US2753263A - Silver halide emulsion containing a polymeric polyamine as an acid dye mordant - Google Patents
Silver halide emulsion containing a polymeric polyamine as an acid dye mordant Download PDFInfo
- Publication number
- US2753263A US2753263A US379467A US37946753A US2753263A US 2753263 A US2753263 A US 2753263A US 379467 A US379467 A US 379467A US 37946753 A US37946753 A US 37946753A US 2753263 A US2753263 A US 2753263A
- Authority
- US
- United States
- Prior art keywords
- polymeric
- silver halide
- photographic
- polyamines
- halide emulsion
- 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
- 229920000768 polyamine Polymers 0.000 title description 60
- 239000000839 emulsion Substances 0.000 title description 41
- -1 Silver halide Chemical class 0.000 title description 30
- 229910052709 silver Inorganic materials 0.000 title description 24
- 239000004332 silver Substances 0.000 title description 24
- 239000000980 acid dye Substances 0.000 title description 9
- 229920000642 polymer Polymers 0.000 description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 30
- 239000000084 colloidal system Substances 0.000 description 18
- 238000006386 neutralization reaction Methods 0.000 description 17
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- 239000000975 dye Substances 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- 108010010803 Gelatin Proteins 0.000 description 10
- 229920000159 gelatin Polymers 0.000 description 10
- 239000008273 gelatin Substances 0.000 description 10
- 235000019322 gelatine Nutrition 0.000 description 10
- 235000011852 gelatine desserts Nutrition 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 9
- 150000003839 salts Chemical group 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 8
- 150000001721 carbon Chemical group 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 229940105305 carbon monoxide Drugs 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- CREXVNNSNOKDHW-UHFFFAOYSA-N azaniumylideneazanide Chemical group N[N] CREXVNNSNOKDHW-UHFFFAOYSA-N 0.000 description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 4
- 229910001864 baryta Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000006268 reductive amination reaction Methods 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 229920002284 Cellulose triacetate Polymers 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 3
- 150000001241 acetals Chemical class 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- OIDPCXKPHYRNKH-UHFFFAOYSA-J chrome alum Chemical compound [K]OS(=O)(=O)O[Cr]1OS(=O)(=O)O1 OIDPCXKPHYRNKH-UHFFFAOYSA-J 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000005213 imbibition Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940117927 ethylene oxide Drugs 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 241000206672 Gelidium Species 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920002494 Zein Polymers 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
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- RZUBARUFLYGOGC-MTHOTQAESA-L acid fuchsin Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=C(N)C(C)=CC(C(=C\2C=C(C(=[NH2+])C=C/2)S([O-])(=O)=O)\C=2C=C(C(N)=CC=2)S([O-])(=O)=O)=C1 RZUBARUFLYGOGC-MTHOTQAESA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000011230 binding agent Substances 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
- 229920003086 cellulose ether Polymers 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 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
- HRMOLDWRTCFZRP-UHFFFAOYSA-L disodium 5-acetamido-3-[(4-acetamidophenyl)diazenyl]-4-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].OC1=C(C(=CC2=CC(=CC(=C12)NC(C)=O)S(=O)(=O)[O-])S(=O)(=O)[O-])N=NC1=CC=C(C=C1)NC(C)=O.[Na+] HRMOLDWRTCFZRP-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 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
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-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
- 150000002431 hydrogen Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 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
- 238000005406 washing Methods 0.000 description 1
- 239000005019 zein Substances 0.000 description 1
- 229940093612 zein Drugs 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
- G03C1/835—Macromolecular substances therefor, e.g. mordants
-
- 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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/22—Subtractive cinematographic processes; Materials therefor; Preparing or processing such materials
- G03C7/25—Dye-imbibition processes; Materials therefor; Preparing or processing such materials
Definitions
- This invention relates to photography and more particularly to photographic materials containing mordanting agents. Still more particularly, it relates to photographic elements having at least one water-permeable colloid silver halide emulsion containing a polymeric polyamine having at least one unsubstituted hydrogen atom on the amine group. The invention also relates to processes of mordanting and dye images utilizing such materials.
- An object of this invention is to provide improvements in the art of mordanting acid dyes in photographic Another object is to provide new photographic film and paper elements wherein the silver halide emulsion layers contain polymeric nitrogenous compounds which do not have a deleterious effect on the silver halide grains. A further object is to A still further object is to provide such It has been discovered that photographic films and papers having a strong mordanting action on acid dyes can be made by incorporating in the. water-permeable 'silver halide emulsions thereof a polymeric polyamine having a main polymer chain consisting solely of carbon atoms and containing a plurality of amino groups .in Which the amino nitrogen has at least one hydrogen atom.
- the polymeric polyamines in question are selected from the class consisting of (a) polymeric polyamines in which the amino nitrogen, having at least one hydrogen atom, is directly attached by a single bond to a carbon atom of the main polymer chain, and (b) polymeric polyamines containing primary amino nitrogen atoms linked to a carbon atom of the main polymer chain through a methylene (-CHz-) group. Mixtures of two or more of the polyamines can be used.
- polymeric polyamines described in the foregoing paragraph are characterized by having a main polymer chain consisting solely of carbon atoms and further char- 'ice acterized by having recurring substituent groups of the formula:
- R1 is H or an alkyl radical of 1 to 12 carbon atoms, i. e., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl; and x is the cardinal number of 0 or 1.
- the compounds comprehended by this general formula have molecular Weights from 300 to 50,000.
- the polymeric polyamines used in accordance with one aspect of this invention are obtained by the reductive amination of a monoolefin/carbon monoxide polymer.
- These polymeric polyamines have a main polymer chain consisting solely of carbon atoms and contain as lateral substituents a plurality of amino groups, Where R1 has the same meaning as above, attached directly to a carbon atom of the main polymer chain.
- R1 has the same meaning as above
- RiNH (n Where n is an integer from 3 to 40 and R1 has the same significance as in Formula I.
- n is an integer from 3 to 40 and R1 has the same significance as in Formula I.
- polymers made from other olefins they will have similar structures except that the -CHz-CH2- is replaced by a radical or a CllHa on2oradical where propylene and isobutylene are used as the olefin.
- the polymeric polyamines used in the silver halide dispersions are obtaine'dby the reduction of a linear polymer containing units selected from the group consisting of acrylonitrile and alpha-methacrylonitrile units, said polymeric polyamineliaving a main polymer chain consisting solely of carbon atoms with the primary amino (-NH2) groups attached to the said main polymer chain through methylene (-CH2) groups which are lateral substituents thereon.
- -NH2 primary amino
- -CH2 methylene
- n is a positive integer of 1 to 10.
- the polymeric polyamines described above that are useful in accordance with the present invention may be made after the manner described in Hoehn U. S. 2,495,255 patented January 20, 1950, and Pinkney U. S. 2,585,583 patented February 12, 1952.
- the useful polymeric polyamines may have a neutralization equivalent from 50 to 1,000 but preferably have a neutral ization equivalent in the range from 150 to 500.
- neutralization equivalent is meant the weight of polyamine required to neutralize one equivalent weight of any strong acid.
- the photographic elements e. g., film or paper hearing at least one water-permeable colloid silver halide emulsion containing one or more of the polymeric polyamines described above can be made in various manners.
- the photographic films or paper can be made by any conventional method and the polymeric polyarnine introduced into the photographic emulsion layer by impregnating it with an aqueous solution of the polymeric polyamine. Since the additionsalts of the polymeric polyamines have a markedly higher solubility than the free bases, the polyamines are generally added in the form of the addition salt. This is conveniently done by dissolving the polymeric polyamine in aqueous acid, e. g., dilute aqueous acetic acid and impregnating the waterpermeable colloid silver halide emulsion layer with the resulting solution.
- aqueous acid e. g., dilute aqueous acetic acid
- the polymeric polyamines can be added to the water-permeable colloid silver halide emulsion prior to coating, that is, an emulsion which is made in the usual manner is admixed with an aqueous solution containing an addition salt, e. g., acetic acid salt of the polymeric amine.
- an addition salt e. g., acetic acid salt of the polymeric amine.
- the water-permeable colloids used in the emulsions may be any of the usual colloids used by photographic manufacturers.
- the colloid may be gelatin, agaragar, albumin, polyglycuronic acid, zein, collodion, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate and interpolymers thereof with unsaturated materials such as ethylene, styrene, maleic acid, etc. which have hydrophilic properties, polyvinyl acetals, e. g., the acetal of polyvinyl alcohol with acetaldehyde or benzaldehyde or water-soluble or hydrophilic cellulose derivatives.
- Suitable hydrophilic or water-permeable colloids of the above types are described in U. S. Patents 2,110,491, 2,211,323, 2,276,322, 2,276,323, 2,286,215 and 2,397,866.
- the proportion of polymeric polyamine to waterpermeable colloid silver halide emulsion may vary over a fairly wide range. Thus from 2.0 to 100.0 grams of the mordant (the polymeric polyamine) in the form of the acid addition salt may be used for each 100 grams of gelatin or other water-permeable colloid used as the binding agent in the emulsion.
- Example I A gelatino silver chloride emulsion of a kind suitable for preparing a photographic printing paper of the contact type was made and 3 one-liter portions were separated. To these 3 emulsions there were added, from a 2% aqueous acetic acid solution, 1.25, 2.5 and 5.0 grams of the acetic acid addition salt of the polyamines obtained by the reductive amination of the polyketones prepared by the copolymerization of ethylene and carbon monoxide in the ratios of 6 to 1, 6.9 to 1 and 10.4 to 1,
- These polyamines had molecular weights of 660, 1100 and 1480 and neutralization equivalents of 574, 352 and 506, respectively. They were prepared after the manner described in Hoehn U. S. Patent No. 2,495,255. The three aqueous emulsions were coated onto a baryta-coated sheet of paper and dried. The resulting photographic papers were exposed to light and then fixed in a 24% aqueous solution of NazSzOaSHzO, washed and dried. The three papers were then treated in an acid dye solution of the following composition:
- Example H An aqueous gelatino silver chloride emulsion of the kind used in making photographic printing papers of the contact type was prepared and divided into several portions.
- No added ingredients were made to one control portion of the emulsion and chrome alum was added to a second portion.
- This solution was added in the quantities given in the following table to further respective portions of the silver chloride 61111117 sion. These portions were then coated onto a barytacoated sheet of paper.
- the respective photographic papers were exposed to a standard negative and then developed for one minute in a solution made of the following constituents:
- chrome alum is an effective mordant, it has the disadvantage that it causes rapid hardening of the emulsion so that often coating cannot be accomplished due to such hardening.
- Example III A gelatino silver iodobromide emulsion of the positive type was prepared for coating. It was divided into portions. To respective portions there were added 3.66 grams of the polyamines listed below per 100 grams of gelatin. The resulting emulsions were coated onto a cellulose triacetate film base bearing a thin gelatin anchor layer and dried. The resulting film elements were fixed in 24% aqueous NazSzOaSI-IzO solution, washed, dried and dipped into a magenta dye solution of the type given in Example I for a period of ten minutes. The films were cut in half and one half was quickly rinsed in water and the other half washed for a period of one hour. The two halves were dried and the dye densities determined as in Example H with the results given in the following table:
- polyamine was obtained by the reduction of a copolymer of 4 to 1 mol ratio and was used in the (b)
- This polymeric poiyamine was obtained by the reduction of a butadienc/methaerylonitrilc copolymer of 4 to 1 mo] ratio and was used in the form of the acetic acid addition salt which was made by dissolving the polyamine in 3 aqueous acetic acid.
- This polymeric polyamine is the same type as (b) but has a 4.5 to 1 mol ratio.
- This polymeric polyamine is the same as I being made from the reductive amination of oxide polymerization product.
- Each of the polymeric polyamines, a, Z7 and c were made after the manner described in U. S. Patent No. 2,585,583.
- the polymeric amide (d) was made after the manner described in U. S. Patent No. 2,495,255.
- Photographic films of the type described in Example iii are useful in making cine color prints by imbibition dye transfer procedures.
- a dry matrix film can be introduced into a dye bath containing any suitable acid dye of the appropriate color and dyed.
- the dyed matrix is rinsed in water or dilute acetic acid and the excess blown oif.
- a premordantcd film of the type described in Example Hi is soaked in water at pH 7 for 10 seconds at 70 F.
- the dyed matrix is then contacted with the premordanted film.
- the matrix and mordanted films are left in emulsion contact for a period of about one minute at 100 to 150 F.
- the two films are then stripped apart and the matrix washed in water and either dried for storage or redyed for a further imbibition printing process.
- Example IV A gelatino-;silver iodobromide emulsion of the positive type was preparedfor coating. .It was divided into two that described in Example the ethylene/carbon men equal portions. No mordant was added to one portion and to the other portion there was added 14.8 gramsof the polymeric amine of butadiene/methacrylonitrile having a neutralization equivalent of 365 described under (b) of Example 111 per grams of gelatin. The resulting emulsions were coated onto cellulose triacetate bases bearing a thin anchoring layer and dried. The resulting light-sensitive elements were exposed and proc essed as follows:
- Example V An emulsion prepared as in Example III was divided into three parts and 27 grams per hundred grams of gelatin of each of the acetate, and iodide salts of the polymeric amine-of butadiene/methacrylonitrile copolymer (BB/MAN) described under (1;) of Example ilIwere added to two of the divided parts respectively. The fifthi portion contained no mordanting agent.”
- Example IV were processed and tested as shown in Example IV except. that the samples were also submitted to one hour washing as in Example Ill and the following results were observed.
- polymeric polyamines In place of the specific polymeric polyamines given in the foregoing examples one may substitute other polymeric amines described in theforegoing patents having the requisite neutralization equivalent. Additional useful polyamines include isobutylene/ethylene/carbon monox ide polymeric amine, propylene/ethylene/carbon monoxe.
- the mordanted films and papers of this invention are useful in various types of dye printing or imbibition printing operations. Thus, they are useful in the preparation of three color dye transfer prints on paper supports, in the preparation of monochrome dyed prints for special effects and for hand colored color prints.
- the present invention is not limited to the use of a baryta-coated paper or a cellulose triacetate film base as the water-permeable silver halide layers containing the polymeric polyamines can be deposited on various supports.
- the support may be composed of practically any type of transparent film or any type of paper which is resistant to photographic processing solutions.
- the film may be composed of superpolymers, e. g., linear polyamides, cellulose nitrate, polyvinyl acetals, cellulose propionate, cellulose mixed esters, cellulose ethers, vinyl chloride and copolymers, styrene, acrylonitrile and copolymers, polyesters, e.
- the photographic films and papers of this invention have the advantage that they have a strong mordanting action on acid dyes.
- a further advantage resides in the fact that the polymeric polyamines cause little or no fog in the resulting light-sensitive silver halide emulsion layers.
- a still further advantage resides in the fact that the polymeric polyamines do not adversely affect the stability of the resulting emulsions. Thus, no significant loss of speed or fogging occurs upon aging of the film elements.
- Another advantage of the invention is that the mordants are easy to use and do not have a significant hardening action on the conventional types of water-permeable colloids.
- a further advantage lies in the fact that polyamines have little or no effect on the physical characteristics of molten photographic emulsions before coating.
- a photographic element comprising a support hearing at least one water-permeable colloid silver halide emulsion layer containing at least one polymeric polyamine containing carbon, hydrogen and nitrogen atoms only and having a main polymer chain consisting solely of carbon atoms, said polyamines being taken from the class consisting of polymeric polyamines in which the amino nitrogen atom has at least one hydrogen atom attached thereto and is directly attached by a single bond to a carbon atom of the main polymer chain and polymeric polyamines containing amino nitrogen atoms directly attached to a carbon atom of the main polymer chain through a single methylene group, said amino nitrogen atoms having at least one hydrogen atom attached thereto, said polyamine having a molecular Weight from 300 to 50,000 and a neutralization equivalent from 50 to 1,000.
- a photographic element comprising a flexible sheet hearing at least one water-permeable colloid silver halide emulsion layer containing a polymeric polyamine having a polymer chain consisting solely of carbon atoms in which the amino nitrogen atom has at least one hydrogen atom attached thereto and the nitrogen atom is directly attached by a single bond to the carbon atom of the main polymer chain, said polyamine having a molecular weight from 300 to 50,000 and a neutralization equivalent from 50 to 1,000.
- a photographic element comprising a flexible sheet bearing at least one water-permeable colloid silver halide emulsion layer containing a polymeric polyamine con sisting of carbon, hydrogen and nitrogen atoms only and having a polymer chain consisting solely of carbon atoms containing primary amino nitrogen atoms directly attached to a carbon atom of the main polymer chain through a single methylene group, said polyamine having a molecular weight from 300 to 50,000 and a neutralization equivalent from 50 to 1,000.
- a photographic element comprising a flexible sheet bearing a water-permeable colloid silver halide emulsion layer containing a polymeric polyamine having a polymer chain consisting solely of carbon atoms having, as the sole units in the polymer chain, recurring intralinear units of the formula:
- n is a positive integer of 3 to 40 and R1 is a member taken from the group consisting of hydrogen and alkyl of 1 to 12 carbon atoms, said polyamines having a molecular weight from 300 to 50,000 and a neutralization equivalent from to 500.
- a photographic element comprising a flexible sheet bearing a water-permeable colloid silver halide emulsion layer containing a polymeric polyamine having a polymer chain consisting solely of carbon atoms having, as the sole units in the polymer chain, recurring intralinear units of the formula:
- n is a positive integer of 1 to 10, said polyamines having a molecular weight from 300 to 50,000 and a new tralization equivalent from 150 to 500.
- a photographic element comprising a flexible sheet bearing a water-permeable colloid silver halide emulsion layer containing a polymeric polyamine having a polymer chain consisting solely of carbon atoms having, as the sole units in the polymer chain, recurring intralinear units of the formula:
- n is an integer of 1 to 10 said polyamines having a molecular weight from 300 to 50,000 and a neutralization equivalent from 150 to 500.
- a photographic film comprising a flexible hydrophobic film base bearing at least one gelatin silver halide emulsion layer containing a polymeric polyamine having a polymer chain consisting solely of carbon atoms having, as the sole units in the polymer chains, recurring intralinear units of the formula:
- n is an integer of 3 to 40, said polyamines having a molecular weight from 300 to 50,000 and a neutralization equivalent from 150 to 500.
- a photographic film comprising a flexible hydrophobic film base hearing at least one gelatin silver halide emulsion layer containing a polymeric polyamine having a polymer chain consisting solely of carbon atoms having,
- n is a positive integer of 1 to 10, said polyamines having a molecular weight from 300 to 50,000 and a neutralization equivalent from 150 to 500.
- a photographic film comprising a flexible hydrophobic film base bearing at least one gelatin silver halide emulsion layer containing a polymeric polyamine having a polymer chain consisting solely of carbon atoms having, as the sole units in the polymer chain, recurring intralinear units of the formula:
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
silver halide emulsion layers.
United States Patent SILVER HALE EMULSIUN CONTAINING A POLYMERIC POLYAMTNE AS AN ACID DYE MORDANT Russell Houston Gray, Middletown Township, Monmouth County, N. .l., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Application September 10, 1953, Serial No. 379,467
16 Claims. (Cl. 95-7) This invention relates to photography and more particularly to photographic materials containing mordanting agents. Still more particularly, it relates to photographic elements having at least one water-permeable colloid silver halide emulsion containing a polymeric polyamine having at least one unsubstituted hydrogen atom on the amine group. The invention also relates to processes of mordanting and dye images utilizing such materials.
Various methods are known for mordanting acid dyes to Water-permeable colloid layers in photographic elements. These methods utilize both inorganic and organic compounds. In case of organic compounds, many of them which are useful in textile mordanting proce dures are not useful in photographic emulsions because the compounds have a deleterious effect on the silver halide grains. Polymeric quaternary salts have been proposed for the mordanting of acid dyes in the form of photographic images, but they have the disadvantage of causing excessive fog and affect the speed of the photographic emulsion. Polymeric quaternary salts also markedly afifect the viscosity and consequently the coating characteristics of the molten emulsion. Consequently, they can only be safely used in nonsensitive layers of photographic elements.
An object of this invention is to provide improvements in the art of mordanting acid dyes in photographic Another object is to provide new photographic film and paper elements wherein the silver halide emulsion layers contain polymeric nitrogenous compounds which do not have a deleterious effect on the silver halide grains. A further object is to A still further object is to provide such It has been discovered that photographic films and papers having a strong mordanting action on acid dyes can be made by incorporating in the. water-permeable 'silver halide emulsions thereof a polymeric polyamine having a main polymer chain consisting solely of carbon atoms and containing a plurality of amino groups .in Which the amino nitrogen has at least one hydrogen atom. The polymeric polyamines in question are selected from the class consisting of (a) polymeric polyamines in which the amino nitrogen, having at least one hydrogen atom, is directly attached by a single bond to a carbon atom of the main polymer chain, and (b) polymeric polyamines containing primary amino nitrogen atoms linked to a carbon atom of the main polymer chain through a methylene (-CHz-) group. Mixtures of two or more of the polyamines can be used.
The polymeric polyamines described in the foregoing paragraph are characterized by having a main polymer chain consisting solely of carbon atoms and further char- 'ice acterized by having recurring substituent groups of the formula:
I (CH RiNH wherein R1 is H or an alkyl radical of 1 to 12 carbon atoms, i. e., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl; and x is the cardinal number of 0 or 1. The compounds comprehended by this general formula have molecular Weights from 300 to 50,000.
The polymeric polyamines used in accordance with one aspect of this invention are obtained by the reductive amination of a monoolefin/carbon monoxide polymer. These polymeric polyamines have a main polymer chain consisting solely of carbon atoms and contain as lateral substituents a plurality of amino groups, Where R1 has the same meaning as above, attached directly to a carbon atom of the main polymer chain. These compounds, when exemplified by those made by the reductive amination of ethylene/carbon monoxide polymers, have a plurality of units of the following general formula:
RiNH (n Where n is an integer from 3 to 40 and R1 has the same significance as in Formula I. In the case of polymers made from other olefins, they will have similar structures except that the -CHz-CH2- is replaced by a radical or a CllHa on2oradical where propylene and isobutylene are used as the olefin.
In another important aspect of the invention, the polymeric polyamines used in the silver halide dispersions are obtaine'dby the reduction of a linear polymer containing units selected from the group consisting of acrylonitrile and alpha-methacrylonitrile units, said polymeric polyamineliaving a main polymer chain consisting solely of carbon atoms with the primary amino (-NH2) groups attached to the said main polymer chain through methylene (-CH2) groups which are lateral substituents thereon. These compounds as exemplified by butadiene/acrylonitrile or alpha-methacrylonitrile copolymers are composed of a plurality of units having the Formulae III and IV below:
wherein n is a positive integer of 1 to 10.
The polymeric polyamines described above that are useful in accordance with the present invention may be made after the manner described in Hoehn U. S. 2,495,255 patented January 20, 1950, and Pinkney U. S. 2,585,583 patented February 12, 1952. The useful polymeric polyamines, however, may have a neutralization equivalent from 50 to 1,000 but preferably have a neutral ization equivalent in the range from 150 to 500. By neutralization equivalent is meant the weight of polyamine required to neutralize one equivalent weight of any strong acid.
The photographic elements, e. g., film or paper hearing at least one water-permeable colloid silver halide emulsion containing one or more of the polymeric polyamines described above can be made in various manners. Thus the photographic films or paper can be made by any conventional method and the polymeric polyarnine introduced into the photographic emulsion layer by impregnating it with an aqueous solution of the polymeric polyamine. Since the additionsalts of the polymeric polyamines have a markedly higher solubility than the free bases, the polyamines are generally added in the form of the addition salt. This is conveniently done by dissolving the polymeric polyamine in aqueous acid, e. g., dilute aqueous acetic acid and impregnating the waterpermeable colloid silver halide emulsion layer with the resulting solution.
Alternatively, the polymeric polyamines can be added to the water-permeable colloid silver halide emulsion prior to coating, that is, an emulsion which is made in the usual manner is admixed with an aqueous solution containing an addition salt, e. g., acetic acid salt of the polymeric amine.
The water-permeable colloids used in the emulsions may be any of the usual colloids used by photographic manufacturers. Thus the colloid may be gelatin, agaragar, albumin, polyglycuronic acid, zein, collodion, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate and interpolymers thereof with unsaturated materials such as ethylene, styrene, maleic acid, etc. which have hydrophilic properties, polyvinyl acetals, e. g., the acetal of polyvinyl alcohol with acetaldehyde or benzaldehyde or water-soluble or hydrophilic cellulose derivatives. Suitable hydrophilic or water-permeable colloids of the above types are described in U. S. Patents 2,110,491, 2,211,323, 2,276,322, 2,276,323, 2,286,215 and 2,397,866.
The proportion of polymeric polyamine to waterpermeable colloid silver halide emulsion may vary over a fairly wide range. Thus from 2.0 to 100.0 grams of the mordant (the polymeric polyamine) in the form of the acid addition salt may be used for each 100 grams of gelatin or other water-permeable colloid used as the binding agent in the emulsion.
The invention will be further illustrated but is not intended to be limited by the following examples:
Example I A gelatino silver chloride emulsion of a kind suitable for preparing a photographic printing paper of the contact type was made and 3 one-liter portions were separated. To these 3 emulsions there were added, from a 2% aqueous acetic acid solution, 1.25, 2.5 and 5.0 grams of the acetic acid addition salt of the polyamines obtained by the reductive amination of the polyketones prepared by the copolymerization of ethylene and carbon monoxide in the ratios of 6 to 1, 6.9 to 1 and 10.4 to 1,
respectively. These polyamines had molecular weights of 660, 1100 and 1480 and neutralization equivalents of 574, 352 and 506, respectively. They were prepared after the manner described in Hoehn U. S. Patent No. 2,495,255. The three aqueous emulsions were coated onto a baryta-coated sheet of paper and dried. The resulting photographic papers were exposed to light and then fixed in a 24% aqueous solution of NazSzOaSHzO, washed and dried. The three papers were then treated in an acid dye solution of the following composition:
Grams Pontacyl Carmine 6B (Colour Index 57) 1.2 NaH2PO4l-I2O 15.0
H2O to make 1.0 liter.
and washed for 15 minutes. It was found that each of the photographic papers were fastly dyed by the acid magenta dye. The photographic emulsion containing the polymeric amine having the neutralization equivalent of 352 retained the greatest amount and that having the neutralization equivalent of 574 the least amount of dye.
Example H An aqueous gelatino silver chloride emulsion of the kind used in making photographic printing papers of the contact type was prepared and divided into several portions. A polymeric polyamine obtained by the reduction of a butadiene/acrylonitrile copolymer of 4 to 1 mol ratio and having a neutralization equivalent of 378 was dissolved in 2% aqueous acetic acid to form the acetic acid addition salt. No added ingredients were made to one control portion of the emulsion and chrome alum was added to a second portion. This solution was added in the quantities given in the following table to further respective portions of the silver chloride 61111117 sion. These portions were then coated onto a barytacoated sheet of paper. The respective photographic papers were exposed to a standard negative and then developed for one minute in a solution made of the following constituents:
Grams N-methyl-p-aminophenol sulfate 1.0 Sodium sulfite 15.0
Hydroquinone 4.0 Sodium carbonate (desiccated) 22.5 Potassium bromide 0.63
Water to make 1.0 liter.
with the results given in the following table:
Print Speed (Seconds of Exposure) 3.5 Months Aging at Grams Polyamine Acetate Salt Per Liter of Em ls Room Fresh Temperature None 20 25 1.42 19 20 2.84 17 18 6.65... 19 20 1.42 gm. chrome alum 25 36 The data given in the above table show that the poly 5 and the dye densities (d2) determined, with: the results given in the following table:
It should be noted that while chrome alum is an effective mordant, it has the disadvantage that it causes rapid hardening of the emulsion so that often coating cannot be accomplished due to such hardening.
Example III A gelatino silver iodobromide emulsion of the positive type was prepared for coating. It was divided into portions. To respective portions there were added 3.66 grams of the polyamines listed below per 100 grams of gelatin. The resulting emulsions were coated onto a cellulose triacetate film base bearing a thin gelatin anchor layer and dried. The resulting film elements were fixed in 24% aqueous NazSzOaSI-IzO solution, washed, dried and dipped into a magenta dye solution of the type given in Example I for a period of ten minutes. The films were cut in half and one half was quickly rinsed in water and the other half washed for a period of one hour. The two halves were dried and the dye densities determined as in Example H with the results given in the following table:
I Percent De- Neutralization crease in Dye Polymeric Polyamine Mord-ant Equivalent Density, 1-
Hour Washs (a) This polymeric utadiene/acrylonitrilc form of the acetic acid addition salt which was madeby dissolving the polyamine in 3% aqueous acetic acid.
polyamine was obtained by the reduction of a copolymer of 4 to 1 mol ratio and was used in the (b) This polymeric poiyamine was obtained by the reduction of a butadienc/methaerylonitrilc copolymer of 4 to 1 mo] ratio and was used in the form of the acetic acid addition salt which was made by dissolving the polyamine in 3 aqueous acetic acid.
(0) This polymeric polyamine is the same type as (b) but has a 4.5 to 1 mol ratio.
(d) This polymeric polyamine is the same as I being made from the reductive amination of oxide polymerization product. Each of the polymeric polyamines, a, Z7 and c were made after the manner described in U. S. Patent No. 2,585,583. The polymeric amide (d) was made after the manner described in U. S. Patent No. 2,495,255.
Photographic films of the type described in Example iii are useful in making cine color prints by imbibition dye transfer procedures. Thus, a dry matrix film can be introduced into a dye bath containing any suitable acid dye of the appropriate color and dyed. The dyed matrix is rinsed in water or dilute acetic acid and the excess blown oif. A premordantcd film of the type described in Example Hi is soaked in water at pH 7 for 10 seconds at 70 F. The dyed matrix is then contacted with the premordanted film. The matrix and mordanted films are left in emulsion contact for a period of about one minute at 100 to 150 F. The two films are then stripped apart and the matrix washed in water and either dried for storage or redyed for a further imbibition printing process. Example IV A gelatino-;silver iodobromide emulsion of the positive type was preparedfor coating. .It was divided into two that described in Example the ethylene/carbon men equal portions. No mordant was added to one portion and to the other portion there was added 14.8 gramsof the polymeric amine of butadiene/methacrylonitrile having a neutralization equivalent of 365 described under (b) of Example 111 per grams of gelatin. The resulting emulsions were coated onto cellulose triacetate bases bearing a thin anchoring layer and dried. The resulting light-sensitive elements were exposed and proc essed as follows:
The element was developed for 3%. minutes in a devel-- oper of the following composition:
Grams N-methyl-p-aminophenol sulfate 0.46 NazSOg 28.0
' Hydroquinone 3.4
Na2CO3H20 10.0 KBr 0.44?
Water to make 1.0 liter.
The element was then rinsed and fixed in the following composition:
a solution having Grams Sodium thiosulfate, Na2S2O3-5HzOt 240.0 Sodium sulfite 10.0 Sodium bisulfite; 25.0
Water to make 1.0 liter.
in the same way. The resolution in terms of lines per millimeter of the resultant transferred dye image which is a measure of mordanting power was determined microscopically andfound to be as shown in the following table:
Resolution (lines/millimeter) Mordant (grams/100 grams of gelatin) i Example V An emulsion prepared as in Example III was divided into three parts and 27 grams per hundred grams of gelatin of each of the acetate, and iodide salts of the polymeric amine-of butadiene/methacrylonitrile copolymer (BB/MAN) described under (1;) of Example ilIwere added to two of the divided parts respectively. The fifthi portion contained no mordanting agent." The samples:
were processed and tested as shown in Example IV except. that the samples were also submitted to one hour washing as in Example Ill and the following results were observed.
In place of the specific polymeric polyamines given in the foregoing examples one may substitute other polymeric amines described in theforegoing patents having the requisite neutralization equivalent. Additional useful polyamines include isobutylene/ethylene/carbon monox ide polymeric amine, propylene/ethylene/carbon monoxe.
ide polymeric amine, isobutylene/ carbon monoxide polymeric amine, propylene/ carbon monoxide polymeric amine, and polyallylamine.
The mordanted films and papers of this invention are useful in various types of dye printing or imbibition printing operations. Thus, they are useful in the preparation of three color dye transfer prints on paper supports, in the preparation of monochrome dyed prints for special effects and for hand colored color prints.
The present invention is not limited to the use of a baryta-coated paper or a cellulose triacetate film base as the water-permeable silver halide layers containing the polymeric polyamines can be deposited on various supports. Thus, the support may be composed of practically any type of transparent film or any type of paper which is resistant to photographic processing solutions. Thus, the film may be composed of superpolymers, e. g., linear polyamides, cellulose nitrate, polyvinyl acetals, cellulose propionate, cellulose mixed esters, cellulose ethers, vinyl chloride and copolymers, styrene, acrylonitrile and copolymers, polyesters, e. g., polyethylene terephthlates, vinyl acetate and copolymers, vinyl fluoride and copolymers, polyvinyl alcohol; transparentized paper, etc. The coated film base of Alles et al. 2,627,088 is especially useful.
The photographic films and papers of this invention have the advantage that they have a strong mordanting action on acid dyes. A further advantage resides in the fact that the polymeric polyamines cause little or no fog in the resulting light-sensitive silver halide emulsion layers. A still further advantage resides in the fact that the polymeric polyamines do not adversely affect the stability of the resulting emulsions. Thus, no significant loss of speed or fogging occurs upon aging of the film elements. Another advantage of the invention is that the mordants are easy to use and do not have a significant hardening action on the conventional types of water-permeable colloids. A further advantage lies in the fact that polyamines have little or no effect on the physical characteristics of molten photographic emulsions before coating.
What is claimed is:
l. A photographic element comprising a support hearing at least one water-permeable colloid silver halide emulsion layer containing at least one polymeric polyamine containing carbon, hydrogen and nitrogen atoms only and having a main polymer chain consisting solely of carbon atoms, said polyamines being taken from the class consisting of polymeric polyamines in which the amino nitrogen atom has at least one hydrogen atom attached thereto and is directly attached by a single bond to a carbon atom of the main polymer chain and polymeric polyamines containing amino nitrogen atoms directly attached to a carbon atom of the main polymer chain through a single methylene group, said amino nitrogen atoms having at least one hydrogen atom attached thereto, said polyamine having a molecular Weight from 300 to 50,000 and a neutralization equivalent from 50 to 1,000.
2. A photographic element comprising a flexible sheet hearing at least one water-permeable colloid silver halide emulsion layer containing a polymeric polyamine having a polymer chain consisting solely of carbon atoms in which the amino nitrogen atom has at least one hydrogen atom attached thereto and the nitrogen atom is directly attached by a single bond to the carbon atom of the main polymer chain, said polyamine having a molecular weight from 300 to 50,000 and a neutralization equivalent from 50 to 1,000.
3. An element as set forth in claim 2 wherein said sheet is a baryta-coated paper.
4. An element as set forth in claim 2 wherein said sheet is a hydrophobic film base.
5. A photographic element comprising a flexible sheet bearing at least one water-permeable colloid silver halide emulsion layer containing a polymeric polyamine con sisting of carbon, hydrogen and nitrogen atoms only and having a polymer chain consisting solely of carbon atoms containing primary amino nitrogen atoms directly attached to a carbon atom of the main polymer chain through a single methylene group, said polyamine having a molecular weight from 300 to 50,000 and a neutralization equivalent from 50 to 1,000.
6. An element as set forth in claim 5 wherein said sheet is a baryta-coated paper.
7. An element as set forth in claim 5 wherein said sheet is a hydrophobic film base.
8. A photographic element comprising a flexible sheet bearing a water-permeable colloid silver halide emulsion layer containing a polymeric polyamine having a polymer chain consisting solely of carbon atoms having, as the sole units in the polymer chain, recurring intralinear units of the formula:
wherein n is a positive integer of 3 to 40 and R1 is a member taken from the group consisting of hydrogen and alkyl of 1 to 12 carbon atoms, said polyamines having a molecular weight from 300 to 50,000 and a neutralization equivalent from to 500.
9. A photographic element comprising a flexible sheet bearing a water-permeable colloid silver halide emulsion layer containing a polymeric polyamine having a polymer chain consisting solely of carbon atoms having, as the sole units in the polymer chain, recurring intralinear units of the formula:
wherein n is a positive integer of 1 to 10, said polyamines having a molecular weight from 300 to 50,000 and a new tralization equivalent from 150 to 500.
10. A photographic element comprising a flexible sheet bearing a water-permeable colloid silver halide emulsion layer containing a polymeric polyamine having a polymer chain consisting solely of carbon atoms having, as the sole units in the polymer chain, recurring intralinear units of the formula:
where n is an integer of 1 to 10 said polyamines having a molecular weight from 300 to 50,000 and a neutralization equivalent from 150 to 500.
11. A photographic film comprising a flexible hydrophobic film base bearing at least one gelatin silver halide emulsion layer containing a polymeric polyamine having a polymer chain consisting solely of carbon atoms having, as the sole units in the polymer chains, recurring intralinear units of the formula:
wherein n is an integer of 3 to 40, said polyamines having a molecular weight from 300 to 50,000 and a neutralization equivalent from 150 to 500.
12. A film element as set forth in claim 11 wherein said base is composed of a polyethylene terephthalate.
13. A photographic film comprising a flexible hydrophobic film base hearing at least one gelatin silver halide emulsion layer containing a polymeric polyamine having a polymer chain consisting solely of carbon atoms having,
as the sole units in the polymer chain, recurring intralinear units of the formula:
H -(UHz--CHzCHg-CH2)n-CH2-- CHr-NH: wherein n is a positive integer of 1 to 10, said polyamines having a molecular weight from 300 to 50,000 and a neutralization equivalent from 150 to 500.
14. A film element as set forth in claim 12 wherein said film base is composed of polyethylene terephthalate.
15. A photographic film comprising a flexible hydrophobic film base bearing at least one gelatin silver halide emulsion layer containing a polymeric polyamine having a polymer chain consisting solely of carbon atoms having, as the sole units in the polymer chain, recurring intralinear units of the formula:
CH; (CH2-CH2-CH:CHa)n-CH:-( J- Ha-NH:
References Cited in the file of this patent UNITED STATES PATENTS 2,423,460 McQueen July 8, 1947 2,486,191 Minsk et a1 Oct. 25, 1949 FOREIGN PATENTS 648,472 Great Britain Ian. 3, 1951
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US379467A US2753263A (en) | 1953-09-10 | 1953-09-10 | Silver halide emulsion containing a polymeric polyamine as an acid dye mordant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US379467A US2753263A (en) | 1953-09-10 | 1953-09-10 | Silver halide emulsion containing a polymeric polyamine as an acid dye mordant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2753263A true US2753263A (en) | 1956-07-03 |
Family
ID=23497384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US379467A Expired - Lifetime US2753263A (en) | 1953-09-10 | 1953-09-10 | Silver halide emulsion containing a polymeric polyamine as an acid dye mordant |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2753263A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3075841A (en) * | 1956-06-19 | 1963-01-29 | Du Pont | Mordant treating process and elements containing same |
| US3174859A (en) * | 1959-09-24 | 1965-03-23 | Gevaert Photo Prod Nv | Process for obtaining multiple photographic positive images by diffusiontransfer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2423460A (en) * | 1944-03-31 | 1947-07-08 | Du Pont | Photographic elements containing polyamide dye intermediate layers |
| US2486191A (en) * | 1946-07-22 | 1949-10-25 | Eastman Kodak Co | Process of polymerizing acrylamide |
| GB648472A (en) * | 1948-02-25 | 1951-01-03 | Kodak Ltd | Improvements in the preparation of photographic emulsions |
-
1953
- 1953-09-10 US US379467A patent/US2753263A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2423460A (en) * | 1944-03-31 | 1947-07-08 | Du Pont | Photographic elements containing polyamide dye intermediate layers |
| US2486191A (en) * | 1946-07-22 | 1949-10-25 | Eastman Kodak Co | Process of polymerizing acrylamide |
| GB648472A (en) * | 1948-02-25 | 1951-01-03 | Kodak Ltd | Improvements in the preparation of photographic emulsions |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3075841A (en) * | 1956-06-19 | 1963-01-29 | Du Pont | Mordant treating process and elements containing same |
| US3174859A (en) * | 1959-09-24 | 1965-03-23 | Gevaert Photo Prod Nv | Process for obtaining multiple photographic positive images by diffusiontransfer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4225665A (en) | Photographic element in which the antistatic layer is interlinked in the base | |
| US3625694A (en) | Polymers polymeric mordants and elements containing same | |
| US3788855A (en) | Novel polymers and photographic elements containing same | |
| US3988157A (en) | Process for adhering hydrophilic layers to dimensionally stable polyester films | |
| EP0188264A2 (en) | Improved antistatic backing layer for a silver halide element | |
| US2892822A (en) | Acrylate copolymers containing quaternary ammonium and tertiary amine salt units | |
| JPH04501324A (en) | Photographic support material consisting of antistatic layer and barrier layer | |
| US2495918A (en) | Poly-n-vinyl lactam photographic silver halide emulsions | |
| US2839401A (en) | Photographic silver halide emulsions containing copolymeric mordants | |
| US2852386A (en) | Hydrophilic compositions | |
| US3075841A (en) | Mordant treating process and elements containing same | |
| US2734825A (en) | morgan | |
| US4166050A (en) | Method of increasing the viscosity of photographic coating solutions | |
| JPS6334457B2 (en) | ||
| US2753263A (en) | Silver halide emulsion containing a polymeric polyamine as an acid dye mordant | |
| US4914018A (en) | Antistatic photographic base and light-sensitive element | |
| US3819379A (en) | Silver halide photographic material for use in color photography | |
| US3211552A (en) | Multilayer photographic element for color photography | |
| US3655407A (en) | Method of coating dilute aqueous emulsions | |
| US3850639A (en) | Hydrophilic colloid silver halide emulsion hardened with a bis(vinyl-sulfonylmethyl) ether and an acrylic compound | |
| US2833650A (en) | Photographic emulsions | |
| US3746547A (en) | Process for producing a photographic light sensitive element | |
| US3832181A (en) | Photosensitive silver halide material containing a hydrophilic colloid hardened with a combination of formaldehyde and bis(vinylsulfonyl-methyl)ether | |
| US4370412A (en) | Aqueous hydrophilic colloid coating composition containing a combination of anionic surfactants | |
| US2615807A (en) | Stripping film and method of stripping |