EP0534218B1 - Matériau photographique à l'halogénure d'argent ayant une meilleure résistance à la désensibilisation et à la pression - Google Patents
Matériau photographique à l'halogénure d'argent ayant une meilleure résistance à la désensibilisation et à la pression Download PDFInfo
- Publication number
- EP0534218B1 EP0534218B1 EP92115267A EP92115267A EP0534218B1 EP 0534218 B1 EP0534218 B1 EP 0534218B1 EP 92115267 A EP92115267 A EP 92115267A EP 92115267 A EP92115267 A EP 92115267A EP 0534218 B1 EP0534218 B1 EP 0534218B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silver halide
- photographic material
- carbon atoms
- light
- halide emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 Silver halide Chemical class 0.000 title claims description 78
- 229910052709 silver Inorganic materials 0.000 title claims description 59
- 239000004332 silver Substances 0.000 title claims description 59
- 239000000463 material Substances 0.000 title claims description 37
- 238000000586 desensitisation Methods 0.000 title description 5
- 239000000839 emulsion Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229920006294 polydialkylsiloxane Polymers 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 11
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 10
- 229920000159 gelatin Polymers 0.000 description 10
- 235000019322 gelatine Nutrition 0.000 description 10
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- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical class NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
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- 235000011852 gelatine desserts Nutrition 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 238000005530 etching Methods 0.000 description 7
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical class OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VERMEZLHWFHDLK-UHFFFAOYSA-N benzene-1,2,3,4-tetrol Chemical class OC1=CC=C(O)C(O)=C1O VERMEZLHWFHDLK-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
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- 238000007792 addition Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 description 4
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- 239000004848 polyfunctional curative Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
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- 238000001556 precipitation Methods 0.000 description 3
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- 239000003381 stabilizer Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
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- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical class [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 2
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- 239000001828 Gelatine Substances 0.000 description 2
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical class [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006172 buffering agent Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- RDJUHLUBPADHNP-UHFFFAOYSA-N 1,2,3,5-tetrahydroxybenzene Chemical compound OC1=CC(O)=C(O)C(O)=C1 RDJUHLUBPADHNP-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
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- 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
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- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
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- 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
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- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol 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
- 239000000276 potassium ferrocyanide Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical class O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- XBMBHKZYEXQONC-UHFFFAOYSA-M sodium;2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethanesulfonate Chemical compound [Na+].CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCS([O-])(=O)=O)C=C1 XBMBHKZYEXQONC-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 125000005420 sulfonamido group Chemical group S(=O)(=O)(N*)* 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000005019 zein Substances 0.000 description 1
- 229940093612 zein Drugs 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—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
Definitions
- the present invention relates to a photosensitive silver halide material for obtaining black-and-white half-tone, dot or line, images having improved resistance to pressure desensitization.
- Photosensitive silver halide materials are commonly used in photolithographic industry to obtain half-tone, dot or line, high contrast images.
- An example of high contrast photographic element having white reflective support is a phototypesetting material intended to produce black type character image on a white background.
- An example of high contrast photographic element having a transparent support is lith film, so called because it is used as contact transparency for exposing lithographic printing plates. The illusion that some areas of a printed image are of intermediate density is created by the viewer's inability to resolve tiny dots or lines of maximum density and background areas of minimum density that separate them. Such images are referred to as half-tone images.
- Pressure sensitivity of the silver halide photographic material can be reduced by the incorporation of various addenda, such as, for example, the addenda described in Research Disclosure , Vol 176, December 1978, Item 17643, Section VI, K; Research Disclosure , Vol 184, August 1979, Item 18431, Section II, H; Research Disclosure , Vol 308, December 1989, Item 308,119, Section VI, K-L; and E.J.Birr, Stabilization of Silver Halide Emulsion, Focal Press, London, 1974, pp. 133-134. Research Disclosure is published by Kenneth Mason Publications, Ltd., Emsworth, Hampshire P010 7DD, England. However, such addenda often affect photographic characteristics without having a substantial effect on pressure sensitivity.
- JP-A-63 116,149 discloses the use of organo-polysiloxanes in the outer layer of photographic materials comprising a core/shell silver halide emulsion layer to prevent formation of pressure fog.
- polyhydroxybenzene to reduce pressure sensitivity is limited in that the high quantity of said compound can deteriorate anti-blocking properties, in particular, it can increase the tendency toward tackiness of the emulsion.
- the present invention relates to a light-sensitive silver halide photographic material to obtain black-and-white half-tone, dot or line, images comprising a support and coated thereon one or more hydrophilic layers, at least one of said hydrophilic layers including a high chloride content silver halide emulsion, comprising a polyhydroxybenzene having the following formula: wherein n is 1,2 or 3, characterized in that the outermost hydrophilic layer comprises a polydialkylsiloxane.
- said polydialkylsiloxane corresponds to the following formula: wherein R1 is an alkyl group having 1 to 3 carbon atoms, R2 is an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 2 carbon atoms and n is a positive integer of from 0 to 2000.
- the present invention relates to a method for obtaining a half-tone, dot or line, image, wherein a silver halide photographic material, comprising a support and coated thereon one or more hydrophilic layers, at least one of said hydrophilic layers including a high chloride content silver halide emulsion, is image-wise exposed for forming said image, and subjected to a photographic process comprising an alkaline developing solution, characterized in that the high-chloride content silver halide emulsion of said photographic material comprises a polyhydroxybenzene derivative of formula wherein n is 1,2 or 3, and in that the outermost hydrophilic layer of said photographic material comprises a polydilakylsiloxane preferably having the following formula: wherein R1 is an alkyl group having 1 to 3 carbon atoms, R2 is an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 2 carbon atoms and n is a positive integer of from 0 to 2000.
- the present invention relates to a light-sensitive silver halide photographic material to obtain black-and-white half-tone, dot or line, images comprising a support and coated thereon one or more hydrophilic layers, at least one of said hydrophilic layers including a high chloride content silver halide emulsion, comprising a polyhydroxybenzene having the following formula: wherein n is 1,2 or 3, characterized in that the outermost hydrophilic layer comprises a polydilakylsiloxane preferably having the following formula: wherein R1 is an alkyl group having 1 to 3 carbon atoms, R2 is an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 2 carbon atoms and n is a positive integer of from 0 to 2000.
- the polyhydroxybenzenes according formula (I) above can be dihydroxybenzene derivatives, trihydroxybenzene derivatives, or tetrahydroxybenzene derivatives.
- dihydroxybenzene are 1,2-dihydroxybenzene, i.e., pyrocatechol, 1,3-dihydroxybenzene, i.e., resorcinol, 1,4-dihydroxybenzene, i.e., hydroquinone.
- trihydroxybenzene 1,2,3-trihydroxybenzene, i.e., pyrogallol, 1,3,5-trihydroxybenzene, i.e., phloroglucinol, 1,2,4-trihydroxybenzene, i.e., hydroxyhydroquinone.
- tetrahydroxybenzene 1,2,3,4-tetrahydroxybenzene, 1,2,4,5-tetrahydroxybenzene, 1,3,4,5-tetrahydroxybenzene.
- Said polyhydroxybenzenes can be unsubstituted or substituted with, for example, halogen, alkyl, alkoxy, amino, amido, sulfonamido, carboxy, and the like. Unsubstituted polyhydroxybenzenes are preferred.
- the polyhydroxybenzenes are added to the photographic emulsion comprising light sensitive silver halide grains and a carrying medium or binder in an amount of from 0.01 to 0.1 moles per mole of silver, preferably of from 0.03 to 0.07 moles per mole of silver.
- the polydialkylsiloxanes according to the formula (II) above are generally added to the carrying medium or binder which forms the outermost layer of the film as an aqueous dispersion in the presence of a suitable dispersing agent, preferably a non-ionic dispersing agent.
- a suitable dispersing agent preferably a non-ionic dispersing agent.
- An aqueous dispersion containing 35% by weight of the silicone polymer is preferred but dispersions containing 1 to 50% by weight of the polymer are suitable.
- Useful polydialkylsiloxanes include commercially available silicone oils such as the trialkyl and trialkoxy endblocked dialkylpolysiloxanes, e.g., dimethylpolysiloxane, diethylpolysiloxane, trimethoxy endblocked dimethylpolysiloxane and triethoxy endblocked dimethylpolysiloxane.
- the polydialkylsiloxanes have molecular weights of from 100 to 150,000, preferably of from 10,000 to 20,000 and a viscosity at 25°C of from 2 to 100,000 centistokes, preferably of from 200 to 800 centistokes.
- the polydialkylsiloxanes can be used in any concentration which is effective for the intended purpose.
- a suitable concentration is of from 0.01 to 0.1, preferably of from 0.02 to 0.08 grams per square meter of the photographic material.
- Suitable dispersing agents are generally of non-ionic type such as alkyl phenyl polyethylene glycol ethers, e.g., nonyl phenyl polyethylene glycol ether, and undecyl phenyl polyethylene glycol ether; alkyl and aralkyl polyether alcohols, e.g., iso-octyl phenyl polyethoxyethanol, nonyl phenyl polyethoxyethanol, and tetradecyl phenyl polyethoxyethanol.
- alkyl phenyl polyethylene glycol ethers e.g., nonyl phenyl polyethylene glycol ether, and undecyl phenyl polyethylene glycol ether
- alkyl and aralkyl polyether alcohols e.g., iso-octyl phenyl polyethoxyethanol, nonyl phenyl polyethoxyethanol, and tetradecyl phenyl polyeth
- Suitable dispersing agents include saponin and the oxyalkylene ethers of hexitol ring dehydration products, e.g., the polyoxyethylene sorbitan monolaurates, monostearates and monooleates which contain 2 to 20 oxyethylene groups divided in three chains; salts of alkyl-substituted aryloxy alkylene ether sulfonates, e.g., sodium p-t-octylphenoxyethoxyethyl sulfonate; sodium dodecyl, tetradecyl and octadecyl sulfates and the dioctyl ester of sodium sulfosuccinic acid. Certain soaps, e.g., morpholine oleate and sodium stearate, can also be used.
- the dispersing agents are used in amount of from 1 to 50%, preferably of from 2 to 20% by weight of the silicone oil.
- the polydialkylsioloxanes can be added in a suitable organic solvent, e.g., amyl acetate, benzene, carbon tetrachloride, ethyl ether, perchloroethylene, petroleum ether, or xylene.
- a suitable organic solvent e.g., amyl acetate, benzene, carbon tetrachloride, ethyl ether, perchloroethylene, petroleum ether, or xylene.
- the organic solvent must not adversely affect the physical or photographic properties of the photographic film.
- any hydrophilic binder known in the art can be used.
- Suitable binders include natural polymers, synthetic resins, polymers and copolymers, and other film forming media.
- the binders may range from thermoplastic to highly cross-linked, and may be coated from aqueous or organic solvents or emulsions.
- Gelatin is the preferred hydrophilic colloid for use in the present invention.
- other water-soluble colloidal substances or mixtures thereof can also be used.
- Exemplary hydrophilic colloidal substances include gelatine derivatives, such as phthalated gelatin and acetylated gelatine, cellulose derivatives, such as carboxymethyl cellulose, starch, casein, zein, synthetic hydrophilic colloids such as polyvinyl alcohol, polyvinyl pyrrolidone, copolymers of acrylic acid esters, acrylonitrile and acrylamides, etc.
- the amount of hydrophilic binder used in practice depends on the dispersing solvent amount and the coating thickness required. Since an excessive amount of binder can reduce maximum density and contrast, for the purpose of the present invention, the binder is advantageously used in an amount lower than 250 grams per mole of silver halide, preferably in an amount of from 20 to 200 grams per mole of silver halide.
- the silver halide emulsions used in the present invention are preferably monodispersed, but emulsions having a wide grain size distribution can also be used.
- the term "monodispersed” refers to an emulsion having a coefficient of variation lower than 45%, preferably lower than 35%, more preferably lower than 20%.
- the emulsions suitable in the present invention are of the type normally employed to obtain halftone, dot and line, images and are usually called lith emulsions.
- Lith emulsions contain preferably at least 50 mole % of silver chloride, more preferably at least 80% of silver chloride and at least about 5% mole of silver bromide.
- the silver halide grains can contain a small amount of silver iodide, in an amount that is usually less than about 5 mole %, preferably less than 1 mole %.
- Other references to lith materials can be found in Research Disclosure 235, November 1983, Item 23510, " Development Nucleation by Hydrazine and Hydrazine derivatives ".
- the silver halide grain average size is lower than about 0.7»m, preferably lower than about 0.4»m, more preferably lower than 0.2»m.
- the term "grain size” refers to the diameter of a circle having the area of the same value as the average area projected by the silver halide crystals seen at the electron microscope.
- the silver halide grains may be those having a regular crystal form, such as a cube or an octahedron, or those having an irregular crystal form, such as a sphere or tablet, etc., or may be those having a composite crystal form. They may be composed of a mixture of grains having different crystal forms.
- the silver halide emulsion may be chemically sensitized with a sulfur sensitizer, such as allylthiocarbamide, thiourea, cysteine, etc.; an active or inert selenium sensitizer; a reducing sensitizer such as stannous salt, a polyamine, etc.; a noble metal sensitizer, such as gold sensitizer, more specifically potassium aurithiocyanate, potassium chloroaurate, potassium chloroplatinate, etc.; or a sensitizer of a water soluble salt such as, for instance, of ruthenium, rhodium, iridium, palladium and the like, more specifically, ammonium chloropalladate, sodium chloropalladite, etc.; each of such sensitizers being employed either alone or in a suitable combination.
- a sulfur sensitizer such as allylthiocarbamide, thiourea, cysteine, etc.
- an active or inert selenium sensitizer such
- the silver halide emulsion may be spectrally sensitized by making it, in addition to its blue light sensitivity, sensitive to, e.g., green light (ortho-sensitive) or sensitive to green and red light (pan-sensitive).
- green light ortho-sensitive
- red light pan-sensitive
- monomethine or polymethine dyes such as acid and basic cyanines, hemicyanines, streptocyanines, merocyanines, oxonoles, hemioxonoles, styryl dyes or others, as well as trinuclear or higher nuclear methine dyes, e.g., rhodacyanines or neocyanines can be used.
- Sensitizers of this kind have been described, for example, in F.M. Hamer, " The Cyanine Dyes and Related Compounds ", 1964 Interscience Publishers, John Wiley and Sons, New York, and in Research Disclosure 308, December 1989, Item 308119, " Photographic Silver Halide Emulsions, Preparation , Addenda, Processing and System ", Section IV.
- the silver halide emulsions can be prepared using a single-jet method, a double-jet method, or a combination of these methods or can be matured using, for instance, an ammonia method, a neutralization method, an acid method, etc.
- water soluble salts are removed from the emulsion with procedures known in the art, such as ultrafiltration.
- the emulsions can contain optical brighteners, antifogging agents and stabilizers, filtering and antihalo dyes, hardeners, coating aids, plasticizers and lubricants and other auxiliary substances, as those described, for instance, in Research Disclosure 17643, V, VI, VIII, X, XI and XII, December 1978.
- the above described emulsions can be coated onto several support bases by adopting various methods, as described in Research Disclosure 17643, XV and XVII, December 1978.
- supports include films of a poly-alpha-olefin (such as polyethylene, polystyrene, etc.), a polyester (such as polyethyleneterephthalate, etc.), cellulose esters (such as cellulose triacetate, etc.), paper, synthetic paper or resin-coated paper and the like.
- a poly-alpha-olefin such as polyethylene, polystyrene, etc.
- a polyester such as polyethyleneterephthalate, etc.
- cellulose esters such as cellulose triacetate, etc.
- paper synthetic paper or resin-coated paper and the like.
- the above emulsions may also contain various additives conveniently used depending upon their purpose.
- additives include, for example, stabilizers or antifoggants such as azaindenes, triazoles, tetrazoles, imidazolium salts, polyhydroxy compounds and others; film hardeners such as of the aldehyde, aziridine, isoxazole, vinylsulfone, acryloyl, triazine type, etc.; developing promoters such as benzyl alcohol, polyoxyethylene type compounds, etc.; image stabilizers such as compounds of the chromane, cumaran, bisphenol type, etc.; and lubricants such as wax, higher fatty acid glycerides, higher alcohol esters of higher fatty acids, etc.
- coating aids modifiers of the permeability in the processing liquids, defoaming agents, antistatic agents and matting agents may be used. References for the kind and for the use of these additives can be found in Research Disclosure 308, December 1989, Item 308119, " Photographic Silver Halide Emulsions, Preparation, Addenda, Processing and System ".
- the photographic material of the present invention can include a hydrazine derivative to obtain high contrast images.
- a hydrazine derivative to obtain high contrast images.
- Any known hydrazine derivatives can be used, such as, for example, hydrazine derivatives described in Research Disclosure 235, November 1983, Item 23510, " Development Nucleation by Hydrazine and Hydrazine derivatives ".
- the present invention relates to a method for obtaining a half-tone, dot or line, image, wherein a silver halide photographic material, comprising a support and coated thereon one or more hydrophilic layers, at least one of said hydrophilic layers including a high chloride content silver halide emulsion, is image-wise exposed for forming said image, and subjected to a photographic process comprising an alkaline developing solution, characterized in that the high-chloride content silver halide emulsion of said photographic material comprises a polyhydroxybenzene of formula: wherein n is 1,2 or 3, and in that the outermost hydrophilic layer of said photographic material comprises a polydialkylsiloxane preferably having the following formula: wherein R1 is an alkyl group having 1 to 3 carbon atoms, R2 is an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 2 carbon atoms and n is a positive integer of from 0 to 2000.
- the present invention does not put any particular restriction on the developing process of the photosensitive material.
- any developing process can be adopted (comprising the developing, fixing and etching steps) which is used to process conventional photographic materials to be used in the lithographic field.
- Such developing process can be performed manually or by using automatic processors, at a processing temperature generally ranging from 18 to 50°C, but also outside said range, if desired.
- the developing solution can contain any known developing agent.
- developing agents which can be used alone or in mixture
- developing solutions can contain preservatives, alkali agents, buffering agents, antifoggants, water softening agents, hardeners, and the like.
- a suitable developing solution which can be used with the photographic material of the present invention is the so-called lith developing solution, which comprises a dihydroxybenzene developing agent, an alkali agent, a small quantity of free sulfite and a buffering agent for the sulfite ions (such as formaline and sodium bisulfite adducts and acetone and sodium bisulfite adducts) to monitor the free sulfite concentration, etc.
- lith developing solution which comprises a dihydroxybenzene developing agent, an alkali agent, a small quantity of free sulfite and a buffering agent for the sulfite ions (such as formaline and sodium bisulfite adducts and acetone and sodium bisulfite adducts) to monitor the free sulfite concentration, etc.
- the fixing solution can have any conventional composition.
- fixing agents which can be used comprise thiosulfates, thiocyanates and sulfur organic compounds, known as fixing agents.
- the fixing solution can further contain water-soluble alluminium salts as hardeners.
- the etching solution can have any conventional composition as well, and, for instance, the compositions described by C.E.K. Mees in " The Theory of the Photographic Process ", McMillan, 1954, pp.
- an etching solution which comprises, as a reducing agent, a permanganate, a ferric salt, a persulfate, a cupric acid, a ceric acid, a hexacyanoferate-(III) or a dichromate, alone or in combination and, possibly, an inorganic acid such as sulfuric acid, and an alcohol; or an etching solution can be used which comprises a reducing agent such as a hexacyanoferrate-(III), ethylenediaminotetracetatoferrate-(III) or the like and a silver halide solvent such as thiosulfate, thiocyanate, thiourea or a derivative thereof and, possibly, an inorganic acid such as sulfuric acid.
- Representative examples of etching solutions are Farmer's solultions comprising potassium ferrocyanide and sodium thiosulfate, an etching solution comprising persulfate, an etching solution comprising
- a cubic monodispersed 0.32 »m silver chlorobromide (40 mole percent bromide) was prepared as follows.
- a solution (A) consisting of 4.700 l water, 0.9 g adenine and 84 g of gelatin was initially introduced into a reaction vessel.
- the components used for the silver halide grain formation were a solution (B) of 5.379 l water and 2380 g silver nitrate and a solution (C) of 5.281 l water, 688 g KCl, 733 g KBr and 0.002 g Na3RhCl6 ⁇ 18H2O.
- Solutions (B) and (C) were introduced into the reaction vessel through two separate inlets simultaneously with a vigorous stirring for a period of 9 minutes with a flow rate of 51.0 ml/min while the pAg of the content into the vessel was maintained at 8.3 and the volume of the content in the vessel was increased from 4764 ml to 5682 ml and the temperature was maintained at 56°C.
- Step 2 was repeated to reduce the content in the reaction vessel from 5682 to 3288 ml.
- Step 4 was repeated.
- step 5 Fifty minutes after beginning, step 5 was repeated.
- Step 4 was repeated.
- step 5 Sixty five minutes after beginning, step 5 was repeated.
- Gelatin (1050 g) was added to the content in the reaction vessel while stirring at 45°C until the gelatin was dissolved.
- the resulting emulsion was gold and sulfur sensitized, optically sensitized at 630 nm, divided into six parts and each part added with a polyhydroxybenzene (additive), as reported in Table 1, and coated onto a polyethylene terephthalate support at a silver coverage of 4.08 m2.
- the coatings A-F were subjected to the pressure sensitivity test consisting in applying a special tungsten carbide stylus with variable weight loading on the surface of unprocessed film.
- the coatings were then processed in 3M RDC V lith developer and evaluated by measuring the minimum weigth necessary to make a visible line.
- the samples were evaluated according the following classification:
- a cubic monodispersed silver chlorobromide emulsion was prepared as described in the previous example 1, chemically and spectrally sensitized, added with hydroquinone as reported in Table 3 and coated according to Example 1.
- a gelatin protective layer comprising silicone was coated onto the emulsion layer as reported in Example 1.
- the coatings A-D were subjected to the pressure sensitivity test as described in the previous example 1.
- a cubic monodispersed silver chlorobromide emulsion was prepared as described in the previous example 1, chemically and spectrally sensitized, and coated using same antikinking agents disclosed in literature, such as polymers of US Patent No. 4,485,170, non-ionic surfactants of JP 62/264,042, and salts of palladium, iridium and tallium of JP 62/229,129.
- the coatings A-E were subjected to the pressure sensitivity test as described in the previous example 1.
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Claims (8)
- Matériau photographique à l'halogénure d'argent sensible à la lumière pour obtenir des images en demi-teintes, en points de trame ou en traits noir et blanc comprenant un support sur lequel sont déposées une ou plusieurs couches hydrophiles, au moins une desdites couches hydrophiles incluant une émulsion d'halogénure d'argent à forte teneur en chlorure, ladite émulsion d'halogénure d'argent comprenant un polyhydroxybenzène de formule:
caractérisée en ce que la couche hydrophile la plus externe comprend un polydialkylsiloxane de formule: - Matériau photographique à l'halogénure d'argent sensible à la lumière selon la revendication 1, caractérisé en ce que ladite émulsion d'halogénure d'argent à forte teneur en chlorure comprend au moins 50% molaire de chlorure d'argent.
- Matériau photographique à l'halogénure d'argent sensible à la lumière selon la revendication 1, caractérisé en ce que ladite émulsion d'halogénure d'argent à forte teneur en chlorure comprend au moins 80% molaire de chlorure d'argent.
- Matériau photographique à l'halogénure d'argent sensible à la lumière selon la revendication 1, caractérisé en ce que ladite émulsion d'halogénure d'argent à forte teneur en chlorure comprend au moins 5% molaire de bromure d'argent.
- Matériau photographique à l'halogénure d'argent sensible à la lumière selon la revendication 1, caractérisé en ce qu'on ajoute ledit polyhydroxybenzène à ladite émulsion d'halogénure d'argent en une quantité allant de 0,01 à 0,1 mole par mole d'argent.
- Matériau photographique à l'halogénure d'argent sensible à la lumière selon la revendication 1, caractérisé en ce qu'on ajoute ledit polydialkylsiloxane à ladite couche hydrophile sous la forme d'une dispersion aqueuse contenant de 1 à 50% en poids dudit dérivé de silicone.
- Matériau photographique à l'halogénure d'argent sensible à la lumière selon la revendication 1, caractérisé en ce qu'on ajoute ledit polydialkylsiloxane en une quantité comprise entre 0,01 et 0,1 g/m².
- Procédé d'obtention d'une image en demi-teintes, points de trame ou traits, dans lequel on expose image par image un matériau photographique à l'halogénure d'argent, comprenant un support sur lequel sont déposées une ou plusieurs couches hydrophiles, au moins une desdites couches hydrophiles incluant une émulsion d'halogénure d'argent à forte teneur en chlorure, pour former ladite image, et en ce que le soumet à un procédé photographique comprenant une solution de développement alcaline, caractérisé en ce que l'émulsion d'halogénure d'argent à forte teneur en chlorure dudit matériau photographique comprend un polyhydroxybenzène de formule:
et en ce que la couche hydrophile la plus externe dudit matériau photographique comprend un polvdialkylsiloxane de formule:
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ITMI912568A IT1251885B (it) | 1991-09-26 | 1991-09-26 | Materiale fotografico agli alogenuri d'argento con una migliorata resistenza alla desensibilizzazione da pressione |
ITMI912568 | 1991-09-26 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0534218A1 EP0534218A1 (fr) | 1993-03-31 |
EP0534218B1 true EP0534218B1 (fr) | 1995-06-21 |
Family
ID=11360769
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92115267A Expired - Lifetime EP0534218B1 (fr) | 1991-09-26 | 1992-09-07 | Matériau photographique à l'halogénure d'argent ayant une meilleure résistance à la désensibilisation et à la pression |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0534218B1 (fr) |
JP (1) | JPH05204074A (fr) |
DE (1) | DE69203064T2 (fr) |
IT (1) | IT1251885B (fr) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09281627A (ja) * | 1996-04-18 | 1997-10-31 | Fuji Photo Film Co Ltd | ハロゲン化銀写真感光材料及びその処理方法 |
GB0329925D0 (en) | 2003-12-24 | 2004-01-28 | Eastman Kodak Co | Imaging element having improved durability |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0209010A3 (fr) * | 1985-07-18 | 1988-08-24 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Eléments photographiques à haut contraste qui présentent une sensibilité réduite à la pression |
-
1991
- 1991-09-26 IT ITMI912568A patent/IT1251885B/it active IP Right Grant
-
1992
- 1992-09-07 EP EP92115267A patent/EP0534218B1/fr not_active Expired - Lifetime
- 1992-09-07 DE DE69203064T patent/DE69203064T2/de not_active Expired - Fee Related
- 1992-09-25 JP JP4256323A patent/JPH05204074A/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
ITMI912568A1 (it) | 1993-03-26 |
ITMI912568A0 (it) | 1991-09-26 |
IT1251885B (it) | 1995-05-26 |
DE69203064D1 (de) | 1995-07-27 |
DE69203064T2 (de) | 1995-12-21 |
EP0534218A1 (fr) | 1993-03-31 |
JPH05204074A (ja) | 1993-08-13 |
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