US3169863A - Pentaerythritol phosphoric acid ester sensitizers for photographic emulsions - Google Patents
Pentaerythritol phosphoric acid ester sensitizers for photographic emulsions Download PDFInfo
- Publication number
- US3169863A US3169863A US286924A US28692463A US3169863A US 3169863 A US3169863 A US 3169863A US 286924 A US286924 A US 286924A US 28692463 A US28692463 A US 28692463A US 3169863 A US3169863 A US 3169863A
- Authority
- US
- United States
- Prior art keywords
- phosphoric acid
- silver halide
- compound
- photographic
- silver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000839 emulsion Substances 0.000 title claims description 28
- BWCQUVUKWGCJCE-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;phosphoric acid Chemical compound OP(O)(O)=O.OCC(CO)(CO)CO BWCQUVUKWGCJCE-UHFFFAOYSA-N 0.000 title 1
- -1 SILVER HALIDE Chemical class 0.000 claims description 27
- 229910052709 silver Inorganic materials 0.000 claims description 18
- 239000004332 silver Substances 0.000 claims description 18
- 239000007859 condensation product Substances 0.000 claims description 12
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 8
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- ITVPBBDAZKBMRP-UHFFFAOYSA-N chloro-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound OP(O)(Cl)=O ITVPBBDAZKBMRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 17
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- DETXZQGDWUJKMO-UHFFFAOYSA-N 2-hydroxymethanesulfonic acid Chemical compound OCS(O)(=O)=O DETXZQGDWUJKMO-UHFFFAOYSA-N 0.000 description 6
- 150000003014 phosphoric acid esters Chemical class 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910001513 alkali metal bromide Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- GLZWNFNQMJAZGY-UHFFFAOYSA-N octaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCO GLZWNFNQMJAZGY-UHFFFAOYSA-N 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- WGKYSFRFMQHMOF-UHFFFAOYSA-N 3-bromo-5-methylpyridine-2-carbonitrile Chemical compound CC1=CN=C(C#N)C(Br)=C1 WGKYSFRFMQHMOF-UHFFFAOYSA-N 0.000 description 1
- FCSKOFQQCWLGMV-UHFFFAOYSA-N 5-{5-[2-chloro-4-(4,5-dihydro-1,3-oxazol-2-yl)phenoxy]pentyl}-3-methylisoxazole Chemical compound O1N=C(C)C=C1CCCCCOC1=CC=C(C=2OCCN=2)C=C1Cl FCSKOFQQCWLGMV-UHFFFAOYSA-N 0.000 description 1
- 241001479434 Agfa Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- IIRDTKBZINWQAW-UHFFFAOYSA-N hexaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCO IIRDTKBZINWQAW-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 229940043349 potassium metabisulfite Drugs 0.000 description 1
- 235000010263 potassium metabisulphite Nutrition 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 239000000837 restrainer Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940076133 sodium carbonate monohydrate Drugs 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
- G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides
-
- 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/305—Additives other than developers
- G03C5/3056—Macromolecular additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/15—Lithographic emulsion
Definitions
- n has the meaning given above, and the degree of condensation X of the product of esterification may be 1 or more, for instance 1-100, preferably 1-10.
- the substituent R may represent H or 3,lh9,853 i atented Feb. 16, l65
- any silver halide emulsions of the developing-out type which provide a high gamma when developed with developers containing formaldehyde may be used.
- the silver salts of such emulsions generally consist of silver chloride in a quantity of at least 50 mole percent. However, it is preferred to use emulsions in which the silver salts consist at least of 65 mole percent of silver chloride and accordingly 35 mole percent or less of silver bromide.
- the emulsions may further contain small amounts of silver iodide, such as 1 to 2 mole percent.
- the quantity of the above phosphoric acid esters to be added to the emulsion depends on the ratio of chloride to bromide in the emulsion, 10 to mg. per mol of silver halide may advantageously be used.
- the emulsions can in addition be chemically sensitized with salts of noble metals, such as gold salts, with sulfur compounds or with reducing agents.
- the emulsions can be optically sensitized with cyanine and merocyanine dyes.
- the developers which may be employed in our invention contain as essential components a phenol type de veloper, such as hydroquinone, an alkali,such as an alkali metal carbonate, sodium or potassium carbonate, formaldehyde bisulfite and a small amount of a restrainer, such as alkali metal bromide.
- a restrainer such as alkali metal bromide.
- the developer can also contain sodium hydroxide, boric acid, a sequesterin g agent.
- alkali metal carbonate and formaldehyde bisulfite the developer can contain, 'as a source of formaldehyde, paraformaldehyde, an alkali metal sulfite and a buffering agent, such as alkali metal bisulfite.
- Such developers are well known in the art and are for instance disclosed in US. Patents 2,184,053, 2,313,523, 2,902,367 and in British Patent 643,411.
- Such developers may contain for instance per one liter 15-25 grams or" hydroquinone, 30-70 grams of formaldehyde bisulfite, 30-90 grams of sodium carbonate monohydrate, 5-20 grams of boric acid and 1-5 grams of alkali metal bromide or 15-25 grams of hydroquinone, 5-10 grams of paraformaldehyde, 1-5 grams of potassium metabisulfite (cryst), 20-40 grams of anhydrous sodium sulphite, 5-15 grams of boric acid and l-5 grams of alkali metal bromide.
- the phosphoric acid esters of the present invention may be added to the above lithographic developers perferably in quantities of 30-300 mg. per liter.
- the addition of the phosphoric acid esters of the present invention to the emulsion and/or to the developer causes the gamma value to rise considerably during development, for instance from about 6-8 to above 15.
- the margin of time during development within which sharpness of raster dots may be obtained is increased from about one minute to 3 to 4 minutes.
- a formaldehyde containing developer having such an addition is less dependent upon temperature. Whereas a developer without this addition reacts to temperature increases of 1 to 2 C. with a marked reduction in the margin of time for development, good results may be obtained with developer temperatures of 15 to 40 C. if these phosphoric acid esters have been added. Owing to the increased time available for processing, the above graphic use.
- the phosphoric acid esters according to the invention are prepared by the usual methods used for esterification, and the degree of condensation of the esters may be infiuenced in the desired direction by varying the reaction time, the reaction temperature and the molar proportions of the reaction components.
- the condensation may for instance be carried through in a liquid alkaline medium, such as in pyridine or triethylamine or other tertiary amines, at temperatures of about 0 to 80 C., preferably to 50 C.
- the crystals may be isolated by suction filtration after some of the phosphorus oxychloride has been removed by evaporation in vacuo, and the crystals may then be washed with methylene chloride on the suction filter.
- condensation time is increased the degree of condensation X increases likewise.
- amount of octaethyleneglycol used for the reaction is increased up to 2 moles there are obtained condensation products in which both end groups are mainly formed by -'-(o cH cH oH- radicals.
- COMPOUND H 19.4 g. of tetraethylene glycol, 31.2 g. of pyridine and 30 g. of ester chloride (Ia) are reacted as described above and worked up. 27 g. of a viscous light brown oil are obtained. The color may be removed from the 10% aqueous solution by means of active charcoal and bleaching earth.
- the ioily liquid presumably consists mainly "of a compound of the following theoretical formula:
- COMPOUND W 41.4 g. of nonaethyleneglycol, 31.2 g. of pyridine and 30 g. of ester chloride (Ia) produce 20 g. of a brown syrupy polycondensate which is diluted with water to a 10% solution and purified with active charcoal and bleaching earth.
- ester chloride (Ia) produces 20 g. of a brown syrupy polycondensate which is diluted with water to a 10% solution and purified with active charcoal and bleaching earth.
- the following theoretical formula may be used to represent the highly viscous polycondensate:
- Example 1 A gelatine-silver halide emulsion the silver halide of which containing 15 mole percent of AgBr and mole percent of AgCl is Washed and then ripened to'maximurn sensitivity and 4-hydroxy-6-rnethyl-l,3,3a,7-tetrazaindole or other stabilizers and a wetting agent are then added, and the emulsion is poured on to a suitable film base (A).
- A suitable film base
- Example 2 An emulsion accordinging to Example 1 is divided into two portions. One portion (A) has no additive while the other portion (B) has added to it 80 mg. of Compound II per mole of silver halide. Each portion is then poured on to a film base. The two samples are then illuminated and developed as in Example 1.
- Example 3 An emulsion according to Example 1 is divided into a portion (A) without additive and a portion (B) with 80 mg. of Compound IH per mole of silver halide as additive, and the portions are poured on to a base and then treated as described under 1.
- Exampl e 4 Film strips (Agfa-lith-ortho) illuminated behind a stepped wedge are developed in the developer mentioned in Example 1 for varying time ranging from 1 to 4 minutes, at C.
- the same film samples are developed in the same developer after the addition of 100 rug/liter of Compound I.
- condensation pro-duct is the condensation product of one mol of a pentaerythritol ester of phosphorochloridic acid and about 1 to 2 mols of a polyethylene glycol.
- condensation product has the formula wherein R represents a member of the group consisting of hydrogen and radicals having the formula ⁇ -o11,-oH,-o
- n represents an integer of at least 3 and X represents an integer of at least 1.
- a light-sensitive photographic material comprising a silver halide emulsion layer in which the silver halide has a silver chloride content of at least SO-mcl percent, which contains a condensation product as defined in claim 1.
- a light-sensitive photographic material comprising a silver halide emulsion layer in which the silver halide has a silver chloride content of at least 50-mol percent, which contains a condensation product as defined in claim 2.
- a light-sensitive photographic material comprising a silver halide emulsion layer in which the silver halide has a silver chloride content of at least 50-mol percent, which contains a condensation product as defined in claim 3.
- Photographic developing composition comprising hydroquinone and formaldehyde, which contains in addition a condensation product as defined in claim 1.
- Photographic developing composition comprising hydroquinone and formaldehyde, which contains in addition a condensation product as defined in claim 2.
- Photographic developing composition comprising hydroquinone and formaldehyde, which contains in addition a condensation product as defined in claim 3.
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEA40784A DE1246403B (de) | 1962-07-21 | 1962-07-21 | Verfahren zur Herstellung photographischer Bilder |
| DEA43236A DE1178297B (de) | 1962-07-21 | 1963-05-31 | Verfahren zur Steigerung der Allgemeinempfind-lichkeit von photographischen Halogensilber-emulsionen und photographische Materialien zur Durchfuehrung des Verfahrens |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3169863A true US3169863A (en) | 1965-02-16 |
Family
ID=25963785
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US286924A Expired - Lifetime US3169863A (en) | 1962-07-21 | 1963-06-11 | Pentaerythritol phosphoric acid ester sensitizers for photographic emulsions |
| US368714A Expired - Lifetime US3385708A (en) | 1962-07-21 | 1964-05-19 | Sensitization of photographic silver halide emulsions |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US368714A Expired - Lifetime US3385708A (en) | 1962-07-21 | 1964-05-19 | Sensitization of photographic silver halide emulsions |
Country Status (6)
| Country | Link |
|---|---|
| US (2) | US3169863A (es) |
| BE (2) | BE648588A (es) |
| CH (2) | CH433977A (es) |
| DE (2) | DE1246403B (es) |
| FR (2) | FR1364351A (es) |
| GB (2) | GB1045183A (es) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3385708A (en) * | 1962-07-21 | 1968-05-28 | Agfa Ag | Sensitization of photographic silver halide emulsions |
| US3443951A (en) * | 1964-07-02 | 1969-05-13 | Agfa Gevaert Nv | Photographic light-sensitive materials containing phosphoric acid ester of aliphatic polyols |
| US3532501A (en) * | 1967-02-10 | 1970-10-06 | Gaf Corp | Water-soluble acid esters of polyoxyalkylenated pentaerythritol in silver halide emulsions |
| CN100400542C (zh) * | 2006-03-30 | 2008-07-09 | 上海大学 | 一种磷酸脂的合成方法 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3264151D1 (en) * | 1981-01-20 | 1985-07-25 | Ciba Geigy Ag | Photographic recording material and process for its preparation |
| US4436811A (en) * | 1981-07-10 | 1984-03-13 | Ciba-Geigy Ag | Photographic material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2531832A (en) * | 1947-06-12 | 1950-11-28 | Du Pont | Silver halide developers containing polyethylene glycols |
| US2956881A (en) * | 1957-03-12 | 1960-10-18 | Eastman Kodak Co | Hemioxonol dyes containing a carbocyclic nucleus and photographic emulsions containing them |
| US2961317A (en) * | 1958-06-19 | 1960-11-22 | Eastman Kodak Co | Holopolar dyes derived from 3-indazolinone |
| US2974158A (en) * | 1953-04-02 | 1961-03-07 | Union Carbide Corp | Preparation of bi-heterocyclic phosphorus containing compounds |
| US3005007A (en) * | 1959-01-19 | 1961-10-17 | Pure Oil Co | Preparation of organophosphorus compounds from glycerol and phosphorus oxyhalides |
| US3090799A (en) * | 1959-11-17 | 1963-05-21 | Agfa Ag | Pentaerythritol esters of phosphoric acids and compositions containing the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1122834B (de) * | 1960-07-01 | 1962-01-25 | Perutz Photowerke G M B H | Verfahren zur partiellen Desensibilisierung und Versteilerung der Gradation von Halogensilberemulsionen |
| BE635167A (es) * | 1962-07-21 |
-
0
- BE BE635167D patent/BE635167A/xx unknown
-
1962
- 1962-07-21 DE DEA40784A patent/DE1246403B/de active Pending
-
1963
- 1963-05-31 DE DEA43236A patent/DE1178297B/de active Pending
- 1963-06-11 US US286924A patent/US3169863A/en not_active Expired - Lifetime
- 1963-06-28 CH CH800363A patent/CH433977A/de unknown
- 1963-07-17 GB GB28321/63A patent/GB1045183A/en not_active Expired
- 1963-07-22 FR FR942158A patent/FR1364351A/fr not_active Expired
-
1964
- 1964-05-19 US US368714A patent/US3385708A/en not_active Expired - Lifetime
- 1964-05-29 BE BE648588D patent/BE648588A/xx unknown
- 1964-05-29 FR FR976351A patent/FR1396860A/fr not_active Expired
- 1964-05-29 CH CH703464A patent/CH450156A/de unknown
- 1964-06-01 GB GB22523/64A patent/GB1045184A/en not_active Expired
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2531832A (en) * | 1947-06-12 | 1950-11-28 | Du Pont | Silver halide developers containing polyethylene glycols |
| US2974158A (en) * | 1953-04-02 | 1961-03-07 | Union Carbide Corp | Preparation of bi-heterocyclic phosphorus containing compounds |
| US2956881A (en) * | 1957-03-12 | 1960-10-18 | Eastman Kodak Co | Hemioxonol dyes containing a carbocyclic nucleus and photographic emulsions containing them |
| US2961317A (en) * | 1958-06-19 | 1960-11-22 | Eastman Kodak Co | Holopolar dyes derived from 3-indazolinone |
| US3005007A (en) * | 1959-01-19 | 1961-10-17 | Pure Oil Co | Preparation of organophosphorus compounds from glycerol and phosphorus oxyhalides |
| US3090799A (en) * | 1959-11-17 | 1963-05-21 | Agfa Ag | Pentaerythritol esters of phosphoric acids and compositions containing the same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3385708A (en) * | 1962-07-21 | 1968-05-28 | Agfa Ag | Sensitization of photographic silver halide emulsions |
| US3443951A (en) * | 1964-07-02 | 1969-05-13 | Agfa Gevaert Nv | Photographic light-sensitive materials containing phosphoric acid ester of aliphatic polyols |
| US3532501A (en) * | 1967-02-10 | 1970-10-06 | Gaf Corp | Water-soluble acid esters of polyoxyalkylenated pentaerythritol in silver halide emulsions |
| CN100400542C (zh) * | 2006-03-30 | 2008-07-09 | 上海大学 | 一种磷酸脂的合成方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1396860A (fr) | 1965-04-23 |
| GB1045183A (en) | 1966-10-12 |
| DE1178297B (de) | 1964-09-17 |
| BE648588A (es) | 1964-11-30 |
| BE635167A (es) | |
| CH450156A (de) | 1968-01-15 |
| US3385708A (en) | 1968-05-28 |
| DE1246403B (de) | 1967-08-03 |
| GB1045184A (en) | 1966-10-12 |
| CH433977A (de) | 1967-04-15 |
| FR1364351A (fr) | 1964-06-19 |
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