that they not only prevent the irreversible agglomeration of individual silver halide particles, but also interfere with recrystallization processes (Ostwald ripening) and thus help maintain the dispersity and crystal habit of the original silver halide dispersion. It should be noted that the effectiveness of cyanines as restrainers of Ostwald ripening is known in the art, see E. Moisar Grundlagen der Photographischen Prozesse Mit Silberhalogeniden, Akad. Verlagsgesellschaft, Vol. 2, pp. 627-631; Frankfurt am Main (1968).
The term radiation-sensitive, as utilized herein, is descriptive of chemical species (silver salts) that are activated by exposure to electromagnetic radiation to typically provide latent images that can be intensified by various photographic development techniques to provide visible images. The subject silver salts are radiation-sensitive and include species that are lightsensitive. However, radiation-sensitive" comprehends responsiveness to activating radiation both withinand without the visible portion of the spectrum. In addition to photosensitivity or visible light sensitivity, radiationsensitive refers to the responsiveness of an activatable silver salt species through a wide segment of electromagnetic radiation including, for example, x-radiation, ultraviolet radiation, infrared radiation and the like.
The preformed, radiation-sensitive silver salt crystals prepared according to the practice of this invention include those of the silver halides typically employed in gelatino-silver halide photographic emulsions, such as silver bromide, silver chloride and silver iodide. Additionally, mixtures of these halides are advantageously utilized, as are co-crystals, such as, for example, silver bromoiodide, silver chlorobromide, silver chloroiodide, silver chlorobromoiodide, and the like.
The non-polymeric peptizers employed in the practice of this invention are cyanines, azacyanines and related compounds, all having the structure:
In the foregoing structure, A is nitrogen or wherein n is 0, l or 2 and W, X and Y are independently selected from the group consisting of hydrogen, alkyl radicals, aryl radicals, cycloalkyl radicals and alkaryl radicals. As defined herein, the terms alkyl, aryl," cycloalkyl" and alkaryl include the substituted derivatives thereof such as, for example, alkyl substituted derivatives, halogensubstituted derivatives, sulfonate-substituted derivatives, carboxyl-substituted derivatives, aryl-substituted derivatives and the like. Where alkyl radicals are employed, it is preferred that they have from 1 to 12 carbon atoms and most preferred that they have from one to four carbon atoms, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and isomers thereof. Where aryl radicals are employed, it is preferred that they be aryl radicals of from 6 to 12 carbon atoms, e.g., benzene, xylene,'toluene, ethyl benzene, butyl benzene, napthylene, chlorobenzene, chlorotoluene, bromonapthylene, and the like. Among the cycloalkyl radicals that can be employed can be listed: cyclopentane, cyclohexane, chlorocyclohexane, bromocyclohexane, and the like. Benzyl radicals and phenethyl radicals are examples of the aryl radicals which can be employed in the dye structures used in this invention.
R and R in the above dye structure are independently collected from the group consisting of alkyl radicals, aryl radicals, cycloalkyl radicals and alkaryl radicals, which radicals are as defined above for W, X and Y. An represents an acid anion such as hydroxide, chloride, bromide, p-toluenesulfonate methanesulfonate, methylsulfate, ethylsulfate, perchlorate, etc. Z and Z each represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing from five to six atoms in the heterocyclic ring, e.g., thiazole, 4- phenylthiazole, 4,5-diphenylthiazole, 4-( 2- thienyl)thiazole, 4-methylthiazole, benzothiazole, 4-
chlorobenzothiazole, 4-methylbenzothiazole, 4- methoxybenzothiazole, 4-ethoxybenzothiazole, 4- phenylbenzothiazole, 5-chlorobenzothiazole, 5- bromobenzothiazole, S-methylbenzothiazole, 5- methoxybenzothiazole, 5-ethoxybenzothiazole, 5- phenylbenzothiazole, 6-chlorobenzothiazole, 6- bromobenzothiazole, 6-methylbenzothiazole, 6- methoxybenzothiazole, -ethoxybenzothiazole, 4- phenyloxazole, benzoxazole, 5-chlorobenzoxazole, 5- methylbenzoxazole, 5-bromobenzoxazole, 5- methoxybenzoxazole, S-ethoxybenzoxazole, 5-
phenylbenzoxazole, l,3-dialkyl, l,3-diaryl or l-alkyl-3- aryl, imidazoles and benzimidazoles, such as 5-chlorol,3-dialkyl benzimidazoles, 5-chloro- -chloro-l,3- diaryl benzimidazoles, 5,6-dichloro-l,3-dialkyl benzimidazoles, 5,6-dichloro-1,3-diaryl benzimidazoles, 5- methoxy-l,3-dialkyl benzimidazoles, 5-methoxy-l,3- diaryl benzimidazoles, 5-methoxy-l,3-diaryl benzimidazoles, 5-cyano-l,3-dialkyl benzimidazoles, 5-cyanol,3-diaryl benzimidazoles, l,3-dialkylnaphth[ 1,2- d]imidazole, l,3-diarylnaphth[2,l-d]-imidazole, 4- methylselenazole, 4-phenylselenazole, selenazole, benzoselenazole, 5-chlorobenzoselenazole, a-naphthothiazole, B-naphthothiazole, quinoline, 6- methylquinoline, 6-methoxyquinoline, 6- ethoxyquinoline, 6-chloroquinoline, 4- methoxyquinoline, 4-ethoxyquinoline, 4-
methylquinoline, 8-methoxyquinoline, B-methylquinoline, 4-chloroquinoline, 3,3-dimethylindolenine, etc.
In the practice of the process of this invention, substantially complete removal of gelatin is effected by enzyme hydrolysis as described in Weiss, Ericson and Herz, J. Colloid and Interface Science, Vol. 23, p. 277 i967). Any enzymes suitable for the intended purpose can be employed, for example, pepsin, trypsin, papain, ficin, pancreatin, and the like. H. T. Proteolytic Takamine, available from Miles Chemical Company, Elkhart, Indiana, has been found to be particularly effective, and is preferred. The amount of enzyme employed will, of course, be dependent upon the activity of the particular enzyme to be used, but, in general, amounts 'in=the range of from about 0.1 to about 2 grams of enzyme per grams of gelatin will be effective.
It is critical to the practice of the present invention that the non-polymeric peptizer be added to the silver halide prior to hydrolysis of the gelatin with the proteolytic enzyme. When this is done, the resulting silver halide particles, after purification, will be found to have retained their original size and morphology. If the nonpolymeric peptizer is added to the dispersion after completion of the gelatin hydrolysis, the dispersion will contain large agglomerates of silver halide particles whose morphology has changed drastically.
The concentration of the non-polymeric peptizer will vary depending upon the size and morphology of the crystals being peptized and on the special characteristics of the particular peptizer. In general, however, levels of non-polymeric peptizer of about 0.05 to about grams per mole of silver halide have been found to be effective and such levels are preferred.
In some cases, it may be desirable to remove the nonpolymeric peptizer from the silver halide surface. In such instances, peptizing compounds which can be desorbed by acid are particularly useful. Since acidinduced desorption of these peptizers causes rapid agglomeration of the silver halide suspension which cannot be reversed by subsequent neutralization, it will be convenient to deposit the silver halide particles first on a suitable support and then to desorb the nonpolymeric peptizer by the acid wash. The resulting silver halide layers, which contain no organic peptizers, retain their original particle size and crystal habit.
It should be recognized that the non-polymeric peptizers employed in the practice of this invention can be cationic, anionic or zwitterionic depending upon the identity of the groups chosen for R and R. For example, when R =R' alkyl (e.g., --C H then the molecule will be a cationic compound, which upon adsorption to silver halide will increase its positive charge density. If both substituents contain acid residue (e.g., R R (CH;), CO Na) then the organic molecule will be anionic and, upon adsorption, will tend to increase the negative charge at the silver halide/solution interface. A similar increase in negative charge density will be observed when the molecule is zwitterionic (e.g., R C H R (CH SO seeWeiss et al., J. Colloid and Interface Science, 23, 277 (1967).
Accordingly, by choosing an appropriate cyanine or mixture of cyanines, most preferably at levels between 0.05 and 1.0 gram per mole of silver halide, it will be possible to adjust the surface charge and zeta-potential at the silver halide/solution interface to an optimum for controlling the stability of the dispersion and the eventual deposition of the silver halide particles by charge control methods.
Since many cyanines are not only strongly adsorbed, but are also colored and efficient spectral sensitizers, their use as peptizers might be limited if they could not be decolorized or removed from the silver halide system. Both processes can be achieved by protonation. This reversible reaction, which is facilitated in cyanines with basic nuclei such as those derived from quinoline or benzimidazole, .decolorizes the dye so that it is no longer a spectral sensitizer. See Feldman et al., J. Phys. Chem., 72, 2008 (1968). Furthermore, as compared with the dye, the colorless protonation product is weakly bound to the silver halide substrate. Hence, as noted above, adsorbed dye can be readily and irreversibly removed from the silver halide surface by treatment with dilute acid.
The following examples are included for a further understanding of the invention.
emulsion (450 ml. per mole) having 3.5 grams of gelatin per silver mole was added to 1000. ml. of 10' M KBr. A solution of anhydro-S,5',6,6 tetrachlorol, l ',3-triethyl-3 -(3-sulfobutyl)benzimidazolocarbocyanine hydroxide (0.012 g.) in methanol ml.) was added to the dispersion. Sufficient dye was used to give monolayer coverage on the silver bromide. The mixture was stirred at 40C. and an aqueous solution of Takamine (0.5 g. in 150 ml.) was added. After stirring for 2 hours, the mixture was centrifuged for 30 minutes at 750 rpm. The supernatant was poured off and the grains were used in 1,000 ml. 10 M KBr. The centrifuged treatment and redispersal in 10 M KBr was repeated twice and yielded a gelatin-free dispersion of dyed cubic silver bromide in 10' M KBr. Electron microscopic examination of the silver bromide particles gave no indication of agglomeration or clumping or of changes in the perfection of the cubic crystal habit. Part B A sheet of polyethylene coated paper was passed for a few seconds through an aqueous colloidal suspension of boehmite alumina. The paper was rinsed with distilled water to remove excess alumina and was dried at about 25C. This dry paper was then passed for a few seconds through the silver bromide suspension prepared in Part A. The coating was then rinsed again with distilled water in order to remove excess silver bromide and was allowed to dry at 25C. Part C A strip of the treated paper of Part B was exposed through a diffraction grating (360-720 nm) containing a superimposed neutral step tablet, developed for about 5 seconds in Kodak Developer D-l9, held briefly in an acetic acid stop bath, fixed and then washed in running water. The resulting silver image extended to about 600 nm.
EXAMPLE 2 A second coating sample prepared as in Example 1 was rinsed consecutively in two 10" M KBr solutions for one minute, the first solution containing 0.1 M HNO;,. Upon exposing and developing as before, no spectral sensitization was observed and the image formed only in the intrinsic adsorption region of the silver bromide. Similar results were obtained when other acids, such as toluene sulfonic acid, were employed. The results indicated that the dye had been removed and electron micrographs gave no evidence of any morphological changes in the silver bromide substrate which was now free of organic surface impurities.
EXAMPLE 3 was added to the dispersion. This provides a. 50 percent surface coverage of the silver bromide. Results similar to those of Example 1 were obtained.
EXAMPLE 4 The same procedure as in Example I was repeated except that a solution of anhydro--chloro-l,l ,3- triethyl-3 3-sulfopropyl benzimidazolocarbocyanine hydroxide (0.01 l g.) in methanol (150 ml.) was added to the dispersion as the peptizer. Again, results equivalent to those of Example 1 were obtained.
EXAMPLE 5 The same procedure as in Example 1 was repeated except that a solution of anhydro-3-methyl-3-( 3- sulfopropyl)-8-azathiacyanine hydroxide (0.008 g.) in methanol (50 ml.) was added to the dispersion as the peptizer. Again, results equivalent to those of Example 1 were obtained except that the resulting image did not extend past the intrinsic sensitivity of the silver bromide.
This invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
What is claimed is:
l. A process for preparing dispersions of silver halides comprising:
A. reacting a water-soluble silver salt with a watersoluble halide in aqueous solution in the presence of gelatin whereby a stable gelatino-silver halide photographic emulsion is formed;
B. adding to said silver halide emulsion at least one dye of the structure wherein:
A is nitrogen or l w \X Y n n is 0. l or 2;
An is an acid anion;
W, X and Y are independently selected from the group consisting of hydrogen, alkyl radicals. aryl radicals, cycloalkyl radicals and alkaryl radicals; and R and R are independently selected from the group consisting of alkyl radicals, aryl radicals, cycloalkyl radicals and alkaryl radicals; and
Z and 2' each represents the non-metallic atoms nec essary to complete a heterocyclic nucleus contain ing five or six atoms in the heterocyclic ring;
C. hydrolyzing said gelatin in the presence of said dye by means of at least one proteolytic enzyme;
D. separating the silver halide and said dye adsorbed thereto, and
E. redispersing said silver halide.
2. The process of claim 1 further comprising the step of removing the dye by protonation.
3. The process of claim 1 wherein the dye is present in a concentration of from about 0.05 to about 10 grams per'mole of silver halide.
4. The process of claim 1 wherein the proteolytic enzyme is present in a concentration of from about 0.1
gram to about 2 grams of enzyme per grams of gelattn.
5. The process of claim 1 wherein the proteolytic enzyme is H. T. Proteolytic Takamine.
6. The process of claim 1 wherein the dye is anhydro- 5,5',6,6-tetrachlorol ,l ,3-triethyl-3-( 3-sulfobutyl)- benzimidazolocarbocyanine hydroxide.
7. The process of claim 1 wherein the dye is anhydro- 5-chl0rol ,l ,3-triethyl-3 3-sulfopropyl )ben- Zimidazolocarbocyanine hydroxide.
8. The process of claim 1 wherein the dye is anhydro- 3-methyl-3'-(3-sulfopropyl)-8-azathiacyanine hydroxide.
9. A process for preparing dispersions of silver halides comprising:
A. reacting a water-soluble silver salt with a watersoluble halide in aqueous solution in the presence of gelatin whereby a stable gelatine silver halide photographic emulsion is formed;
B. adding to said silver halide emulsion from about 0.05 to about 10 grams per mole of silver halide of at least one dye of the structure wherein:
A is nitrogen or An is an acid anion;
W, X and Y are independently selected from the group consisting of hydrogen, alkyl radicals, aryl radicals, cycloalkyl radicals and alkaryl radicals; and R and R are independently selected from the group consisting of alkyl radicals, aryl radicals, cycloalkyl radicals and alkaryl radicals; and
Z and Z each represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing five or six atoms in the heterocyclic ring;
C. hydrolyzing said gelatin in the presence of said dye by means from about 0.1 gram to about 2 grams of at least one proteolytic enzyme per 100 grams of gelatin;
D. separating the silver halide and said dye adsorbed thereto, and
E. redispersing said silver halide.
10. The process of claim 9 further comprising the step of removing the dye by protonation.
11. The process of claim 9 wherein the proteolytic enzyme is H. T. Proteolytic Takamine.
12. The process of claim 9 wherein the dye is anhydro-5,5,6,6'-tetrachlorol ,l ',3-triethyl-3'-( 3- sulfobutyl(benzimidazolocarbocyanine hydroxide.
13. The process of claim 9 wherein the dye is anhydro-5-chlorol ,l ,3-triethyl-3'-( 3-sulfopropyl )benzimidazolocarbocyanine hydroxide.
14. The process of claim 9 wherein the dye is anhydro-3 methyl-3-'-(3-sulfopropyl)-8-azathiacyanine hydroxide.
15. A photographic silver halide emulsion prepared by process comprising:
A. reacting a water-soluble silver salt with a watersoluble halide in aqueous solution in the presence of gelatin whereby a stable gelatino silver halide photographic emulsion is formed;
B. adding to said silver halide emulsion at least one dye of the structure wherein:
A is nitrogen or n is 0, l or 2;
An is an acid anion;
W, X and Y are independently selected from the group consisting of hydrogen, alkyl radicals, aryl radicals, cycloalkyl radicals and alkaryl radicals; and R and R are independently selected from the group consisting of alkyl radicals, aryl radicals, cycloalkyl radicals and alkaryl radicals; and Z and Z each represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing five or six atoms in the heterocyclic ring;
C. hydrolyzing said gelatin in the presence of said dye by means of at least one proteolytic enzyme;
D. separating the silver halide and said dye adsorbed thereto, and
E. redispersing said silver halide.
16. A photographic element comprising a support having deposited thereon a silver halide emulsion prepared by a process comprising:
A. reacting a water-soluble silver salt with a watersoluble halide in aqueous solution in the presence of gelatin whereby a stable gelatino-silver halide photographic emulsion is formed; B. adding to said silver halide emulsion at least one dye of the structure wherein:
' A is nitrogen or An is an acid anion;
W, X and Y are independently selected from the group consisting of hydrogen, alkyl radicals, aryl radicals, cycloalkyl radicals and alkaryl radicals; and R and R are independently selected from the group consisting of alkyl radicals, aryl radicals, cycloalkyl radicals and alkaryl radicals; and
Z and Z each represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing five or six atoms in the heterocyclic ring;
C. hydrolyzing said gelatin in the presence of said dye by means of at least one proteolytic enzyme;
D. separating the silver halide and said dye absorbed thereto, and
E. redispersing said silver halide.
Claims (16)
1. A PROCESS FOR PREPARING DISPERSIONS OF SILVER HALIDES COMPRISING: A. REACTING A WATER-SOLUBLE SILVER SALT WITH A WATER-SOLUBLE HALIDE IN AQUEOUS SOLUTION IN THE PRESENCE OF GELATIN WHEREBY A STABEL GELATINO-SILVER HALIDE PHOTOGRAPHIC EMULSION IS FORMED; B. ADDING TO SAID SILVER HALIDE EMULSION AT LEAST ONE DYE OF THE STRUCTURE
2. The process of claim 1 further comprising the step of removing the dye by protonation.
3. The process of claim 1 wherein the dye is present in a concentration of from about 0.05 to about 10 grams per mole of silver halide.
4. The process of claim 1 wherein the proteolytic enzyme is present in a concentration of from about 0.1 gram to about 2 grams of enzyme per 100 grams of gelatin.
5. The process of claim 1 wherein the proteolytic enzyme is H. T. Proteolytic Takamine.
6. The process of claim 1 wherein the dye is anhydro-5,5'' ,6,6'' -tetrachloro-1,1'' ,3-triethyl-3''-(3-sulfobutyl)benzimidazolocarbocyanine hydroxide.
7. The proCess of claim 1 wherein the dye is anhydro-5-chloro-1, 1'',3-triethyl-3''-(3-sulfopropyl)benzimidazolocarbocyanine hydroxide.
8. The process of claim 1 wherein the dye is anhydro-3-methyl-3''-(3-sulfopropyl)-8-azathiacyanine hydroxide.
9. A process for preparing dispersions of silver halides comprising: A. reacting a water-soluble silver salt with a water-soluble halide in aqueous solution in the presence of gelatin whereby a stable gelatino silver halide photographic emulsion is formed; B. adding to said silver halide emulsion from about 0.05 to about 10 grams per mole of silver halide of at least one dye of the structure
10. The process of claim 9 further comprising the step of removing the dye by protonation.
11. The process of claim 9 wherein the proteolytic enzyme is H. T. Proteolytic Takamine.
12. The process of claim 9 wherein the dye is anhydro-5,5'' ,6, 6''-tetrachloro-1,1'' ,3-triethyl-3''-(3-sulfobutyl(benzimidazolocarbocyanine hydroxide.
13. The process of claim 9 wherein the dye is anhydro-5-chloro-1,1'' ,3-triethyl-3'' -(3-sulfopropyl)benzimidazolocarbocyanine hydroxide.
14. The process of claim 9 wherein the dye is anhvdro-3-methyl-3'' -(3-sulfopropyl)-8-azathiacyanine hydroxide.
15. A photographic silver halide emulsion prepared by process comprising: A. reacting a water-soluble silver salt with a water-soluble halide in aqueous solution in the presence of gelatin whereby a stable gelatino silver halide photographic emulsion is formed; B. adding to said silver halide emulsion at least one dye of the structure
16. A photographic element comprising a support having deposited thereon a silver halide emulsion prepared by a process comprising: A. reacting a water-soluble silver salt with a water-soluble halide in aqueous solution in the presence of gelatin whereby a stable gelatino-silver halide photographic emulsion is formed; B. adding to said silver halide emulsion at least one dye of the structure
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US00388316A US3850645A (en) | 1973-08-14 | 1973-08-14 | Non-polymeric peptizers for silver halide suspensions |
| CA204,202A CA1025266A (en) | 1973-08-14 | 1974-07-05 | Non-polymeric peptizers for silver halide suspensions |
| GB3502874A GB1454452A (en) | 1973-08-14 | 1974-08-08 | Binderless silver halide dispersions and photographic materials containing them |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US00388316A US3850645A (en) | 1973-08-14 | 1973-08-14 | Non-polymeric peptizers for silver halide suspensions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3850645A true US3850645A (en) | 1974-11-26 |
Family
ID=23533611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00388316A Expired - Lifetime US3850645A (en) | 1973-08-14 | 1973-08-14 | Non-polymeric peptizers for silver halide suspensions |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US3850645A (en) |
| CA (1) | CA1025266A (en) |
| GB (1) | GB1454452A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5965345A (en) * | 1995-12-12 | 1999-10-12 | Eastman Kodak Company | Co-dispersion of sensitizing dyes |
| EP1045283A1 (en) * | 1999-04-16 | 2000-10-18 | Agfa-Gevaert N.V. | Radiation-sensitive emulsion, light-sensitive silver halide photographic film material and radiographic intensifying screen-film combination |
| US6200743B1 (en) | 1999-04-16 | 2001-03-13 | Agfa-Gevaert, N.V. | Radiation-sensitive emulsion, light-sensitive silver halide photographic film material and radiographic intensifying screen-film combination |
| US6472137B1 (en) * | 1999-11-26 | 2002-10-29 | Agfa-Gevaert | Light-sensitive silver halide photographic film material and radiographic intensifying screen-film combination |
| US20040096775A1 (en) * | 2001-03-21 | 2004-05-20 | Urs Lehmann | Optical recording materials having high storage density |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2080050A (en) * | 1934-08-03 | 1937-05-11 | Ilford Ltd | Sensitization of photographic emulsions |
| US2441529A (en) * | 1943-12-28 | 1948-05-11 | Eastman Kodak Co | Carbocyanine dyes containing a mesocycloalkyl group |
| US2578178A (en) * | 1949-12-16 | 1951-12-11 | Gen Aniline & Film Corp | Azathiazolone cyanine dyes and their preparation |
| US3130197A (en) * | 1961-07-14 | 1964-04-21 | Basf Ag | Production of azamonomethinecyanines of the benzothiazole series |
| US3496065A (en) * | 1966-03-11 | 1970-02-17 | Minnesota Mining & Mfg | Treatment of gelatin with nucleic acid-degrading enzymes |
| US3620737A (en) * | 1968-08-09 | 1971-11-16 | Eastman Kodak Co | Etching of differentially hardened plates by enzymes |
| US3697282A (en) * | 1968-11-09 | 1972-10-10 | Agfa Gevaert Ag | Silver halide emulsions which are spectrally sensitized and which contain color couplers |
-
1973
- 1973-08-14 US US00388316A patent/US3850645A/en not_active Expired - Lifetime
-
1974
- 1974-07-05 CA CA204,202A patent/CA1025266A/en not_active Expired
- 1974-08-08 GB GB3502874A patent/GB1454452A/en not_active Expired
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2080050A (en) * | 1934-08-03 | 1937-05-11 | Ilford Ltd | Sensitization of photographic emulsions |
| US2441529A (en) * | 1943-12-28 | 1948-05-11 | Eastman Kodak Co | Carbocyanine dyes containing a mesocycloalkyl group |
| US2578178A (en) * | 1949-12-16 | 1951-12-11 | Gen Aniline & Film Corp | Azathiazolone cyanine dyes and their preparation |
| US3130197A (en) * | 1961-07-14 | 1964-04-21 | Basf Ag | Production of azamonomethinecyanines of the benzothiazole series |
| US3496065A (en) * | 1966-03-11 | 1970-02-17 | Minnesota Mining & Mfg | Treatment of gelatin with nucleic acid-degrading enzymes |
| US3620737A (en) * | 1968-08-09 | 1971-11-16 | Eastman Kodak Co | Etching of differentially hardened plates by enzymes |
| US3697282A (en) * | 1968-11-09 | 1972-10-10 | Agfa Gevaert Ag | Silver halide emulsions which are spectrally sensitized and which contain color couplers |
Non-Patent Citations (1)
| Title |
|---|
| Harrow et al; Laboratory Manual of Biochem. 1960, W. B. Saunderg Co., Phila., pages 70 71. * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5965345A (en) * | 1995-12-12 | 1999-10-12 | Eastman Kodak Company | Co-dispersion of sensitizing dyes |
| EP1045283A1 (en) * | 1999-04-16 | 2000-10-18 | Agfa-Gevaert N.V. | Radiation-sensitive emulsion, light-sensitive silver halide photographic film material and radiographic intensifying screen-film combination |
| US6200743B1 (en) | 1999-04-16 | 2001-03-13 | Agfa-Gevaert, N.V. | Radiation-sensitive emulsion, light-sensitive silver halide photographic film material and radiographic intensifying screen-film combination |
| US6472137B1 (en) * | 1999-11-26 | 2002-10-29 | Agfa-Gevaert | Light-sensitive silver halide photographic film material and radiographic intensifying screen-film combination |
| US20040096775A1 (en) * | 2001-03-21 | 2004-05-20 | Urs Lehmann | Optical recording materials having high storage density |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1454452A (en) | 1976-11-03 |
| CA1025266A (en) | 1978-01-31 |
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