GB2265020A - Silver halide emulsions with increased speed - Google Patents
Silver halide emulsions with increased speed Download PDFInfo
- Publication number
- GB2265020A GB2265020A GB9205535A GB9205535A GB2265020A GB 2265020 A GB2265020 A GB 2265020A GB 9205535 A GB9205535 A GB 9205535A GB 9205535 A GB9205535 A GB 9205535A GB 2265020 A GB2265020 A GB 2265020A
- Authority
- GB
- United Kingdom
- Prior art keywords
- silver halide
- solution
- silver
- speed
- 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.)
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- -1 Silver halide Chemical class 0.000 title claims abstract description 50
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 46
- 239000004332 silver Substances 0.000 title claims abstract description 46
- 239000000839 emulsion Substances 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 5
- 206010070834 Sensitisation Diseases 0.000 claims abstract description 4
- 239000007844 bleaching agent Substances 0.000 claims abstract 2
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 230000008313 sensitization Effects 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract description 27
- 235000006408 oxalic acid Nutrition 0.000 abstract description 9
- 150000003839 salts Chemical class 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 42
- 108010010803 Gelatin Proteins 0.000 description 24
- 229920000159 gelatin Polymers 0.000 description 24
- 239000008273 gelatin Substances 0.000 description 24
- 235000019322 gelatine Nutrition 0.000 description 24
- 235000011852 gelatine desserts Nutrition 0.000 description 24
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 239000002585 base Substances 0.000 description 12
- 238000011160 research Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000004848 polyfunctional curative Substances 0.000 description 6
- 159000000000 sodium salts Chemical class 0.000 description 6
- QYSXJUFSXHHAJI-YRZJJWOYSA-N vitamin D3 Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-YRZJJWOYSA-N 0.000 description 6
- YTYYEFNWTBPCBV-UHFFFAOYSA-N ClN1NC(=CC(=N1)Cl)O Chemical compound ClN1NC(=CC(=N1)Cl)O YTYYEFNWTBPCBV-UHFFFAOYSA-N 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229940039748 oxalate Drugs 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 239000000654 additive Substances 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- GQRWKGBOBWHKHP-UHFFFAOYSA-N 2,3,6-trimethylquinoxaline Chemical compound N1=C(C)C(C)=NC2=CC(C)=CC=C21 GQRWKGBOBWHKHP-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- DSVIHYOAKPVFEH-UHFFFAOYSA-N 4-(hydroxymethyl)-4-methyl-1-phenylpyrazolidin-3-one Chemical compound N1C(=O)C(C)(CO)CN1C1=CC=CC=C1 DSVIHYOAKPVFEH-UHFFFAOYSA-N 0.000 description 1
- ONMOULMPIIOVTQ-UHFFFAOYSA-N 98-47-5 Chemical compound OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004285 Potassium sulphite Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 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
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- VBDHXZDMTDITCG-UHFFFAOYSA-N diazanium hydron disulfite Chemical compound [H+].[H+].[NH4+].[NH4+].[O-]S([O-])=O.[O-]S([O-])=O VBDHXZDMTDITCG-UHFFFAOYSA-N 0.000 description 1
- BBLSYMNDKUHQAG-UHFFFAOYSA-L dilithium;sulfite Chemical compound [Li+].[Li+].[O-]S([O-])=O BBLSYMNDKUHQAG-UHFFFAOYSA-L 0.000 description 1
- ITOXSIXYCZOWLP-UHFFFAOYSA-L dipotassium;benzene-1,4-diol;carbonate Chemical compound [K+].[K+].[O-]C([O-])=O.OC1=CC=C(O)C=C1 ITOXSIXYCZOWLP-UHFFFAOYSA-L 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PDMYFWLNGXIKEP-UHFFFAOYSA-K gold(3+);trithiocyanate Chemical compound [Au+3].[S-]C#N.[S-]C#N.[S-]C#N PDMYFWLNGXIKEP-UHFFFAOYSA-K 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- UXIDHQPACNSJJP-UHFFFAOYSA-M sodium;2-[2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC([O-])=O UXIDHQPACNSJJP-UHFFFAOYSA-M 0.000 description 1
- 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 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/28—Silver dye bleach processes; Materials therefor; Preparing or processing such materials
-
- 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
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/10—Organic substances
Abstract
A silver halide emulsion with increased speed is obtained by adding a water-soluble salt of oxalic acid, preferably during chemical sensitisation. The silver halide emulsion may be part of a silver dye bleach material.
Description
PHOTOGRAPHIC SILVER HALIDE EMULSIONS WITH INCREASED SPEED
The present invention relates to photographic silver halide emulsions with increased speed. Photographic silver halide emulsions are usually prepared by mixing a soluble silver salt with a soluble alkali metal halide salt in the presence of a colloid, particularly gelatin. Then causing the silver halide crystals to increase in size by the addition of more halide and alkali metal until they have reached the requisite size and are of the requisite habit. If such silver halide emulsions are to be of high speed it is required that they be chemically sensitized to increase their speed and contrast.
It is known that the speed of photographic silver halide emulsions obtained in this way can be increased further by different methods. Known methods of improving the sensitivity characteristics of silver halide emulsion layers by treatment in a vacuum or with hydrogen gas. For most photographic purposes, of course, treatment in vacuum or in hydrogen gas is impracticable.
It is therefore the object of the present invention to provide silver halide emulsions with higher speed.
According to the present invention there is provided a method of increasing the speed of radiation-sensitive photographic silver halide negative-working emulsion layers by incorporating a soluble salt of oxalic acid in said layers.
The incorporation of the soluble salt of oxalic acid may be accomplished during chemical sensitization, before coating or before exposing the coated emulsion layer by light.
It is to be understood that the soluble salt of oxalic acid may be added to the emulsion before the commencement of chemical sensitization or it may be added to the emulsion with the chemical sensitizers.
In a preferred embodiment of the invention, the soluble salt of oxalic acid is added to the coating solution just before coating or it may be added to the coating solution by continuous injection just before the coating head. It is to be understood that the soluble salt of oxalic acid may be added to any layer of the photographic material.
In a further preferred embodiment of the invention, the soluble salt of oxalic acid is added to a photographic material by soaking the material in a solution of a soluble salt of oxalic acid for between 1 and 10 minutes. The material then is dried and exposure to light is then made in the usual way.
The amount of oxalate anions which is necessary to achieve optimum results depends on type and grain size of the emulsion.
Generally the oxalate anions are used in an amount ranging from 0.5 to 500 g per mole of silver halide. Preferably it is used in an amount of 5 to 100 g per mole of silver halide. The oxalate anions can be added as alkali salts, for example as sodium oxalate or as other soluble salts of oxalic acid.
The silver halide emulsions used in the present invention can be comprised of silver bromide, silver chloride, silver chlorobromide, silver chloroiodide, silver bromoiodide, silver chlorobromoiodide, or mixtures thereof. The emulsions can include coarse, medium or fine silver halide grains and they may have different shapes.
The photographic emulsions of the present invention can be prepared by any of the methods described in P. Glafkides, "Chimie et Physique Photographique", Paul Montel, 1967, G. F Duffin, "Photographic Emulsion Chemistry", The Focal Press, 1966 and
V. L. Zelikman et al., "Making and Coating Photographic Emulsions", The Focal Press, 1964. That is, the emulsion may be prepared by an acid process, neutral process or ammonia process.
Soluble silver salts may be reacted with soluble halide salts by the single-jet method, double-jet method or a combination thereof.
The "reverse mixing method" wherein silver halide grains are formed in the presence of excess silver ions may also be used.
The "controlled double-jet method" wherein the medium for forming silver halide grains is kept at a constant level of pAg may be used for producing silver halide emulsions comprising grains of a substantially uniform size with regular crystal shapes.
Other methods for the preparation of silver halide emulsions which can be used for the present invention are described, for example, in Research Disclosure No. 17643, December 1978, RD No.
22534, January 1983 and RD No. 23212, August 1983.
The emulsions of the present invention can be chemically sensitized by any of the known procedures described for example in Research Disclosure No. 17643 of December 1978 and in RD No.
22534 of January 1983.
The emulsions of the present Invention may be spectrally sensitized, for example in accordance with Research Disclosure
No. 17643, Sections IIIA and IV, or in accordance with Research
Disclosure No. 22534, pages 24 to 28.
The binders or dispersants for the silver halides and image dyes, if present, to be used are the conventional colloids, for example gelatin or gelatin derivatives, if appropriate in combination with other colloids. Suitable binders or dispersants are described for example in Research Disclosure No. 17643,
Section IX.
Section X of this Research Disclosure has also disclosed compounds which can be used as hardeners for the silver halide.
A large number of further additives can be added to the silver halide emulsions, for example anti-fogging agents, stabilizers and agents for reducing the pressure sensitivity. These and
further additives are known and have been described, for example, in C.E.K. Mees, "The Theory of the Photographic Process", 2nd edition, Macmillan 1985, pages 677 to 680, and in Research
Disclosure No. 17643, Sections V-VIII, XI-XIV, XVI, XX and XXI.
For processing the material according to the invention known processes are used which comprise the conventional stages.
The present invention includes silver halide emulsions which have been prepared by the processes of the invention as hereinbefore set forth and also silver halide photographic material which comprises at least one such emulsion layer coated on a photographic film base.
The photographic base may be any of the bases used for photographic film materials, for example transparent bases such as cellulose triacetate, cellulose acetate-butyrate or biaxially oriented polyethhylene terephthalate or opaque bases such as baryta coated paper base or polyethylene coated paper base as well as metal foils, glass plates and ceramic plates.
The photographic material of the present invention may be black and white photographic material, colour photographic material, X-ray photographic materialeor graphic arts photographic material.
The accompanying examples will serve to illustrate the invention. In these examples x means by weight.
Example 1
1559g of a 5.1% aqueous gelatin solution and 298g of a polydisperse silver bromoiodide emulsion are mixed with one another at 40 C. The silver halide contains 71g of gelatin/kg and 57g of Ag/kg as silver bromoiodide with 5.2 mol% of iodide, and the mean particle size is 0.55 um. The silver halide emulsion has been chemically sensitized with thiosulphate and gold thiocyanate to the optimum speed.
lig of a 0.2% solution of the blue sensizizer of the formula (1) is added to this mixture at 40 C and the mixture is stirred for 30 minutes. Afterwards, 23g of a 1% solution of 5-methyl7-hydroxy-2,3,4-triazaindolizine and 16g of a 4.6% solution of the sodium salt of dibutylnaphthalenesulfonic acid are added.
477g of this solution are taken and different quantities of a 10% solution of potassium oxalate are added. The weight of these coating solutions is adjusted to 250g.
60g of this mixture are coated per m2 of a transparent polyester base, together with a gelatin supercoat which contains i.5g of gelatin per m2 and 48mg of the gelatin hardener, 2,4-dichloro-6-hydroxy-triazine (potassium salt).
Table (1) shows the sensitometric speed of the coated samples after exposure to blue light and development for 3 minutes in developer A and subsequent fixing.
Developer A Ethylenediaminetetraacetic acid (sodium salt) 3.90g Potassium sulphite 16.90g Sodium sulphite, anhydrous 35.40g Sodium Thiosulphate, anhydrous 0.90g Potassium carbonate, anhydrous 23.60g Potassium bicarbonate 13.30g Potassium acetate 0.55g Potassium bromide 3.50g Lithium sulphite 0.63g Benzotriazole 0.50g l-Phenyl-4-methylpyrazolidone 0.50g Hydroquinone 8.00g Ethyldiglycol 20.00g Water to make up 1000ml TABLE 1
Potassium oxalate per mole log speed at 50% of D-Max silver 21.6g 0.49 64.8g 0.43 None (Reference) 0.60 Contrast, Maximum density and fog remain unchanged, the speed is increased with increasing amount of potassium oxalate.
In this table and in all the following tables a lower log speed figure indicates a higher effective photographic speed.
Example 2
1559g of a 5.1% aqueous gelatin solution and 298g of the emulsion of example 1 are mixed with one another at 400 C.
23g of a 0.22% solution of the green sensitizer of the formula (2) is added to this mixture at 400 C and the mixture is stirred for 30 minutes. Afterwards, 23g of a 1% solution of 5-methyl7-hydroxy-2,3,4-triazaindolizine and 16g of a 4.6% solution of the sodium salt of dibutylnaphthalenesulfonic acid are added.
480g of this solution are taken and different quantities of a 10% solution of potassium oxalate are added. The weight of these coating solutions is adjusted to 250g.
60g of this mixture are coated per m2 of a transparent polyester base, together with a gelatin supercoat which contains 1.5g of gelatin per m2 and 48mg of the gelatin hardener, 2,4-dichloro-6-hydroxy-triazine (potassium salt).
Table (2) shows the sensitometric speed of the coated samples after exposure to green light and development for 3 minutes in developer A of example 1 and subsequent fixing.
TABLE 2
Potassium oxalate per mole log speed at 50% of D-Max silver 21.6g -0.34 64.8g -0.24 None (Reference) 0.02 Contrast, Maximum density and fog remain unchanged, speed is increased with increasing amount of potassium oxalate.
Example 3
1559g of a 5.1% aqueous gelatin solution and 298g of the emulsion of example 1 are mixed with one another at 40 C.
16g of a 0.138% solution of the red sensitizer of the formula (3) as indicated in table I is added to this mixture at 400 C and the mixture is stirred for 30 minutes. Afterwards, 23g of a 1% solution of 5-methyl-7-hydroxy-2,3,4-triazaindolizine and 16g of a 4.6% solution of the sodium salt of dibutylnaphthalenesulfonic acid are added. 478g of this solution are taken and different quantities of a 10% solution of potassium oxalate are added. The weight of these coating solutions is adjusted to 250g.
60g of this mixture are coated per m2 of a transparent polyester base, together with a gelatin supercoat which contains 1.5g of gelatin per m2 and 48mg of the gelatin hardener, 2,4-dichloro-6-hydroxy-triazine (potassium salt).
Table (3) shows the sensitometric speed of the coated samples after exposure to red light and development for 3 minutes in developer A of example 1 and subsequent fixing.
TABLE 3
Potassium oxalate per mole log speed at 50% of D-Max silver 21.6g -0.20 64.8g -0.26 None (Reference) -0.16 Contrast, Maximum density and fog remain unchanged, speed is increased with increasing amount of potassium oxalate.
Example 4
932g of a 5.6% aqueous gelatin solution and 199g of the polydisperse emulsion of example 1 are mixed with one another at 40 C.
7g of a 0.2% solution of the blue sensitizer of the formula (1) is added to this mixture at 40 C and the mixture is stirred for 30 minutes. Afterwards, 20g of a 1% solution of 5-methyl 7-hydroxy-2,3,4-triazaindolizine, 16g of a 4.6% solution of the sodium salt of dibutylnaphthalenesulfonic acid and 774g of a 0.861% solution of azo dye of the formula (4) are added. 487g of this solution are taken and different quantities of a 10% solution of potassium oxalate are added. The weight of these coating solutions is adjusted to 250g.
90g of this mixture are coated per m2 of a transparent polyester base, together with a gelatin supercoat which contains 1.5g of gelatin per m2 and 48mg of the gelatin hardener, 2,4-dichloro-6-hydroxy-triazine (potassium salt).
The coated samples are exposed to blue light in the usual manner and processed at 30 C as follows:
1. Developing 3 minutes bath 1 2. Washing 1 minute 3. Bleaching 1 3 minutes bath 2 4. Washing 1 minute 5. Fixing 3 minutes bath 3 6. Washing 4 minutes Bath 1 is the same as the Developer from example 11 and baths 2 and 3 are of the following composition:
Bath 2 - Bleaching Bath m-Nitrobenzenesulphonic acid 7.1g Sulphuric acid (100%) 41.5g Ethyldiglycol 2,3,6-Trimethylquinoxaline 1 .1g Potassium iodide 9.0g Potassium bisulphate 1.0g bis-(#Cyanoethyl )-sulphoethylphosphine 3.0g Water to make up 1000ml
Bath 3 - Fixing Bath Ammonium thiosulphate 200.0g Ethylenediaminetetraacetic acid 1.0g Ammonium sulphite Ammonium bisulphite 8.2g Water to make up 1000ml Table 4 shows the sensitometric speed after exposure and processing.
TABLE 4
Potassium oxalate per mole log speed at 50% of D-Max silver 21.6g 1.40 64.0g 1.45 None (Reference) 1.66 Contrast, Maximum density-and fog remain unchanged, speed is increased.
Example 5
828g of a 8.2% aqueous gelatin solution and 255g of the emulsion of example 1 are mixed with one another at 40 C.
19g of a 0.22% solution of the sensizizer of the formula (2) is added to this mixture at 40 C and the mixture is stirred for 30 minutes. Afterwards, 20g of a 1% solution of 5-methyl7-hydroxy-2,3,4-triazaindolizine, 16g of a 4.6% solution of the sodium salt of dibutylnaphthalenesulfonic acid and 777g of a 1.103% solution of azo dye of the formula (5) are added. 479g of this solution are taken and different quantities of a 10% solution of potassium oxalate are added. The weight of these coating solutions is adjusted to 250g.
70g of this mixture are coated per m2 of a transparent polyester base, together with a gelatin supercoat which contains 1.5g of gelatin per m2 and 48mg of the gelatin hardener, 2,4-dichloro-6-hydroxy-triazine (potassium salt).
The coated samples are exposed to green light in the usual manner and processed as described in example 4.
Table 5 shows the sensitometric speed after exposure and processing.
TABLE 5
Potassium oxalate per mole log speed at 50% of D-Max silver 21.6g 0.46 64.0g 0.54 None (Reference) 0.81 Contrast, Maximum density and fog remain unchanged, speed is increased.
Example 6
Sheets of the Cibachr Transparent Photographic material
CTD-F7 which is commercially available was soaked for 1 minute in solutions of potassium oxalate of different concentrations.
Afterwards, the sheets were dried and exposed to white light in the usual manner and processed as described in example 4.
Table 6 shows the sensitometric speed after exposure and processing.
TABLE 6
Potassium oxalate per liter log speed at Densiy 0.8 Blue Green Red 1.5g 1.04 1.53 1.58 2.9g 1.02 1.47 1.56 5.8g 1.03 1.41 1.55 11.5g 1.05 1.33 1.51 23.0g 0.98 1.22 1.42 46.0g 0.96 1.20 1.32 92.0g 1.02 1.30 1.29 184.0g 1.04 1.30 1.36 None (Reference) 1.17 1.55 1.68 Contrast, Maximum density and fog remain unchanged, speed is increased.
Example 7
Sheets of the Black-and-White Photographic material Multigrade III RC DELUXE which is commercially available was soaked for 1 minute in solutions of potassium oxalate of different concentrations. Afterwards, the sheets were dried and exposed to white light in the usual manner and processed in Developer B for 1 minute at 200 C and subsequent fixing.
Developer B Diethylenetriaminepentaacetic acid, sodium salt 25.2g Sodium sulphit 150.0g Potassium carbonate Hydroquinone 30.0g Dimezone S 3.0g Potassium bromide 5.0g Benzotriazole 0.2g Sodium hydroxide 2.2g Water to make up 1000ml Table 7 shows the sensitometric speed after exposure and processing.
TABLE 7
Potassium oxalate per liter log speed at 50% of D-Max 5.8g 0.37 11.5g 0.34 23.0g 0.30 46.0g 0.25 92 .0g 0.27 184.0g 0.29 None (Reference) 0.39 Contrast, Maximum density and fog remain unchanged, speed is increased.
Claims (8)
1. A silver halide emulsion with increased speed which is
characterised in that it contains oxalate anions.
2. A silver halide emulsion according to claim 1
characterised in that the amount of oxalate anion is
from 0.5 to 500g per mole of silver halide in the
emulsion.
3. A silver halide emulsion according to claim 1
characterised in that the amount of oxalate anion is
from 5 to 100g per mole of silver halide in the
emulsion.
4. A silver halide emulsion according to claim 1
characterised in that the oxalate anions are
incorporated during chemical sensitization.
5. A silver halide emulsion according to claim 1
characterised in that the oxalate anions are
incorporated before coating.
6. A silver halide emulsion according to claim 1
characterised in that the oxalate anions are
incorporated before exposure.
7. A photographic silver halide material which is
characterised in that it comprises at least one silver
halide emulsion layer as claimed in claims 4-6.
8. A silver dye bleach material which is characterised in
that it comprises at least one silver halide emulsion
layer as claimed in claims 4-6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9205535A GB2265020A (en) | 1992-03-13 | 1992-03-13 | Silver halide emulsions with increased speed |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9205535A GB2265020A (en) | 1992-03-13 | 1992-03-13 | Silver halide emulsions with increased speed |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB9205535D0 GB9205535D0 (en) | 1992-04-29 |
| GB2265020A true GB2265020A (en) | 1993-09-15 |
Family
ID=10712096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9205535A Withdrawn GB2265020A (en) | 1992-03-13 | 1992-03-13 | Silver halide emulsions with increased speed |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2265020A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1172691A1 (en) * | 2000-07-12 | 2002-01-16 | ILFORD Imaging Switzerland GmbH | Method of processing photographic silver-dye-bleach materials and bleaching solution preparations therefor |
| CN102338981A (en) * | 2010-07-23 | 2012-02-01 | 中国科学院理化技术研究所 | Efficient sensibilization method suitable for platy silver halides particle emulsion |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB253380A (en) * | 1925-07-24 | 1926-06-17 | Edwin Ernest Jelley | Improvements relating to the production of photographs on paper parchment and the like |
-
1992
- 1992-03-13 GB GB9205535A patent/GB2265020A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB253380A (en) * | 1925-07-24 | 1926-06-17 | Edwin Ernest Jelley | Improvements relating to the production of photographs on paper parchment and the like |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1172691A1 (en) * | 2000-07-12 | 2002-01-16 | ILFORD Imaging Switzerland GmbH | Method of processing photographic silver-dye-bleach materials and bleaching solution preparations therefor |
| CN102338981A (en) * | 2010-07-23 | 2012-02-01 | 中国科学院理化技术研究所 | Efficient sensibilization method suitable for platy silver halides particle emulsion |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9205535D0 (en) | 1992-04-29 |
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| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |