US3532502A - Silver salts of pyridine carboxylic acids and photographic emulsions containing the same - Google Patents
Silver salts of pyridine carboxylic acids and photographic emulsions containing the same Download PDFInfo
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- US3532502A US3532502A US684956A US3532502DA US3532502A US 3532502 A US3532502 A US 3532502A US 684956 A US684956 A US 684956A US 3532502D A US3532502D A US 3532502DA US 3532502 A US3532502 A US 3532502A
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- United States
- Prior art keywords
- silver
- photographic
- emulsion
- carboxylic acids
- pyridine carboxylic
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- 239000000839 emulsion Substances 0.000 title description 30
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical class OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 title description 20
- -1 silver halides Chemical class 0.000 description 16
- 229910052709 silver Inorganic materials 0.000 description 11
- 239000004332 silver Substances 0.000 description 11
- 229940009188 silver Drugs 0.000 description 11
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 108010010803 Gelatin Proteins 0.000 description 7
- 150000001875 compounds Chemical group 0.000 description 7
- 229920000159 gelatin Polymers 0.000 description 7
- 239000008273 gelatin Substances 0.000 description 7
- 235000019322 gelatine Nutrition 0.000 description 7
- 235000011852 gelatine desserts Nutrition 0.000 description 7
- 150000003378 silver Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 229940081066 picolinic acid Drugs 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000004848 polyfunctional curative Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- GJGOWHNOGHVUJK-UHFFFAOYSA-M silver;pyridine-2-carboxylate Chemical compound [Ag+].[O-]C(=O)C1=CC=CC=N1 GJGOWHNOGHVUJK-UHFFFAOYSA-M 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- HAAYBYDROVFKPU-UHFFFAOYSA-N silver;azane;nitrate Chemical compound N.N.[Ag+].[O-][N+]([O-])=O HAAYBYDROVFKPU-UHFFFAOYSA-N 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl 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
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 2
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical group 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229940100890 silver compound Drugs 0.000 description 2
- 150000003379 silver compounds Chemical class 0.000 description 2
- JUDUFOKGIZUSFP-UHFFFAOYSA-M silver;4-methylbenzenesulfonate Chemical compound [Ag+].CC1=CC=C(S([O-])(=O)=O)C=C1 JUDUFOKGIZUSFP-UHFFFAOYSA-M 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical group COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920002678 cellulose Chemical class 0.000 description 1
- 239000001913 cellulose Chemical class 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000002508 contact lithography Methods 0.000 description 1
- 150000002012 dioxanes Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 239000010956 nickel silver Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001282 polysaccharide Chemical class 0.000 description 1
- 239000005017 polysaccharide Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 230000033458 reproduction Effects 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 229960001516 silver nitrate Drugs 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
Definitions
- This invention relates to light sensitive compositions. In one of its aspects this invention relates to certain novel light sensitive organic silver compounds. In another of its aspects, this invention relates to photographic systems and methods that employ organic silver compounds.
- the silver halides known in the prio art are generally the basis of photographic systems which have been found to be practical for photographic purposes. Certain organic acid silver salts have also been mentioned as being light sensitive and capable of development. However, the. known organic acid silver salts have never achieved significant commercial recognition as their sensitiviy to light is two to three times lower than that of the slowest silver halides generally used in present photographic elements.
- photographic systems employ as a light-sensitive element a silver salt of a pyridine carboxylic acid having the following formula:
- R represents substituents in one or more positions on the ring and can be hydrogen atoms, alkyl groups, alkoxy groups, carboxylic acid groups, carboxyalkylene groups, groups containing a carboxylic acid silver salt radical, and the like.
- R substituents are hydrogen atoms, carboxy groups, groups containing carboxylic acid silver salt radicals and the like.
- substantially all of the carboxy radicals on said compound form carboxylic acid silver salt radicals.
- Typical preferred compounds which form silver salts useful in photographic emulsions include picolinic acid having the formula:
- An important feature of this invention is the discovery of an organic silver salt which has a photographic speed comparable with conventional silver halide contact papers. Moreover, the ripening step often used with silver halide emulsions is not necessary with the new compounds of this invention to produce high sensitivity photographic elements.
- a radiation sensitive silver picolinate is to react a pyridine carboxylic acid, such as picolinic acid, with a soluble silver salt such as silver nitrate.
- the reaction proceeds in aqueous solution; preferably the temperature is maintained at from about 30 C. to about 40 C.
- any water-soluble silver salt can be used in the reaction such as silver sulfate, silver acetate, silver nitrate, silver perchlorate, and the like, or it can be a silver salt such as p-toluene sulfonate silver salt, and other suitable organo-silver complexes.
- Organic silver salts can also be chosen that will release to the solution, upon reaction with the pyridine carboxylic acid, an organic ion that is useful in a photographic emulsion, such as an acid, dye, hardener, etc.
- an organic ion that is useful in a photographic emulsion, such as an acid, dye, hardener, etc.
- silver p-toluenesulfonate, uopn reaction with picolinic acid will release sulfonic acid which contributes acid for a photographic emulsion.
- the silver salt is preferably silver nitrate or ammoniacal silver nitrate. The use of ammoniacal silver nitrate is preferred as it allows one to reduce the gelatin concentration in the preparation of an emulsion and increases the speed of the resultant emulsion.
- a hydrophilic colloid such as pigskin gelatin is used as the film forming binder.
- various colloids can be used in combination with the gelatin as vehicels or binding agents in the photographic emulsions ad elements employed in the practice of this invention.
- binding materials generally employed for this purpose including, for example, colloidal albumin, water soluble vinyl polymers as exemplified by mono and polysaccharides, cellulose derivatives, proteins, water soluble polyacrylamides, polyvinyl pyrrolidone and the like.
- the vehicle or binding agents can contain dispersed polymerized vinyl compounds, particularly those which increase the dimensional stability of photographic materials.
- Suitable synthetic polymers of this type include the Water insoluble acrylic interpolymers such as those containing units of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates and the like.
- the various layers of the photographic elements of this invention can be hardened with any suitable hardener, including for example, aldehyde hardeners, aziridine hardeners, hardeners which are derivatives of dioxane, oxypolysaccharides such as oxy-starch, oxy plant gums and the like.
- suitable hardener including for example, aldehyde hardeners, aziridine hardeners, hardeners which are derivatives of dioxane, oxypolysaccharides such as oxy-starch, oxy plant gums and the like.
- Typical flexible supports include those generally employed for photographic elements such as cellulose nitrate film, cellulose acetate film, polyvinylacetal film, polystyrene film, polyethylene terephthalate film and related films or resinous materials as well as, thin glass films, paper, and the like.
- Supports, such as paper, which are partially acetylated or coated with baryta or an a-olefin polymer, particularly a polymer of an a-olefin containing 2-10 carbon atoms, as exemplified by polyethylene, polypropylene, ethylene butene copolymers and the like also give good results.
- the photographic emulsions and elements of this invention can also contain additional addenda, particularly those known to be beneficial in photographic materials of this nature.
- they can contain stabilizers or antifoggants such as organic azoles, azaindenes, mercaptans, metal salts such as cadmium, lead, mercury, gold or other noble metal salts, spectral sensitizers such as the cyanines, merocyanines, complex (trinuclear) cyanines, complex (trinuclear) merocyanines, styryls, hemicyanines, speed increasing materials, such as polyalkylene glycols, onium salts and thio ethers, plasticizers, coating aids such as anionic, non-ionic and amphoteric surface active compounds and the like.
- stabilizers or antifoggants such as organic azoles, azaindenes, mercaptans, metal salts such as cadmium, lead, mercury, gold or other noble metal salts
- Inorganic and organic compounds may be added to the emulsion to adjust the pH value. Acids such as nitric, sulfuric, p-toluene sulfonic and the like may be used for this purpose.
- the optimum photographic properties for a pigskin gelatin emulsion are obtained at a pH of about 4. Depending upon the particular binding agents and addendum incorporated in the emulsion, the pH can be approximately adjusted to obtain the desired properties.
- the organic silver salts can be coated on a film support by any suitable emulsion coating method to produce a light sensitive layer on the support.
- the development and fixing of emulsions containing the silver salt of pyridine carboxylic acids can be generally carried out by methods applicable to silver halide emulsions.
- a developer which has been found especially satisfactory is sodium hydroxide-hydroquinone-elon developer.
- the following developing solution may be used:
- All those developing solutions may be used between 23 C. and 32 C. and, in general, the development rate increases with the pH of the developer.
- the fixing solution can generally be any fixing solution used for silver halide emulsions.
- EXAMPLE 1 Eight grams of pigskin gelatin are swollen in ml. of water. Twenty-five ml. of 0.6 N picolinic acid are added to this solution. Twenty-five ml. of 0.2 N silver nitrate are then added dropwise while stirring the mixture. The pH is maintained at about 4. The precipitation temperature is maintained at about 40 C. The emulsion is coated on a paper support at a coverage rate of 6 to 7 mg. of silver per dm. and is dried.
- the coated paper is exposed for 2 seconds to a tungsten 100 w. lamp placed at 20 cm. from an original.
- the exposed coating is then developed for 5 seconds in a developer obtained by mixing 500 ml. of composition A with 3 ml. of composition B:
- Composition A Elon 2.25 Na SO anhydrous 7.0 Hydroquinone 9.0 N212CO3 Water, to make 1 liter.
- Composition B KBr 1.0
- the D of the developed print is about 1.3 and the contrast is about 0.90.
- the photographic speed of the silver picolinate coated paper is approximately that of a conventional contact speed silver chloride paper.
- EXAMPLE 2 Twelve grams of pigskin gelatin are disposed in 230 ml. of water. Twenty ml. of 0.6 N picolinic acid are then added. Fifty ml. of ammoniacal silver nitrate are then added to the mixture over a period of about 20 minutes. The pH is maintained at about 4. Precipitation conditions are maintained for this mixture at about 40 C.
- the emulsion is coated on a paper support at a coverage rate of 6 to 7 mg. of silver per dm. and dried.
- the coated paper is then dried, exposed, developed and fixed as in Example 1.
- the coated paper has a photographic speed suitable for contact printing, approximately that of a silver chloride emulsion.
- the finished print has a neutral-tone silver image of good gradation.
- the D of developed image was about 1.4 and the contrast was about 0.95.
- the emulsion is coated on a paper support as mentioned in Example 2.
- the coated paper is then dried and exposed for 2 seconds to a tungsten 300 w. lamp placed at 30 cm. from an original.
- the exposed paper is then developed and fixed as in Example 1.
- the finished print has a neutral-tone silver image of good gradation.
- D of the deevloped image is about 1.05 (above fog) and the contrast was about 0.83.
- a photographic emulsion comprising a compound having the formula:
- R represents substituents in one or more positions on the ring of hydrogen atoms, alkyl groups, alkoxy groups, carboxylic acid groups, carboxyalkylene groups, or groups containing a carboxylic acid silver salt radical.
- a photographic element comprising a support and at least one layer thereon comprising an emulsion according to claim 1.
- a photographic element according to claim 5 wherein said emulsion comprises silver picolinate.
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Pyridine Compounds (AREA)
Description
United States Patent "ice 2 Int. (:1. dose 1/02 US. Cl. 96114.6 6 Claims ABSTRACT OF THE DISCLOSURE This invention relates to silver salts of pyridine carboxylic acids and processes for preparing the same. In one aspect emulsions of the new silver salts exhibit photographic properties.
This invention relates to light sensitive compositions. In one of its aspects this invention relates to certain novel light sensitive organic silver compounds. In another of its aspects, this invention relates to photographic systems and methods that employ organic silver compounds.
The silver halides known in the prio art are generally the basis of photographic systems which have been found to be practical for photographic purposes. Certain organic acid silver salts have also been mentioned as being light sensitive and capable of development. However, the. known organic acid silver salts have never achieved significant commercial recognition as their sensitiviy to light is two to three times lower than that of the slowest silver halides generally used in present photographic elements.
It is accordingly an object of the present invention to provide a novel organic silver salt having sensitivity to radiation similar to that achieved in silver chloride emulsions. Another object is to provide a novel photographic system comprising the novel organic sil-ver salts. Another object is to provide novel means for obtaining photographic reproductions. Another object is to provide a photographic element containing a novel organic silver salt. Still another object is to provide an organic silver salt system with a photographic speed similar to that of conventional contact silver halide papers. Other objects and advantages will appear from the following descrip tion and claims.
According to the present invention photographic systems employ as a light-sensitive element a silver salt of a pyridine carboxylic acid having the following formula:
wherein R represents substituents in one or more positions on the ring and can be hydrogen atoms, alkyl groups, alkoxy groups, carboxylic acid groups, carboxyalkylene groups, groups containing a carboxylic acid silver salt radical, and the like. Preferably the R substituents are hydrogen atoms, carboxy groups, groups containing carboxylic acid silver salt radicals and the like. In certain preferred embodiments substantially all of the carboxy radicals on said compound form carboxylic acid silver salt radicals.
3,532,502 Patented Oct. 6, 1970 Typical preferred compounds which form silver salts useful in photographic emulsions include picolinic acid having the formula:
/C 0 OH quinolinic acid or pyridine-2,3-dicarboxy1ic acid having the following formula:
1 C O OH i0 0 OH and like compounds.
An important feature of this invention is the discovery of an organic silver salt which has a photographic speed comparable with conventional silver halide contact papers. Moreover, the ripening step often used with silver halide emulsions is not necessary with the new compounds of this invention to produce high sensitivity photographic elements.
Various methods may be used to make the silver salt of pyridine carboxylic acids. For example, one method for the synthesis of a radiation sensitive silver picolinate is to react a pyridine carboxylic acid, such as picolinic acid, with a soluble silver salt such as silver nitrate. The reaction proceeds in aqueous solution; preferably the temperature is maintained at from about 30 C. to about 40 C. Generally any water-soluble silver salt can be used in the reaction such as silver sulfate, silver acetate, silver nitrate, silver perchlorate, and the like, or it can be a silver salt such as p-toluene sulfonate silver salt, and other suitable organo-silver complexes. Organic silver salts can also be chosen that will release to the solution, upon reaction with the pyridine carboxylic acid, an organic ion that is useful in a photographic emulsion, such as an acid, dye, hardener, etc. For example, silver p-toluenesulfonate, uopn reaction with picolinic acid will release sulfonic acid which contributes acid for a photographic emulsion. However, in the present invention the silver salt is preferably silver nitrate or ammoniacal silver nitrate. The use of ammoniacal silver nitrate is preferred as it allows one to reduce the gelatin concentration in the preparation of an emulsion and increases the speed of the resultant emulsion.
In a preferred embodiment of this invention a hydrophilic colloid such as pigskin gelatin is used as the film forming binder. However, various colloids can be used in combination with the gelatin as vehicels or binding agents in the photographic emulsions ad elements employed in the practice of this invention. Among such materials are the natural and/or synethetic [binding materials generally employed for this purpose including, for example, colloidal albumin, water soluble vinyl polymers as exemplified by mono and polysaccharides, cellulose derivatives, proteins, water soluble polyacrylamides, polyvinyl pyrrolidone and the like. In addition to the hydrophilic colloids, the vehicle or binding agents can contain dispersed polymerized vinyl compounds, particularly those which increase the dimensional stability of photographic materials. Suitable synthetic polymers of this type include the Water insoluble acrylic interpolymers such as those containing units of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates and the like.
The various layers of the photographic elements of this invention can be hardened with any suitable hardener, including for example, aldehyde hardeners, aziridine hardeners, hardeners which are derivatives of dioxane, oxypolysaccharides such as oxy-starch, oxy plant gums and the like.
The photographic layers described herein can be coated on a wide variety of supports. Typical flexible supports include those generally employed for photographic elements such as cellulose nitrate film, cellulose acetate film, polyvinylacetal film, polystyrene film, polyethylene terephthalate film and related films or resinous materials as well as, thin glass films, paper, and the like. Supports, such as paper, which are partially acetylated or coated with baryta or an a-olefin polymer, particularly a polymer of an a-olefin containing 2-10 carbon atoms, as exemplified by polyethylene, polypropylene, ethylene butene copolymers and the like also give good results.
The photographic emulsions and elements of this invention can also contain additional addenda, particularly those known to be beneficial in photographic materials of this nature. For example, they can contain stabilizers or antifoggants such as organic azoles, azaindenes, mercaptans, metal salts such as cadmium, lead, mercury, gold or other noble metal salts, spectral sensitizers such as the cyanines, merocyanines, complex (trinuclear) cyanines, complex (trinuclear) merocyanines, styryls, hemicyanines, speed increasing materials, such as polyalkylene glycols, onium salts and thio ethers, plasticizers, coating aids such as anionic, non-ionic and amphoteric surface active compounds and the like.
Inorganic and organic compounds may be added to the emulsion to adjust the pH value. Acids such as nitric, sulfuric, p-toluene sulfonic and the like may be used for this purpose. The optimum photographic properties for a pigskin gelatin emulsion are obtained at a pH of about 4. Depending upon the particular binding agents and addendum incorporated in the emulsion, the pH can be approximately adjusted to obtain the desired properties.
The organic silver salts can be coated on a film support by any suitable emulsion coating method to produce a light sensitive layer on the support.
The development and fixing of emulsions containing the silver salt of pyridine carboxylic acids can be generally carried out by methods applicable to silver halide emulsions. A developer which has been found especially satisfactory is sodium hydroxide-hydroquinone-elon developer.
For example, when the development is carried out in a rapid process machine (for 1 to 2 seconds), the following developing solution may be used:
Water1 liter Ethanol100 ml. Elon g. Na SO anhydrous50 g. Hydroquinone15 g. NaOH-15 g. Potassium bromide2 g. pH=l1 Other developing solutions need longer development times. For example, the developing time is about 15 seconds with the following developer.
Water-1 liter Elon-2 g.
Na SO anhydrous g. Hydroquinone-5 g. Na2CO3'-25 g. Potassium bromide-1 g. pH: 10
All those developing solutions may be used between 23 C. and 32 C. and, in general, the development rate increases with the pH of the developer.
The fixing solution can generally be any fixing solution used for silver halide emulsions.
The invention can be further illustrated by the following examples of preferred embodiments thereof, although it will be understood that the examples are included merely for purposes of illustration and are not intended to limit the scope of the invention unless otherwise indicated.
EXAMPLE 1 Eight grams of pigskin gelatin are swollen in ml. of water. Twenty-five ml. of 0.6 N picolinic acid are added to this solution. Twenty-five ml. of 0.2 N silver nitrate are then added dropwise while stirring the mixture. The pH is maintained at about 4. The precipitation temperature is maintained at about 40 C. The emulsion is coated on a paper support at a coverage rate of 6 to 7 mg. of silver per dm. and is dried.
The coated paper is exposed for 2 seconds to a tungsten 100 w. lamp placed at 20 cm. from an original. The exposed coating is then developed for 5 seconds in a developer obtained by mixing 500 ml. of composition A with 3 ml. of composition B:
Composition A Elon 2.25 Na SO anhydrous 7.0 Hydroquinone 9.0 N212CO3 Water, to make 1 liter.
Composition B KBr 1.0
Benzothiazole 0.20
Water, to make 1 liter.
and fixed with a hypo solution. The D of the developed print is about 1.3 and the contrast is about 0.90. After exposing the images to a 250 w. xenon lamp for 4 hours no increase in fog is noticeable whereas the fog increase in a control silver chloride reflex copying type paper processed under the same conditions is 0.15.
The photographic speed of the silver picolinate coated paper is approximately that of a conventional contact speed silver chloride paper.
EXAMPLE 2 Twelve grams of pigskin gelatin are disposed in 230 ml. of water. Twenty ml. of 0.6 N picolinic acid are then added. Fifty ml. of ammoniacal silver nitrate are then added to the mixture over a period of about 20 minutes. The pH is maintained at about 4. Precipitation conditions are maintained for this mixture at about 40 C.
The emulsion is coated on a paper support at a coverage rate of 6 to 7 mg. of silver per dm. and dried. The coated paper is then dried, exposed, developed and fixed as in Example 1. The coated paper has a photographic speed suitable for contact printing, approximately that of a silver chloride emulsion. The finished print has a neutral-tone silver image of good gradation. The D of developed image was about 1.4 and the contrast was about 0.95.
EXAMPLE 3 Precipitation conditions of Example 2 are repeated, but picolinic acid is replaced by an equivalent amount of quinolinic acid.
The emulsion is coated on a paper support as mentioned in Example 2. The coated paper is then dried and exposed for 2 seconds to a tungsten 300 w. lamp placed at 30 cm. from an original. The exposed paper is then developed and fixed as in Example 1. The finished print has a neutral-tone silver image of good gradation. The
D of the deevloped image is about 1.05 (above fog) and the contrast was about 0.83.
Similar images are obtained with other silver salts of pyridine carboxylic acids such as isonicotinic acid, pyridine-2, 6-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, and the like.
The invention has been described with reference to preferred embodiments thereof, but it will be understood that variations and modifications of the invention can be made within the scope of the following claims.
We claim:
1. A photographic emulsion comprising a compound having the formula:
wherein R represents substituents in one or more positions on the ring of hydrogen atoms, alkyl groups, alkoxy groups, carboxylic acid groups, carboxyalkylene groups, or groups containing a carboxylic acid silver salt radical.
2. An emulsion according to claim 1 wherein said emulsion comprises silver picolinate.
3. An emulsion according to claim 1 wherein said emulsion comprises pigskin gelatin.
4. An emulsion according to claim 1 wherein substantially all R substituents on said compound are hydrogen atoms or groups containing a carboxylic acid silver salt radical.
5. A photographic element comprising a support and at least one layer thereon comprising an emulsion according to claim 1.
6. A photographic element according to claim 5 wherein said emulsion comprises silver picolinate.
NORMAN G. TORCHIN, Primary Examiner J. R. HIGHTOWER, Assistant Examiner
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR120945A FR1543449A (en) | 1967-09-14 | 1967-09-14 | New photosensitive compositions, new photographic materials and their preparation process |
Publications (1)
Publication Number | Publication Date |
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US3532502A true US3532502A (en) | 1970-10-06 |
Family
ID=8638286
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US684956A Expired - Lifetime US3532502A (en) | 1967-09-14 | 1967-11-22 | Silver salts of pyridine carboxylic acids and photographic emulsions containing the same |
Country Status (5)
Country | Link |
---|---|
US (1) | US3532502A (en) |
BE (1) | BE717140A (en) |
DE (1) | DE1797309A1 (en) |
FR (1) | FR1543449A (en) |
GB (1) | GB1224540A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3960908A (en) * | 1973-01-22 | 1976-06-01 | Fuji Photo Film Co., Ltd. | Process for preparing organosilver carboxylates |
US4157289A (en) * | 1977-05-06 | 1979-06-05 | Fuji Photo Film Co., Ltd. | Process for preparing slightly soluble silver salt grains |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3330663A (en) * | 1964-08-14 | 1967-07-11 | Agfa Gevaert Ag | Silver salts of sulfur-containing aliphatic carboxylic acids as lightsensitive compounds |
-
1967
- 1967-09-14 FR FR120945A patent/FR1543449A/en not_active Expired
- 1967-11-22 US US684956A patent/US3532502A/en not_active Expired - Lifetime
-
1968
- 1968-06-25 BE BE717140D patent/BE717140A/xx unknown
- 1968-09-11 DE DE19681797309 patent/DE1797309A1/en active Pending
- 1968-09-12 GB GB43420/68A patent/GB1224540A/en not_active Expired
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3330663A (en) * | 1964-08-14 | 1967-07-11 | Agfa Gevaert Ag | Silver salts of sulfur-containing aliphatic carboxylic acids as lightsensitive compounds |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3960908A (en) * | 1973-01-22 | 1976-06-01 | Fuji Photo Film Co., Ltd. | Process for preparing organosilver carboxylates |
US4157289A (en) * | 1977-05-06 | 1979-06-05 | Fuji Photo Film Co., Ltd. | Process for preparing slightly soluble silver salt grains |
Also Published As
Publication number | Publication date |
---|---|
FR1543449A (en) | 1968-10-25 |
DE1797309A1 (en) | 1971-11-25 |
GB1224540A (en) | 1971-03-10 |
BE717140A (en) | 1968-12-02 |
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