EP0465728A1 - Stabilization of tabular grains by pyrimidine derivatives - Google Patents
Stabilization of tabular grains by pyrimidine derivatives Download PDFInfo
- Publication number
- EP0465728A1 EP0465728A1 EP90201842A EP90201842A EP0465728A1 EP 0465728 A1 EP0465728 A1 EP 0465728A1 EP 90201842 A EP90201842 A EP 90201842A EP 90201842 A EP90201842 A EP 90201842A EP 0465728 A1 EP0465728 A1 EP 0465728A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- photographic material
- material according
- emulsion
- grains
- tabular
- 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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- 150000003230 pyrimidines Chemical class 0.000 title claims 2
- 230000006641 stabilisation Effects 0.000 title description 6
- 238000011105 stabilization Methods 0.000 title description 6
- 229940083082 pyrimidine derivative acting on arteriolar smooth muscle Drugs 0.000 title 1
- 239000000839 emulsion Substances 0.000 claims abstract description 54
- -1 silver halide Chemical class 0.000 claims abstract description 41
- 239000004332 silver Substances 0.000 claims abstract description 21
- 229910052709 silver Inorganic materials 0.000 claims abstract description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical group C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 4
- VSWICNJIUPRZIK-UHFFFAOYSA-N 2-piperideine Chemical group C1CNC=CC1 VSWICNJIUPRZIK-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical group C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims abstract description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical group C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 claims abstract description 3
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- 125000003226 pyrazolyl group Chemical group 0.000 claims abstract description 3
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- 229910052804 chromium Inorganic materials 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- RZILCCPWPBTYDO-UHFFFAOYSA-N fluometuron Chemical compound CN(C)C(=O)NC1=CC=CC(C(F)(F)F)=C1 RZILCCPWPBTYDO-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 1
- AKCUHGBLDXXTOM-UHFFFAOYSA-N hydroxy-oxo-phenyl-sulfanylidene-$l^{6}-sulfane Chemical compound SS(=O)(=O)C1=CC=CC=C1 AKCUHGBLDXXTOM-UHFFFAOYSA-N 0.000 description 1
- WYASEAQTEQVOJE-UHFFFAOYSA-N hydroxy-phenyl-sulfanylidene-$l^{4}-sulfane Chemical compound OS(=S)C1=CC=CC=C1 WYASEAQTEQVOJE-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ZAKLKBFCSHJIRI-UHFFFAOYSA-N mucochloric acid Natural products OC1OC(=O)C(Cl)=C1Cl ZAKLKBFCSHJIRI-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 150000004957 nitroimidazoles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 1
- 229950005308 oxymethurea Drugs 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 125000000612 phthaloyl group Chemical group C(C=1C(C(=O)*)=CC=CC1)(=O)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 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
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- UGZVCHWAXABBHR-UHFFFAOYSA-O pyridin-1-ium-1-carboxamide Chemical class NC(=O)[N+]1=CC=CC=C1 UGZVCHWAXABBHR-UHFFFAOYSA-O 0.000 description 1
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical class SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 description 1
- 150000003246 quinazolines Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 235000017709 saponins Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-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
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- JJJPTTANZGDADF-UHFFFAOYSA-N thiadiazole-4-thiol Chemical class SC1=CSN=N1 JJJPTTANZGDADF-UHFFFAOYSA-N 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000005019 zein Substances 0.000 description 1
- 229940093612 zein Drugs 0.000 description 1
- 239000004711 α-olefin 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/16—X-ray, infrared, or ultraviolet ray processes
- G03C5/17—X-ray, infrared, or ultraviolet ray processes using screens to intensify X-ray images
-
- 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
- G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
-
- 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
- G03C1/0051—Tabular grain emulsions
Definitions
- the present invention relates to photographic silver halide emulsion technology and more specifically to the stabilization of tabular silver halide emulsion grains.
- Tabular grains are known in the photographic art for quite some time. As early as 1961 Berry et al described the preparation and growth of tabular silver bromoiodide grains in Photographic Science and Engineering, Vol 5, No 6. A discussion of tabular grains appeared in Duffin, Photographic Emulsion Chemistry, Focal Press, 1966, p. 66-72. Early patent literature includes Bogg US 4,063,951, Lewis US 4,067,739 and Maternaghan US 4,150,994, US 4,184,877 and US 4,184,878. However the tabular grains described herein cannot be regarded as showing a high diameter to thickness ratio, commonly termed aspect ratio. In a number of US applications filed Sep. 30, 1982 and issued in 1984 tabular grains with high aspect ratio and their advantages in photographic applications are described.
- So Wilgus US 4,434,226 discloses tabular silver bromoiodide grains having a thickness less than 0.3 micron, a diameter of at least 0.6 micron and an average aspect ratio greater than 8:1 and accounting for at least 50 percent of the total projected area of all the emulsion grains.
- Kofron US 4,439,520 discloses similar grains which are spectrally sensitized.
- Abbott US 4,425,425 describes radiographic materials containing tabular grains with aspect ratio of at least 8:1 and Abbott US 4,425,426 discloses similar grains with an aspect ratio between 5:1 and 8:1.
- Solberg US 4,433,048 protects tabular silver bromoiodide grains with inhomogeneously distributed iodide.
- a survey on high aspect ratio silver halide emulsions appeared in Research Disclosure, Vol 225, Jan 1983, Item 22534.
- High aspect ratio tabular grains exhibit several pronounced photographic advantages. Thanks to their particular morphology greater amounts of certain spectral sensitizers can be adsorbed per mole silver halide compared to classical globular grains. As a consequence such spectrally sensitized tabular grains show a wide separation between their blue speed and minus blue speed. Sharpness of photographic images can be improved using tabular grains thanks to their lower light scattering properties again compared to conventional globular emulsion grains. In color negative materials the conventional sequence of the light sensitive layers can be altered and the yellow filter layer can be omitted. In developed black-and-white images high covering power is obtained even at high hardening levels; alternatively reduced silver halide coverages can be achieved if wanted resulting again in improved sharpness.
- the high light absorption of tabular grains in the spectrally sensitized region effectively reduces the "cross-over" which is the dominant factor for sharpness in a screen-film pair.
- the "cross-over” is a measure of the photographic reponse of the respective emulsion layers to the exposure from the screen located at the opposite side of the double coated film. This emission has penetrated the second emulsion layer and the support, resulting in a reduced sharpness of the finally obtained radiographic image.
- tabular grain emulsions need to be stabilized by antifoggants or stabilizers which minimize the fog increase during the processing of freshly coated photographic elements and/or the fog increase during extended storage periods of the said elements.
- antifoggants or stabilizers which minimize the fog increase during the processing of freshly coated photographic elements and/or the fog increase during extended storage periods of the said elements.
- Numerous classes of chemical compounds can be added as fog-inhibiting agent or stabilizer to conventional silver halide emulsions. Suitable examples are e.g.
- heterocyclic nitrogen-containing compounds such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles (preferably 5-methyl-benzotriazole), nitrobenzotriazoles, mercaptopyrimidines, mercaptotriazines, benzothiazoline-2-thione and oxazoline-thione.
- a especially useful class of compounds constitutute the azaindenes e.g.
- triazaindenes triazaindenes, tetrazaindenes and pentazaindenes, especially those described by Birr in Z. Wiss. Phot. 47 (1952), pages 2-58 and the azaindenes disclosed by Heimbach in US 2,444,607, 2,444,609, 2,449,225 and 2,450,397.
- the best commonly known and most widely used azaindene is 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene, furtheron abbreviated as TAI.
- Other classes include triazolopyrimidines such as those described in GB 1,203,757, GB 1,209,146, JA-Appl. 75-39537, and GB 1,500,278 and other compounds such as benzenethiosulphonic acid, benzenethiosulphinic acid and benzenethiosulphonic acid amide compounds.
- a widely used class of stabilizers is the class of mercaptotetrazoles, in particular 1-phenyl-5-mercaptotetrazole.
- a set of specific substituted 1-phenyl-mercaptotetrazoles is disclosed as stabilizers for tabular grain emulsions in US 4,888,273.
- TAI partially desorb spectral sensitizers from the grain surface, deteriorating in this way the speed in the corresponding spectral region, and in the case of double coated radiographic elements, increasing the cross-over due to a hypsochromic spectral shift of the desorbed green spectral sensitizer in the gelatin phase.
- Lowering the tetraazaindene concentration renders the stabilization ineffective.
- This problem with tetraazaindene stabilization gets more important in the case of low iodide content of the silver bromoiodide grains and is utmost severe with silver bromide emulsions containing no iodide at all.
- tabular grains with minor or no iodide content are preferred because of their faster development and fixation rate compared to emulsions containing substantial amounts of iodide.
- the desorption of spectral sensitizer is partially overcome by adding at the finalling stage of the emulsion preparation a certain amount of a soluble iodide salt but in this case the grain surface is partially converted to AgBrl which results in an inferior sensitivity.
- Tabular grains having a minimal average aspect ratio of 4:1, and accounting for at least 50 % of the total projected area of all the emulsion grains are effectively stabilized with a mercapto-substituted pyrimidine derivative represented by the following general formula : wherein :
- the stabilizer of use according to the invention is combined with another stabilizer of the tetraazaindene type e.g. 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene (TAI).
- TAI 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene
- the most effective stabilizing agent of these specific examples is Compound 1.
- the stabilizers used according to the present invention can be added to a processing solution, e.g. a development bath, but preferably they are added to the photographic material itself. They can be added to any of the hydrophylic colloid layers of the photographic material, e.g. a non-light-sensitive intermediate layer, but preferably they are contained in the light-sensitive emulsion layer(s) where they are most easily adsorbed to the tabular silver halide grains in order to exercise properly their stabilizing function. They can be added in the form of an aqueous solution or a solution in an organic solvent, e.g. a methanolic solution, or in the form of a dispersion, e.g. a gelatineous dispersion possibly containing high-boiling oilformers. They are present in a concentration ranging preferably between 10- 7 and 10- 3 mole per mole silver halide.
- a compound according to the present invention can be used as the sole stabilizing agent or it can be combined with any other representative substance of other known stabilizer classes.
- a tetraazaindene stabilizer e.g. 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene (TAI).
- TAI 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene
- This tetrazaindene stabilizer is preferably present in a concentration ranging from 10- 6 to 10- 3 mole per mole silver halide.
- the photographic tabular silver halide emulsions can be used in various types of photographic elements such as e.g. in photographic elements for graphic arts, for so-called amateur or professional still black-and- white and color photography, diffusion transfer reversal photographic elements, low-speed duplicating elements or high-speed camera sensitive elements and in motion picture recording.
- the emulsions are incorporated in a highly sensitive radiographic element.
- the photographic element can contain one single emulsion layer or it can be built up by two or even more emulsion layers.
- the material contains blue, green and red sensitive layers each of which can be single or multiple.
- the photographic material can contain several non-light sensitive layers, e.g. a protective layer, one or more backing layers, one or more subbing layers, and one or more intermediate layers.
- a protective layer e.g. a protective layer, one or more backing layers, one or more subbing layers, and one or more intermediate layers.
- an emulsion layer is provided on both sides of a transparent support covered on each side by a protective layer.
- the halide composition of the tabular silver halide emulsions used according to the present invention is not specifically limited and may be any composition selected from e.g. silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, and silver chlorobromoiodide.
- a tabular silver bromoiodide emulsion is used, most preferably with a low iodide content up to 1 % or no iodide at all.
- the tabular emulsion grains can be prepared by any method known in the art, e.g. by the methods disclosed in Research Disclosure, Vol 225, Jan 1983, Item 22534 cited above or by any similar or other method.
- Their minimal average aspect ratio is 4:1.
- Preferably their minimal average diameter is 0.6 micron and their maximal average thickness is 0.3 micron.
- the emulsion can be desalted in the usual ways e.g. by dialysis, by flocculation and re-dispersing, or by ultrafiltration.
- Two or more types of tabular silver halide emulsions that have been prepared differently can be mixed for forming a photographic emulsion for use in accordance with the present invention.
- the size distribution of the tabular silver halide particles of the photographic emulsions to be used according to the present invention can be monodisperse or heterodisperse.
- the tabular silver halide emulsions in connection with the present invention can be chemically sensitized as described e.g. in "Chimie et Physique Photographique” by P. Glafkides, in “Photographic Emulsion Chemistry” by G.F. Duffin, in “Making and Coating Photographic Emulsion” by V.L. Zelikman et al, and in "Die Grundlagen der Photographischen mit Silberhalogeniden” edited by H. Frieser and published by Akademische Verlagsgesellschaft (1968).
- chemical sensitization can be carried out by effecting the ripening in the presence of small amounts of compounds containing sulphur e.g.
- emulsions can be sensitized also by means of gold-sulphur ripeners or by means of reductors e.g. tin compounds as described in GB 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds.
- reductors e.g. tin compounds as described in GB 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds.
- the tabular silver halide emulsions can be spectrally sensitized with methine dyes such as those described by F.M. Hamer in "The Cyanine Dyes and Related Compounds", 1964, John Wiley & Sons.
- Dyes that can be used for the purpose of spectral sensitization include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
- Particularly valuable dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.
- a survey of useful chemical classes of spectral sensitizing dyes and specific useful examples in connection with tabular grains is given in the already cited Research Disclosure Item 22534.
- spectral sensitization traditionally follows the completion of chemical sensitization. However, in connection with tabular grains, it is specifically considered that spectral sensitization can occur simultaneously with or even precede completely the chemical sensitization step.
- green sensitization is preferred in connection with the actual tendency in medical X-ray practice to use screens containing green light emitting phosphors.
- preferred green sensitizing compounds include anhydro-5,5'-dichloro-9-ethyl-3,3'-di-(3-sul- phobutyl)-oxacarbocyanine and the sulfopropyl containing analogous compound.
- epitaxial deposition can occur at any stage of the emulsion preparation at the surface of the tabular grains, e.g by the addition of soluble silver salts or by the addition of very fine silver halide grains capable of Ostwald ripening. Epitaxial deposition at selected edge or corner sites is preferred. In this case the presence of a so-called site director, e.g. iodide ions can be beneficial.
- site director e.g. iodide ions
- the binder is a hydrophilic colloid, preferably gelatin.
- Gelatin can, however, be replaced in part or integrallly by synthetic, semi-synthetic, or natural polymers.
- Synthetic substitutes for gelatin are e.g. polyvinyl alcohol, poly-N-vinyl pyrrolidone, polyvinyl imidazole, polyvinyl pyrazole, polyacrylamide, polyacrylic acid, and derivatives thereof, in particular copolymers thereof.
- Natural substitutes for gelatin are e.g. other proteins such as zein, albumin and casein, cellulose, saccharides, starch, and alginates.
- the semi-synthetic substitutes for gelatin are modified natural products e.g. gelatin derivatives obtained by conversion of gelatin with alkylating or acylating agents or by grafting of polymerizable monomers on gelatin, and cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose, phthaloyl cellulose, and cellulose sulphates.
- modified natural products e.g. gelatin derivatives obtained by conversion of gelatin with alkylating or acylating agents or by grafting of polymerizable monomers on gelatin
- cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose, phthaloyl cellulose, and cellulose sulphates.
- the gelatin can be lime-treated or acid-treated gelatin.
- the preparation of such gelatin types has been described in e.g. "The Science and Technology of Gelatin", edited by A.G. Ward and A. Courts, Academic Press 1977, page 295 and next pages.
- the gelatin can also be an enzyme-treated gelatin as described in Bull. Soc. Sci. Phot. Japan, N 16, page 30 (1966).
- the binder of the photographic element can be hardened with appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type e.g. 1,3-vinylsulphonyl-2-propanol, chromium salts e.g. chromium acetate and chromium alum, aldehydes e.g. formaldehyde, glyoxal, and glutaraldehyde, N-methylol compounds e.g. dimethylolurea and methyloldimethylhydantoin, dioxan derivatives e.g.
- appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type e.g. 1,3-vinylsulphonyl-2-propanol, chromium salts e.g. chromium acetate and chro
- the photographic element of the present invention may further comprise various kinds of surface-active agents in the photographic emulsion layer or in at least one other hydrophilic colloid layer.
- Suitable surface-active agents include non-ionic agents such as saponins, alkylene oxides e.g.
- polyethylene glycol polyethylene glycol/polypropylene glycol condensation products, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or alkylamides, silicone-polyethylene oxide adducts, glycidol derivatives, fatty acid esters of polyhydric alcohols and alkyl esters of saccharides; anionic agents comprising an acid group such as a carboxy, sulpho, phospho, sulphuric or phosphoric ester group; ampholytic agents such as aminoacids, aminoalkyl sulphonic acids, aminoalkyl sulphates or phosphates, alkyl betaines, and amine-N-oxides; and cationic agents such as alkylamine salts, aliphatic, aromatic, or heterocyclic quaternary ammonium salts, aliphatic or heterocyclic ring
- Such surface-active agents can be used for various purposes e.g. as coating aids, as compounds preventing electric charges, as compounds improving slidability, as compounds facilitating dispersive emulsification, as compounds preventing or reducing adhesion, and as compounds improving the photographic characteristics e.g higher contrast, sensitization, and development acceleration.
- Preferred surface-active coating agents are compounds containing perfluorinated alkyl groups.
- Development acceleration can be accomplished with the aid of various compounds, preferably polyalkylene derivatives having a molecular weight of at least 400 such as those described in e.g. US 3,038,805 - 4,038,075 - 4,292,400.
- the photographic element of the present invention may further comprise various other additives such as e.g. compounds improving the dimensional stability of the photographic element, UV-absorbers, spacing agents and plasticizers.
- Suitable additives for improving the dimensional stability of the photographic element are e.g. dispersions of a water-soluble or hardly soluble synthetic polymer e.g. polymers of alkyl(meth)acrylates, alkoxy-(meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters, acrylonitriles, olefins, and styrenes, or copolymers of the above with acrylic acids, methacrylic acids, Alpha-Beta-unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulphoalkyl (meth)acrylates, and styrene sulphonic acids.
- a water-soluble or hardly soluble synthetic polymer e.g. polymers of alkyl(meth)acrylates, alkoxy-(meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl est
- the average particle size of spacing agents is comprised between 0.2 and 10 um.
- Spacing agents can be soluble or insoluble in alkali. Alkali-insoluble spacing agents usually remain permanently in the photographic element, whereas alkali-soluble spacing agents usually are removed therefrom in an alkaline processing bath.
- Suitable spacing agents can be made e.g. of polymethyl methacrylate, of copolymers of acrylic acid and methyl methacrylate, and of hydroxypropylmethyl cellulose hexahydroph- thalate. Other suitable spacing agents have been described in US 4,614,708.
- the support of the photographic material may be opaque or transparent, e.g. a paper support or resin support.
- a paper support preference is given to one coated at one or both sides with an alpha-olefin polymer, e.g. a polyethylene layer which optionally contains an anti-halation dye or pigment.
- an organic resin support e.g. cellulose nitrate film, cellulose acetate film, poly(vinyl acetal) film, polystyrene film, poly(ethylene terephthalate) film, polycarbonate film, polyvinylchloride film or poly-alpha-olefin films such as polyethylene or polypropylene film.
- organic resin film is preferably comprised between 0.07 and 0.35 mm.
- These organic resin supports are preferably coated with a subbing layer which can contain water insoluble particles such as silica or titanium dioxide.
- the two emulsion layers are preferably coated on both sides of a transparent blue colored poly(ethylene terephthalate) film.
- the photographic material containing tabular grains stabilized according to the present invention can be image-wise exposed by any convenient radiation source in accordance with its specific application.
- suitable commercially available green light emitting screens are KODAK LANEX and AGFA CURIX ORTHO.
- the photographic elements in connection with the present invention are preferably processed in an automatically operated apparatus.
- commercially available X-ray material processors are CURIX U 242, marketed by AGFA-GEVAERT N.V. and KODAK RP-X-OMAT M6AN, marketed by EASTMAN KODAK Co.
- tabular grains had an average thickness of 0.20 micron and an average aspect ratio of 6.6 as determined by the method described by Abott et al in GB 2,110,402. Of the total projected area 80 % was covered with tabular grains.
- the emulsion was divided in aliquot portions. Each portion was spectrally sensitized to the green spectral region with 935 mg of anhydro-5,5'-dichloro-9-ethyl-3,3'-di-(3-sulphobutyl)-oxacarbocyanine and then chemically sensitized by means of 15.1 umole/mole AgNO 3 of sodium thiosulphate, 1.73 umole/mole AgN0 3 of chloroauric acid and 1.32 mmole/mole AgN0 3 of potassium thiocyanate. The time of chemical senstization was adjusted for each sample in order to obtain an optimal fog/density ratio after coating and processing.
- each emulsion sample was coated on both sides of a polyethyleneterephtalate film at a silver coverage of 2 x 3.0 g expressed as AgN0 3 /m 2 .
- a protective layer containing 1.1 g gelatin/m 2 was applied on both sides and as a hardener formaldehyde was used.
- the coated samples were exposed to green light having a peak emission at 545 nm through a continuous tone wedge. Part of the samples were stored at 57 ° C and 34 % relative humidity in order to simulate an extended shelf life period. Processing was performed in a X-ray film processor (90 s cycle) using following processing solutions : a developing solution adjusted to pH 10.1 comprising hydrochinon, 1-phenyl-5-pyrazolidinone, potassium sulphite, 5-nitroindazole and glutaric dialdehyde as mean ingredients and a conventional fixing solution comprising ammonium thiosulphate adjusted to pH 4.3.
- Table 1 illustrates the sensitometric results of the stabilization of the described tabular grains by 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene (TAI) and 2-mercapto-4-hydroxy-6-carboxy-quinazoline (compound 1), a stabilizer of the present invention. Sensitivities are expressed as relative arithmetic values, sample 1 having reference value 100. Table 2 presents the corpual cross-over values.
- TAI 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene
- compound 1 2-mercapto-4-hydroxy-6-carboxy-quinazoline
Abstract
A photographic element is disclosed containing a silver halide emulsion comprising tabular grains having an average aspect ratio of at least 4:1, which is stabilized by a mercapto-substituted pyrimidine derivative corresponding to the general formula :
wherein :
wherein :
- R = hydrogen, a saturated or olefinically unsaturated aliphatic group or aryl;
- Z = the ring members required for completing a condensed benzene, cyclopentene or cyclohexene ring, or a heterocyclic ring selected from the group consisting of pyridine, tetrahydropyridine, pyrimidine, pyrrole, furan, thiophene, oxazole, isoaxazole, imidazole or pyrazole ring; and wherein R or Z contains at least one carboxy or sulfo group.
Description
- The present invention relates to photographic silver halide emulsion technology and more specifically to the stabilization of tabular silver halide emulsion grains.
- Tabular grains are known in the photographic art for quite some time. As early as 1961 Berry et al described the preparation and growth of tabular silver bromoiodide grains in Photographic Science and Engineering, Vol 5, No 6. A discussion of tabular grains appeared in Duffin, Photographic Emulsion Chemistry, Focal Press, 1966, p. 66-72. Early patent literature includes Bogg US 4,063,951, Lewis US 4,067,739 and Maternaghan US 4,150,994, US 4,184,877 and US 4,184,878. However the tabular grains described herein cannot be regarded as showing a high diameter to thickness ratio, commonly termed aspect ratio. In a number of US applications filed Sep. 30, 1982 and issued in 1984 tabular grains with high aspect ratio and their advantages in photographic applications are described. So Wilgus US 4,434,226 discloses tabular silver bromoiodide grains having a thickness less than 0.3 micron, a diameter of at least 0.6 micron and an average aspect ratio greater than 8:1 and accounting for at least 50 percent of the total projected area of all the emulsion grains. Kofron US 4,439,520 discloses similar grains which are spectrally sensitized. Abbott US 4,425,425 describes radiographic materials containing tabular grains with aspect ratio of at least 8:1 and Abbott US 4,425,426 discloses similar grains with an aspect ratio between 5:1 and 8:1. Solberg US 4,433,048 protects tabular silver bromoiodide grains with inhomogeneously distributed iodide. A survey on high aspect ratio silver halide emulsions appeared in Research Disclosure, Vol 225, Jan 1983, Item 22534.
- High aspect ratio tabular grains exhibit several pronounced photographic advantages. Thanks to their particular morphology greater amounts of certain spectral sensitizers can be adsorbed per mole silver halide compared to classical globular grains. As a consequence such spectrally sensitized tabular grains show a wide separation between their blue speed and minus blue speed. Sharpness of photographic images can be improved using tabular grains thanks to their lower light scattering properties again compared to conventional globular emulsion grains. In color negative materials the conventional sequence of the light sensitive layers can be altered and the yellow filter layer can be omitted. In developed black-and-white images high covering power is obtained even at high hardening levels; alternatively reduced silver halide coverages can be achieved if wanted resulting again in improved sharpness. In the especially important application field of radiographic materials where highly sensitive radiographic emulsions are coated on both sides of a transparent support the high light absorption of tabular grains in the spectrally sensitized region effectively reduces the "cross-over" which is the dominant factor for sharpness in a screen-film pair. The "cross-over" is a measure of the photographic reponse of the respective emulsion layers to the exposure from the screen located at the opposite side of the double coated film. This emission has penetrated the second emulsion layer and the support, resulting in a reduced sharpness of the finally obtained radiographic image.
- Like conventional emulsions tabular grain emulsions need to be stabilized by antifoggants or stabilizers which minimize the fog increase during the processing of freshly coated photographic elements and/or the fog increase during extended storage periods of the said elements. Numerous classes of chemical compounds can be added as fog-inhibiting agent or stabilizer to conventional silver halide emulsions. Suitable examples are e.g. the heterocyclic nitrogen-containing compounds such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles (preferably 5-methyl-benzotriazole), nitrobenzotriazoles, mercaptopyrimidines, mercaptotriazines, benzothiazoline-2-thione and oxazoline-thione. A especially useful class of compounds constitutute the azaindenes, e.g. triazaindenes, tetrazaindenes and pentazaindenes, especially those described by Birr in Z. Wiss. Phot. 47 (1952), pages 2-58 and the azaindenes disclosed by Heimbach in US 2,444,607, 2,444,609, 2,449,225 and 2,450,397. The best commonly known and most widely used azaindene is 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene, furtheron abbreviated as TAI. Other classes include triazolopyrimidines such as those described in GB 1,203,757, GB 1,209,146, JA-Appl. 75-39537, and GB 1,500,278 and other compounds such as benzenethiosulphonic acid, benzenethiosulphinic acid and benzenethiosulphonic acid amide compounds.
- A widely used class of stabilizers is the class of mercaptotetrazoles, in particular 1-phenyl-5-mercaptotetrazole. A set of specific substituted 1-phenyl-mercaptotetrazoles is disclosed as stabilizers for tabular grain emulsions in US 4,888,273.
- A general survey of stabilizers and antifoggants is given in Research Disclosure N° 17643 (1978), Chapter VI.
- Particular problems arise in trying to stabilize highly sensitive silver bromoiodide or bromide tabular grains. Several of the familiar classes of stabilizers, e.g. mercapto-compounds, tend to desensitize the tabular grains too strongly in the concentration range where they are effective as stabilizers. Tetraazaindenes too are deficient in stabilizing high aspect ratio tabular grains, as was stated already in US 4,888,273, cited above. Experimental evidence shows that tetraazaindenes, e.g. TAI partially desorb spectral sensitizers from the grain surface, deteriorating in this way the speed in the corresponding spectral region, and in the case of double coated radiographic elements, increasing the cross-over due to a hypsochromic spectral shift of the desorbed green spectral sensitizer in the gelatin phase. Lowering the tetraazaindene concentration renders the stabilization ineffective. This problem with tetraazaindene stabilization gets more important in the case of low iodide content of the silver bromoiodide grains and is utmost severe with silver bromide emulsions containing no iodide at all. However, for application in double-side coated radiographic materials, tabular grains with minor or no iodide content are preferred because of their faster development and fixation rate compared to emulsions containing substantial amounts of iodide. The desorption of spectral sensitizer is partially overcome by adding at the finalling stage of the emulsion preparation a certain amount of a soluble iodide salt but in this case the grain surface is partially converted to AgBrl which results in an inferior sensitivity.
- It is an object of the present invention to provide an effective stabilization system for tabular grains.
- It is a further object of the present invention to stabilize effectively highly sensitive silver bromoiodide and silver bromide tabular grain emulsions without deteriorating the cross-over percentage, when the emulsion is double-side coated in a radiographic element.
-
- R = hydrogen, a saturated or olefinically unsaturated aliphatic group or aryl;
- Z = the ring members required for completing a condensed benzene, cyclopentene or cyclohexene ring, or a heterocyclic ring selected from the group consisting of pyridine, tetrahydropyridine, pyrimidine, pyrrole, furan, thiophene, oxazole, isoaxazole, imidazole or pyrazole ring; on the condition that R or Z contains at least one carboxy or sulfo group.
- In a preferred embodiment the stabilizer of use according to the invention is combined with another stabilizer of the tetraazaindene type e.g. 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene (TAI).
- Although the compounds of the present invention were already known in the art from US 3,692,527 cited above, their specific and surprising effectiveness for stabilizing tabular grains, surpassing more familiar classes of stabilizers is for the first time recognized and disclosed. It was further very surprising to discover that partial or total replacement of a tetraazaindene stabilizer by a compound according to the invention could overcome the desorption of spectral sensitizer caused by the said tetraazaindene.
-
- The most effective stabilizing agent of these specific examples is Compound 1.
- The stabilizers used according to the present invention can be added to a processing solution, e.g. a development bath, but preferably they are added to the photographic material itself. They can be added to any of the hydrophylic colloid layers of the photographic material, e.g. a non-light-sensitive intermediate layer, but preferably they are contained in the light-sensitive emulsion layer(s) where they are most easily adsorbed to the tabular silver halide grains in order to exercise properly their stabilizing function. They can be added in the form of an aqueous solution or a solution in an organic solvent, e.g. a methanolic solution, or in the form of a dispersion, e.g. a gelatineous dispersion possibly containing high-boiling oilformers. They are present in a concentration ranging preferably between 10-7 and 10-3 mole per mole silver halide.
- A compound according to the present invention can be used as the sole stabilizing agent or it can be combined with any other representative substance of other known stabilizer classes. Preferably it is combined with a tetraazaindene stabilizer, e.g. 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene (TAI). This tetrazaindene stabilizer is preferably present in a concentration ranging from 10-6 to 10-3 mole per mole silver halide.
- The photographic tabular silver halide emulsions can be used in various types of photographic elements such as e.g. in photographic elements for graphic arts, for so-called amateur or professional still black-and- white and color photography, diffusion transfer reversal photographic elements, low-speed duplicating elements or high-speed camera sensitive elements and in motion picture recording. In a preferred embodiment of the present invention the emulsions are incorporated in a highly sensitive radiographic element.
- The photographic element can contain one single emulsion layer or it can be built up by two or even more emulsion layers. In the case of color photography the material contains blue, green and red sensitive layers each of which can be single or multiple. Beside the light sensitive emulsion layer(s) the photographic material can contain several non-light sensitive layers, e.g. a protective layer, one or more backing layers, one or more subbing layers, and one or more intermediate layers. In the preferred embodiment of a radiographic element an emulsion layer is provided on both sides of a transparent support covered on each side by a protective layer.
- The halide composition of the tabular silver halide emulsions used according to the present invention is not specifically limited and may be any composition selected from e.g. silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, and silver chlorobromoiodide. However in the preferred embodiment of a highly sensitive radiographic material a tabular silver bromoiodide emulsion is used, most preferably with a low iodide content up to 1 % or no iodide at all.
- The tabular emulsion grains can be prepared by any method known in the art, e.g. by the methods disclosed in Research Disclosure, Vol 225, Jan 1983, Item 22534 cited above or by any similar or other method. Their minimal average aspect ratio is 4:1. Preferably their minimal average diameter is 0.6 micron and their maximal average thickness is 0.3 micron.
- The emulsion can be desalted in the usual ways e.g. by dialysis, by flocculation and re-dispersing, or by ultrafiltration.
- Two or more types of tabular silver halide emulsions that have been prepared differently can be mixed for forming a photographic emulsion for use in accordance with the present invention.
- The size distribution of the tabular silver halide particles of the photographic emulsions to be used according to the present invention can be monodisperse or heterodisperse.
- The tabular silver halide emulsions in connection with the present invention can be chemically sensitized as described e.g. in "Chimie et Physique Photographique" by P. Glafkides, in "Photographic Emulsion Chemistry" by G.F. Duffin, in "Making and Coating Photographic Emulsion" by V.L. Zelikman et al, and in "Die Grundlagen der Photographischen Prozesse mit Silberhalogeniden" edited by H. Frieser and published by Akademische Verlagsgesellschaft (1968). As described in said literature chemical sensitization can be carried out by effecting the ripening in the presence of small amounts of compounds containing sulphur e.g. thiosulphate, thiocyanate, thioureas, sulphites, mercapto compounds, and rhodamines. The emulsions can be sensitized also by means of gold-sulphur ripeners or by means of reductors e.g. tin compounds as described in GB 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds.
- The tabular silver halide emulsions can be spectrally sensitized with methine dyes such as those described by F.M. Hamer in "The Cyanine Dyes and Related Compounds", 1964, John Wiley & Sons. Dyes that can be used for the purpose of spectral sensitization include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly valuable dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. A survey of useful chemical classes of spectral sensitizing dyes and specific useful examples in connection with tabular grains is given in the already cited Research Disclosure Item 22534.
- In classical emulsion preparation spectral sensitization traditionally follows the completion of chemical sensitization. However, in connection with tabular grains, it is specifically considered that spectral sensitization can occur simultaneously with or even precede completely the chemical sensitization step.
- In the preferred embodiment of a radiographic element green sensitization is preferred in connection with the actual tendency in medical X-ray practice to use screens containing green light emitting phosphors. In this case preferred green sensitizing compounds include anhydro-5,5'-dichloro-9-ethyl-3,3'-di-(3-sul- phobutyl)-oxacarbocyanine and the sulfopropyl containing analogous compound.
- It is specifically contemplated that epitaxial deposition can occur at any stage of the emulsion preparation at the surface of the tabular grains, e.g by the addition of soluble silver salts or by the addition of very fine silver halide grains capable of Ostwald ripening. Epitaxial deposition at selected edge or corner sites is preferred. In this case the presence of a so-called site director, e.g. iodide ions can be beneficial.
- Besides the silver halide another essential component of a light-sensitive emulsion layer is the binder. The binder is a hydrophilic colloid, preferably gelatin. Gelatin can, however, be replaced in part or integrallly by synthetic, semi-synthetic, or natural polymers. Synthetic substitutes for gelatin are e.g. polyvinyl alcohol, poly-N-vinyl pyrrolidone, polyvinyl imidazole, polyvinyl pyrazole, polyacrylamide, polyacrylic acid, and derivatives thereof, in particular copolymers thereof. Natural substitutes for gelatin are e.g. other proteins such as zein, albumin and casein, cellulose, saccharides, starch, and alginates. In general, the semi-synthetic substitutes for gelatin are modified natural products e.g. gelatin derivatives obtained by conversion of gelatin with alkylating or acylating agents or by grafting of polymerizable monomers on gelatin, and cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose, phthaloyl cellulose, and cellulose sulphates.
- The gelatin can be lime-treated or acid-treated gelatin. The preparation of such gelatin types has been described in e.g. "The Science and Technology of Gelatin", edited by A.G. Ward and A. Courts, Academic Press 1977, page 295 and next pages. The gelatin can also be an enzyme-treated gelatin as described in Bull. Soc. Sci. Phot. Japan, N 16, page 30 (1966).
- The binder of the photographic element, especially when the binder used is gelatin, can be hardened with appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type e.g. 1,3-vinylsulphonyl-2-propanol, chromium salts e.g. chromium acetate and chromium alum, aldehydes e.g. formaldehyde, glyoxal, and glutaraldehyde, N-methylol compounds e.g. dimethylolurea and methyloldimethylhydantoin, dioxan derivatives e.g. 2,3-dihydroxy-dioxan, active vinyl compounds e.g. 1,3,5-triacryloyl-hexahydro-s-triazine, active halogen compounds e.g. 2,4-dichloro-6-hydroxy-s-triazine, and mucohalogenic acids e.g. mucochloric acid and mucophenoxychloric acid. These hardeners can be used alone or in combination. The binders can also be hardened with fast-reacting hardeners such as carbamoylpyridinium salts as disclosed in US 4,063,952.
- The photographic element of the present invention may further comprise various kinds of surface-active agents in the photographic emulsion layer or in at least one other hydrophilic colloid layer. Suitable surface-active agents include non-ionic agents such as saponins, alkylene oxides e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensation products, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or alkylamides, silicone-polyethylene oxide adducts, glycidol derivatives, fatty acid esters of polyhydric alcohols and alkyl esters of saccharides; anionic agents comprising an acid group such as a carboxy, sulpho, phospho, sulphuric or phosphoric ester group; ampholytic agents such as aminoacids, aminoalkyl sulphonic acids, aminoalkyl sulphates or phosphates, alkyl betaines, and amine-N-oxides; and cationic agents such as alkylamine salts, aliphatic, aromatic, or heterocyclic quaternary ammonium salts, aliphatic or heterocyclic ring-containing phosphonium or sulphonium salts. Such surface-active agents can be used for various purposes e.g. as coating aids, as compounds preventing electric charges, as compounds improving slidability, as compounds facilitating dispersive emulsification, as compounds preventing or reducing adhesion, and as compounds improving the photographic characteristics e.g higher contrast, sensitization, and development acceleration. Preferred surface-active coating agents are compounds containing perfluorinated alkyl groups.
- Development acceleration can be accomplished with the aid of various compounds, preferably polyalkylene derivatives having a molecular weight of at least 400 such as those described in e.g. US 3,038,805 - 4,038,075 - 4,292,400.
- The photographic element of the present invention may further comprise various other additives such as e.g. compounds improving the dimensional stability of the photographic element, UV-absorbers, spacing agents and plasticizers.
- Suitable additives for improving the dimensional stability of the photographic element are e.g. dispersions of a water-soluble or hardly soluble synthetic polymer e.g. polymers of alkyl(meth)acrylates, alkoxy-(meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters, acrylonitriles, olefins, and styrenes, or copolymers of the above with acrylic acids, methacrylic acids, Alpha-Beta-unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulphoalkyl (meth)acrylates, and styrene sulphonic acids.
- In general, the average particle size of spacing agents is comprised between 0.2 and 10 um. Spacing agents can be soluble or insoluble in alkali. Alkali-insoluble spacing agents usually remain permanently in the photographic element, whereas alkali-soluble spacing agents usually are removed therefrom in an alkaline processing bath. Suitable spacing agents can be made e.g. of polymethyl methacrylate, of copolymers of acrylic acid and methyl methacrylate, and of hydroxypropylmethyl cellulose hexahydroph- thalate. Other suitable spacing agents have been described in US 4,614,708.
- The support of the photographic material may be opaque or transparent, e.g. a paper support or resin support. When a paper support is used preference is given to one coated at one or both sides with an alpha-olefin polymer, e.g. a polyethylene layer which optionally contains an anti-halation dye or pigment. It is also possible to use an organic resin support e.g. cellulose nitrate film, cellulose acetate film, poly(vinyl acetal) film, polystyrene film, poly(ethylene terephthalate) film, polycarbonate film, polyvinylchloride film or poly-alpha-olefin films such as polyethylene or polypropylene film. The thickness of such organic resin film is preferably comprised between 0.07 and 0.35 mm. These organic resin supports are preferably coated with a subbing layer which can contain water insoluble particles such as silica or titanium dioxide. In the preferred embodiment of a medical radiographic element the two emulsion layers are preferably coated on both sides of a transparent blue colored poly(ethylene terephthalate) film.
- The photographic material containing tabular grains stabilized according to the present invention can be image-wise exposed by any convenient radiation source in accordance with its specific application. For the preferred embodiment of green sensitized X-ray materials, suitable commercially available green light emitting screens are KODAK LANEX and AGFA CURIX ORTHO.
- The photographic elements in connection with the present invention are preferably processed in an automatically operated apparatus. For the case of the radiographic application commercially available X-ray material processors are CURIX U 242, marketed by AGFA-GEVAERT N.V. and KODAK RP-X-OMAT M6AN, marketed by EASTMAN KODAK Co.
- The following example illustrates the invention without however limiting it thereto.
- To a vessel containing 3180 ml of deionized water, 18.54 g of KBr and 12.5 g of inert gelatin at pH 5.8 and 70 ° C were added 25 ml of a 2.94 molar AgN03 solution and 25 ml of a 2.94 molar KBr solution in 28 seconds by a double jet precipitation technique. Then 475 ml of a solution containing 47.5 g of phtaloylgelatin were added followed by a physical ripening period of 10 min. In order to adjust the pBr to 2.03 a 2.94 molar solution of AgNO 3 was added at a rate of 5 ml/s during 564 seconds. Thereupon 928 ml of a 2.94 molar AgN03 solution and a 2.94 molar KBr solution were added simultaneously at a rate being initially 5 ml/s and increasing linearly to 49 ml/s. The pBr was maintained during this precipitation stage at a fixed value of 2.03. Finally the pH was adjusted to 3.5 by means of a sulphuric acid solution and the temperature was decreased to 40 C. After washing 160 g of inert gelatin was added and the pH and pAg were adjusted to 5.5 and 7.64 respectively.
- The thus obtained tabular grains had an average thickness of 0.20 micron and an average aspect ratio of 6.6 as determined by the method described by Abott et al in GB 2,110,402. Of the total projected area 80 % was covered with tabular grains.
- During the next stage of the preparation the emulsion was divided in aliquot portions. Each portion was spectrally sensitized to the green spectral region with 935 mg of anhydro-5,5'-dichloro-9-ethyl-3,3'-di-(3-sulphobutyl)-oxacarbocyanine and then chemically sensitized by means of 15.1 umole/mole AgNO 3 of sodium thiosulphate, 1.73 umole/mole AgN03 of chloroauric acid and 1.32 mmole/mole AgN03 of potassium thiocyanate. The time of chemical senstization was adjusted for each sample in order to obtain an optimal fog/density ratio after coating and processing. Then the emulsion samples were cooled and to each sample the desired amount of stabilizer was added (see table 1). Hereafter each emulsion sample was coated on both sides of a polyethyleneterephtalate film at a silver coverage of 2 x 3.0 g expressed as AgN03/m2. A protective layer containing 1.1 g gelatin/m2 was applied on both sides and as a hardener formaldehyde was used.
- The coated samples were exposed to green light having a peak emission at 545 nm through a continuous tone wedge. Part of the samples were stored at 57 ° C and 34 % relative humidity in order to simulate an extended shelf life period. Processing was performed in a X-ray film processor (90 s cycle) using following processing solutions : a developing solution adjusted to pH 10.1 comprising hydrochinon, 1-phenyl-5-pyrazolidinone, potassium sulphite, 5-nitroindazole and glutaric dialdehyde as mean ingredients and a conventional fixing solution comprising ammonium thiosulphate adjusted to pH 4.3.
- The cross-over percentage was determined as follows. A film-screen element, consisting of a double side coated emulsion sample in close contact with a single green emitting screen at the side of the X-ray source and a white paper replacing the second screen at the other side was exposed to varying doses of X-rays. After processing these elements the sensitometric curves (density as a function of the X-ray dose) were determined. From the difference in sensitivity, log E, between those two layers the % cross-over was calculated according to the following equation :
% cross-over = 100 / antilog ( log E) - Table 1 illustrates the sensitometric results of the stabilization of the described tabular grains by 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene (TAI) and 2-mercapto-4-hydroxy-6-carboxy-quinazoline (compound 1), a stabilizer of the present invention. Sensitivities are expressed as relative arithmetic values, sample 1 having reference value 100. Table 2 presents the procentual cross-over values.
- The results of table 1 and 2 show that the use of TAI as sole stabilizer cannot limit the fog increase after conditioning the materials for 3 days at 57 ° C and 34 % RH without severely deteriorating the cross-over. On the contrary the quinazoline derivative according to the present invention, combined with TAI, significantly reduces the fog increase after conditioning without significant variation in cross-over percentage.
Claims (10)
1. Photographic material comprising a support and at least one light sensitive emulsion layer containing tabular silver halide grains having an average aspect ratio of at least 4:1 and accounting for at least 50 % of the total projected area of all the grains characterized in that said emulsion is stabilized by a mercapto-sustituted pyrimidine derivative represented by the general formula :
wherein :
wherein :
R = hydrogen, a saturated or olefinically unsaturated aliphatic group or aryl;
Z = the ring members required for completing a condensed benzene, cyclopentene or cyclohexene ring, or a heterocyclic ring selected from the group consisting of pyridine, tetrahydropyridine, pyrimidine, pyrrole, furan, thiophene, oxazole, isoaxazole, imidazole or pyrazole ring; and wherein R or Z contains at least one carboxy or sulfo group.
3. Photographic material according to claims 1 and 2 characterized in that said stabilizer is added to the emulsion in a concentration ranging from 10-7 mole to 10-3 mole per mole silver halide.
4. Photographic material according to any of claims 1 to 3 characterized in that said stabilizer is combined with a stabilizer of the tetraazaindene type.
5. Photographic material according to claim 4 characterized in that said tetraazaindene stabilizer is 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene.
6. Photographic material according to any of claims 1 to 5 characterized in that the grains of said tabular emulsion exhibit a minimal average diameter of 0.6 micron and maximal average thickness of 0.3 micron.
7. Photographic material according to any of claims 1 to 6 characterized in that said photographic material is a radiographic X-ray recording material.
8. Photographic material according to claim 7 characterized in that said radiographic material comprises a high speed tabular bromoiodide emulsion coated on both sides of a transparent support.
9. Photographic material according to claim 8 characterized in that said radiographic material is green sensitized.
10. Photographic material according to any of claims 1 to 9 characterized in that said tabular grains have undergone epitaxial deposition on their surface.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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EP90201842A EP0465728A1 (en) | 1990-07-09 | 1990-07-09 | Stabilization of tabular grains by pyrimidine derivatives |
JP19490591A JPH04234034A (en) | 1990-07-09 | 1991-07-08 | Stabilization of plate-shaped particle with pyrimidine derivative |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP90201842A EP0465728A1 (en) | 1990-07-09 | 1990-07-09 | Stabilization of tabular grains by pyrimidine derivatives |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0465728A1 true EP0465728A1 (en) | 1992-01-15 |
Family
ID=8205064
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90201842A Withdrawn EP0465728A1 (en) | 1990-07-09 | 1990-07-09 | Stabilization of tabular grains by pyrimidine derivatives |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0465728A1 (en) |
JP (1) | JPH04234034A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5576432A (en) * | 1994-12-23 | 1996-11-19 | Eastman Kodak Company | Process for the manufacture of dihydropyrimidines |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20000015014A (en) * | 1998-08-26 | 2000-03-15 | 김영환 | New photoresist monomer, polymer, and photoresist compound |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2073677A5 (en) * | 1969-12-13 | 1971-10-01 | Agfa Gevaert Ag | |
US4425426A (en) * | 1982-09-30 | 1984-01-10 | Eastman Kodak Company | Radiographic elements exhibiting reduced crossover |
EP0244718A2 (en) * | 1986-05-08 | 1987-11-11 | Minnesota Mining And Manufacturing Company | Light-sensitive silver halide emulsion and radiographic elements with an improved image quality and reduced residual stain |
-
1990
- 1990-07-09 EP EP90201842A patent/EP0465728A1/en not_active Withdrawn
-
1991
- 1991-07-08 JP JP19490591A patent/JPH04234034A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2073677A5 (en) * | 1969-12-13 | 1971-10-01 | Agfa Gevaert Ag | |
US4425426A (en) * | 1982-09-30 | 1984-01-10 | Eastman Kodak Company | Radiographic elements exhibiting reduced crossover |
US4425426B1 (en) * | 1982-09-30 | 1988-08-09 | ||
EP0244718A2 (en) * | 1986-05-08 | 1987-11-11 | Minnesota Mining And Manufacturing Company | Light-sensitive silver halide emulsion and radiographic elements with an improved image quality and reduced residual stain |
Non-Patent Citations (1)
Title |
---|
JOURNAL OF IMAGING SCIENCE vol. 32, no. 4, July/August 1988, pages 160-177, Springfield, VA, US; J.E. MASKASKY: "Epitaxial Selective Site Sensitization of Tabular Grain Emulsions" * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5576432A (en) * | 1994-12-23 | 1996-11-19 | Eastman Kodak Company | Process for the manufacture of dihydropyrimidines |
Also Published As
Publication number | Publication date |
---|---|
JPH04234034A (en) | 1992-08-21 |
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