DE1283672B - Process for increasing the general sensitivity of photographic silver halide emulsions and photographic materials for carrying out the process - Google Patents
Process for increasing the general sensitivity of photographic silver halide emulsions and photographic materials for carrying out the processInfo
- Publication number
- DE1283672B DE1283672B DEA48971A DEA0048971A DE1283672B DE 1283672 B DE1283672 B DE 1283672B DE A48971 A DEA48971 A DE A48971A DE A0048971 A DEA0048971 A DE A0048971A DE 1283672 B DE1283672 B DE 1283672B
- Authority
- DE
- Germany
- Prior art keywords
- photographic
- carrying
- silver halide
- increasing
- halide emulsions
- 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.)
- Pending
Links
- 239000000839 emulsion Substances 0.000 title claims description 16
- 229910052709 silver Inorganic materials 0.000 title claims description 11
- 239000004332 silver Substances 0.000 title claims description 11
- 238000000034 method Methods 0.000 title claims description 9
- 230000035945 sensitivity Effects 0.000 title claims description 9
- -1 silver halide Chemical class 0.000 title claims description 6
- 239000000463 material Substances 0.000 title claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007859 condensation product Substances 0.000 claims description 4
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 4
- 229920000151 polyglycol Polymers 0.000 claims description 3
- 239000010695 polyglycol Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BATLWRNADYHVRU-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;phosphoric acid Chemical class OP(O)(O)=O.OP(O)(O)=O.OCC(CO)(CO)CO BATLWRNADYHVRU-UHFFFAOYSA-N 0.000 description 1
- HDGMAACKJSBLMW-UHFFFAOYSA-N 4-amino-2-methylphenol Chemical compound CC1=CC(N)=CC=C1O HDGMAACKJSBLMW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000004519 manufacturing process Methods 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
- YWOITFUKFOYODT-UHFFFAOYSA-N methanol;sodium Chemical compound [Na].OC YWOITFUKFOYODT-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/04—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
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Steigerung der Allgemeinempfindlichkeit von photographischen Halogensilberemulsionen und photographische Materialien zur Durchführung des Verfahrens Zusatz zum Patent: 1 178 297 Das deutsche Patent 1 178 297 betrifft ein Verfahren zur Steigerung der Allgemeinempfindlichkeit von photographischen Halogensilberemulsionen mit zumindest 50 Molprozent Bromsilber, wobei man die Emulsionen in Gegenwart von Polyglykolderivaten entwickelt, wobei als Polyglykolderivate Kondensationsprodukte aus spirocyclischen Pentaerythritbis-(phosphorsäuremonoh@tlogeniden) und Polyäthylenglykolen mit 3 bis 50 Äthylenoxydresten verwendet werden.Process for increasing the general sensitivity of photographic Halide silver emulsions and photographic materials for carrying out the process Addendum to the patent: 1 178 297 The German patent 1 178 297 relates to a method to increase the general sensitivity of photographic silver halide emulsions with at least 50 mole percent bromide silver, the emulsions being in the presence of Polyglycol derivatives developed, with condensation products as polyglycol derivatives from spirocyclic pentaerythritol bis (phosphoric acid monoh @ tlogeniden) and polyethylene glycols with 3 to 50 ethylene oxide residues can be used.
Bei der weiteren Bearbeitung des Verfahrens wurde nun gefunden, daß mit Vorteil solche spirocyclischen Pentaerythrit-bis-phosphorsäureester verwendet werden können, die mehr als 50 und bis zu 100 Äthylenoxydeinheiten pro Estergruppierung enthalten. fJberraschenderweise bringen diese Verbindungen im Vergleich zu den im deutschen Patent 1 178 297 vorgeschlagenen Verbindungstypen eine weitere Empfindlichkeitssteigertrng bei gleichermaßen geringer schleiernder Wirkung. Diese Eigenschaft ist beispielsweise für die Herstellung hochempfindlicher Halogensilberemulsionen von größtem Interesse. Bei Verwendung der erfindungsgemäßen Phosphorsäureester kann auf den Einsatz von Antischleiermitteln verzichtet werden, die bekanntlich die Empfindlichkeit einer Emulsion herabsetzen.In the further processing of the process it has now been found that Such spirocyclic pentaerythritol bis-phosphoric acid esters are advantageously used can be that more than 50 and up to 100 ethylene oxide units per ester grouping contain. Surprisingly, these compounds, compared to the im German Patent 1,178,297 proposed connection types a further increase in sensitivity with an equally low fogging effect. This property is for example of great interest for the production of highly sensitive halogen silver emulsions. When using the phosphoric acid esters according to the invention, the use of Antifoggants are dispensed with, which are known to reduce the sensitivity of a Reduce emulsion.
L.': ie genannten Umsetzungsprodukte können durch Kondensation von spirocyclischen Phospltorsütrreestern der allgemeinen Formel worin X = Chlor oder Brorn bedeutet. ntit einem E'olväth ylcnglykol der allgemeinen Formel 1-10 CH-, . _ 0), --- l1 11 worin n eine Athl mehr als 50 und bis zu 11x) bedeutet, erhalten werden, wobei die genannten Glykole vorztrgs\,%eise in Mengen von etwa I bis 2 Mol pro Liter der angeführten Halogenide eingesetzt werden.L. ': The reaction products mentioned can be obtained by condensation of spirocyclic phosphorus acid esters of the general formula where X = chlorine or bromine. with an E'olväth ylcnglykol of the general formula 1-10 CH-,. _ 0), --- 11 11 in which n is an athlete more than 50 and up to 11x), the glycols mentioned are preferably used in amounts of about 1 to 2 mol per liter of the halides mentioned .
Die 1._'ntsetzungsprodukte können auch durch Erwärmen der Komponenten auf etwa 11x) bis 180 C im Vakuum erhalten werden. wobei der in Hreiheit gesetzte Chforwasserstofrdurch die Gasphase entfernt wird.The 1 ._ 'continuation products can also be obtained by heating the components to about 11x) to 180 ° C. in vacuo. where the honorable one Hydrogen chloride is removed by the gas phase.
Die bei diesen Reaktionen gewonnenen Substanzen sind im aflgenteinen @iasserl(islirh. Sie werden hevorzugt den photographischen Halogensilherernulsiortsschichten zugesetzt. wobei Mengen von etwa 10 bis 2011 rng pro Mol Halogensilber verwendet werden. jedoch eignen sie sich auch als Zusatzstoffe zu Entwicklcrlösungen. wobei sie vorzugsweise in Mengen von 30 his 6011 rng pro Liter angewendet werden.The substances obtained in these reactions are in aflgenuine @iasserl (islirh. They are preferred to the photographic halogen silver emulsion layers added. with amounts of about 10 to 2011 rng per mole of halosilver used will. however, they are also suitable as additives to developer solutions. whereby they are preferably used in amounts of 30 to 6011 mg per liter.
Als pltotographisclte Halogensilherernulsiorten eignen sich insbesondere Bromiocisilhererntrlsiorten. deren Halogensilhersalze zu etwa 1 his l11 iNlolprozent aus Jodsilber bestehen. vorzugsweise werden die obigen 1`ntsetzungsprodukte den Emulsionen zuLlesetzt. nachdem diese auf optimale Empfindlichkeit gereift %\orden sind. Die Emulsionen können in an @ sich bekannter Weise Schwetelsensihilisatoren. Goldsalze oder andere Mittel zur Steigerung der Empfindlichkeit so«ie Stabilisatoren. -«je Azaindolizine. optische Sertsihilisatoren und @l@ir@ungsmittel entltaltert. 6 g der Verbindung und 40 g Polyäthylenglykol mit 90 Äthylenoxydeinheiten werden im Vakuum von ungefähr 15 mm Quecksilbersäule auf eine Temperatur von etwa 100 bis 120"C erhitzt, wobei Chlorwasserstoff' in großen Mengen entweicht. Nach Beendigung der Reaktion wird mit Methanol-Natriumalkoholat-Lösung neutralisiert und anschließend der Alkohol im Vakuum entfernt. Es werden 42 g eines farblosen wachsartigen Produktes erhalten.Particularly suitable types of halogenated silver emulsifiers are bromide-based silver emulsions. the halosilver salts of which consist of about 1 to l11 percent iodide of silver. The above decomposition products are preferably added to the emulsions. after they have matured to optimum sensitivity. The emulsions can be Schwetelsensihilisatoren in a manner known per se. Gold salts or other means to increase sensitivity, so called stabilizers. - «each azaindolizine. optical Sertsihilisatoren and @l @ ir @ mittel removed. 6 g of compound and 40 g of polyethylene glycol with 90 ethylene oxide units are heated in a vacuum of about 15 mm of mercury to a temperature of about 100 to 120 "C, with large amounts of hydrogen chloride escaping. After the reaction has ended, the reaction is neutralized with methanol-sodium alcoholate solution and then the Alcohol removed in vacuo, giving 42 g of a colorless, waxy product.
Photographische Anwendung Eine Bromjodsilber-Gelatine-Emulsion, die pro Kilogramm Gießlösung 0,3 Mol Halogensilber mit einem Jodgehalt von 6 Molprozent, bezogen auf 1 Mol Halogensilber, enthält, wurde mit den erforderlichen Zusatzstoffen, wie Netzmitteln, optischen Sensibilisatoren, Stabilisatoren und Härtungsmitteln, versehen und auf einen geeigneten Filmträger vergossen (Probe A). In Parallelversuchen wurden der Emulsion als Gießzusatz noch folgende Substanzen pro Kilogramm Emulsion zugegeben: Probe B 200 mg eines Polyäthylenglykols mit 90 Äthylenoxydeinheiten.Photographic application A silver bromide gelatin emulsion which 0.3 mol of halogen silver with an iodine content of 6 mol percent per kilogram of casting solution, based on 1 mole of halogen silver, has been treated with the necessary additives, such as wetting agents, optical sensitizers, stabilizers and hardeners, provided and cast on a suitable film carrier (sample A). In parallel experiments the following substances per kilogram of emulsion were added to the emulsion as a pouring additive added: sample B 200 mg of a polyethylene glycol with 90 ethylene oxide units.
Probe C 20(? mg des in der oben beschriebenen Weise hergestellten
spirocyclischen Phosphorsäureesters. Alle Proben wurden in einem Sensitometer hinter
einem Graustufenkeil belichtet und 10 Minuten in einem Entwickler der folgenden
Zusammensetzung bei 18"C entwickelt: Natriumsulfit, sicc................ 70 g Borax
.......................... 7 g Hydrochinon . . . . . . . . . . . . . . . . . . .
. 3,5 g Monomethyl-p-aminophenol ...... 3,5 g Natriumcitrat . . . . . . .
. . . . . . . . . . . . 7 g Kaliumbromid . . . . . . . . . . . . . . . . . . 0,4
g Mit Wasser auf 1 1 auffüllen.
Claims (3)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US368714A US3385708A (en) | 1962-07-21 | 1964-05-19 | Sensitization of photographic silver halide emulsions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1283672B true DE1283672B (en) | 1968-11-21 |
Family
ID=23452437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEA48971A Pending DE1283672B (en) | 1964-05-19 | 1965-04-17 | Process for increasing the general sensitivity of photographic silver halide emulsions and photographic materials for carrying out the process |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1283672B (en) |
-
1965
- 1965-04-17 DE DEA48971A patent/DE1283672B/en active Pending
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