US3625697A - Sensitization of light-sensitive silver halide photographic emulsions - Google Patents
Sensitization of light-sensitive silver halide photographic emulsions Download PDFInfo
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- US3625697A US3625697A US884022A US3625697DA US3625697A US 3625697 A US3625697 A US 3625697A US 884022 A US884022 A US 884022A US 3625697D A US3625697D A US 3625697DA US 3625697 A US3625697 A US 3625697A
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- silver halide
- emulsion
- light
- compound
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- 239000000839 emulsion Substances 0.000 title abstract description 48
- -1 silver halide Chemical class 0.000 title abstract description 24
- 229910052709 silver Inorganic materials 0.000 title abstract description 23
- 239000004332 silver Substances 0.000 title abstract description 23
- 206010070834 Sensitisation Diseases 0.000 title description 7
- 230000008313 sensitization Effects 0.000 title description 7
- 150000001875 compounds Chemical class 0.000 abstract description 32
- 229920001281 polyalkylene Polymers 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000001235 sensitizing effect Effects 0.000 abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 3
- SONNWYBIRXJNDC-VIFPVBQESA-N phenylephrine Chemical class CNC[C@H](O)C1=CC=CC(O)=C1 SONNWYBIRXJNDC-VIFPVBQESA-N 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 125000001033 ether group Chemical group 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 5
- 230000005070 ripening Effects 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 229920002284 Cellulose triacetate Polymers 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- 229940045105 silver iodide Drugs 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical compound O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 1
- WJMFXQBNYLYADA-UHFFFAOYSA-N 1-(3,4-dihydroxyphenyl)-6,7-dihydroxy-1,2-dihydronaphthalene-2,3-dicarboxylic acid Chemical compound C12=CC(O)=C(O)C=C2C=C(C(O)=O)C(C(=O)O)C1C1=CC=C(O)C(O)=C1 WJMFXQBNYLYADA-UHFFFAOYSA-N 0.000 description 1
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 101150029512 SCG2 gene Proteins 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- ZUIVNYGZFPOXFW-UHFFFAOYSA-N chembl1717603 Chemical compound N1=C(C)C=C(O)N2N=CN=C21 ZUIVNYGZFPOXFW-UHFFFAOYSA-N 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 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
- YUWVDIIHTJLPRI-UHFFFAOYSA-N phenylhydrazine;sulfuric acid Chemical compound OS(O)(=O)=O.NNC1=CC=CC=C1 YUWVDIIHTJLPRI-UHFFFAOYSA-N 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005406 washing Methods 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
- G03C1/08—Sensitivity-increasing substances
- G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
- G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
Definitions
- Light-sensitive silver halide emulsions are sensitized by incorporating into the emulsion, a sensitizing amount (0.1- 1000 mg./ kg.) of a compound of the formula:
- W (OH2CH20) (CH2OHgO) CHg C/H2 or (OHCH2O)D- and which is not bonded through an oxygen atom to B;
- A is a lower alkylene group, or a polyalkylene ether group having the formula E E (CHgCH20)p CH2CH3 or -(CHCH O) -CHCH2 provided that A and A are not both polyalkylene ether groups at the same time, and p is an integer of 2 to 30;
- B and B are NH or O, provided that both are not O at the same time;
- R is a lower alkyl group, a phenyl group, an aralkyl group or -(CH COOR', wherein q is an integer of 1 to 3, and R is a lower alkyl group; and
- X is a divalent group of the formula:
- This invention relates to a light-sensitive silver halide photographic emulsion sensitized by incorporating therein a sulfur-containing compound which will be described below.
- the known chemical sensitization process of this kind is severely restricted as far as the amount of the compound to be added, and has such disadvantages that if the amount exceeds a definite limit, the emulsion is greatly increased in fog and becomes low in stability during storage of the resulting film at an elevated temperature. Further, if a photographic emulsion is subjected to high temperature ripening in the presence of such a sensitizer as mentioned above, usually, only fogging of the emulsion is increased while the desired increase in sensitivity can not be attained after a definite sensitivity has been reached.
- the object of the present invention is to provide silver halide photographic emulsions improved in photographic properties, which are less in fog formation and which are increased in sensitivity.
- the compounds employed in the present invention have many characteristics different from those of the conventional chemical sensitizers. For example, they are usable as additives prior to coating and, when used in combination with chemical sensitizers, they can further increase the sensitivity of silver halide photographic emulsions without any accompanying fog formation.
- the sensitizing compounds useful in the present invention are represented by the formula ABCO--BA"SR '-ABCOBASR wherein A is a lower alkylene group, or a polyalkylene ether group of the formula (CH CH O) (CH2OHzO) CHz-CHz 0r OHCHzO),,- and which is not bonded through an oxygen atom to B;
- A is a lower alkylene group, or a polyalkylene ether group of the formula -(CH CH O) ,-CH CH or CH CH CHCHzO )HoH2 provided that A and A are not both polyalkylene ether groups at the same time, and p is an integer of 2 to 30;
- B and B are NH or O, provided that both are not O- at the same time;
- R is a lower alkyl group, a phenyl group, an aralkyl group or (CH ),,'COOR, wherein q is an integer of 1 to 3 and R is a lower alkyl group; and
- X is a divalent group of the formula S, O,
- R is a lower alkyl group.
- the thus obtained compounds employed in the present invention may be added to emulsions at any stage during the second ripening. Most desirably, however, they are preferably added at the beginning of the second ripening. Silver halide emulsions containing these compounds are increased in gamma, photographic speed and maximum density and make is possible to obtain light-sensitive photographic materials having improved storability.
- the above-mentioned compound useful in the present invention may be added to a silver halide emulsion after dissolving the compound in water or in a water-miscible organic solvent such as methanol or ethanol.
- the amount of the compound to be added varies depending on the kind of the compound or of the silver halide emulsion employed, but is ordinarily in the range of 0.1 mg.-1'000 mg. per kg. of silver halide emulsion.
- the compounds employed in the present invention are applicable to all types of silver halide emulsions such as silver chlorobromide emulsion, silver iodobromide emulsion, etc. Further the emulsions may have been subjected to gold sensitization or sulfur sensitization, and may have been incorporated with spectral sensitizers, polyalkylene oxide type sensitizers, various stabilizers, hardeners and coating aids.
- the compounds employed in the present invention can be applied not only to monochhromatic photographic emulsions but also to color photographic emulsions containing oil-soluble or water-soluble color couplers.
- the silver halide photographic emulsions of the present invention which are obtained in the above-mentioned manner are coated onto common supports such as, for example, glass, cellulose triacetate film bases, polyester film bases or baryta papers.
- EXAMPLE 1 A silver halide emulsion comprising 2 mole percent of silver iodide and 98 mole percent of silver bromide was subjected to second ripening by the use of a sulfur sensitizer and a gold sensitizer to prepare a silver iodobromide emulsion for high speed photographic negatives. This emulsion was divided into portions of 100 g. each, and the divided emulsions were individually incorporated with the present compounds set forth in Table 1 below. The thus treated emulsions were coated onto cellulose triacetate film bases and were then dried to prepare samples.
- the speed is a relative value measured by assuming as 100 the speed of the nonineorporated sample.
- the speed is a relative value measured by assuming as 100 the speed of the nonineorporated sample.
- EXAMPLE 2 A neutral photographic emulsion for photographic negatives, which comprised 5 mole percent of silver iodide and 95 mole percent of silver bromide, was added with given amounts of a sulfur sensitizer and a gold sensitizer, and was then divided into portions of 100 g. each. The divided emulsions were individually incorporated with the present compounds set forth in Table 2 below. Each emulsion was maintained at 56 C. and was subjected to second ripening so as to attain the maximum density. Subsequently, 20 mg. per 100 g. of the emulsion of 4-hydroxy- 6-methyl-1,3,3a,7-tetrazaindene were added, and then suitable amounts of a film hardener and a coating aid were added.
- a magenta coupler then added as a magenta coupler a given amount of a dispersion prepared by dissolving at an elevated temperature l (2,4,6 trichlorophenyl)-3-[3-(2,4-di-tertamylphenoxyacetamide) benzarnide] 5 pyrazolone in a mixture comprising di-n-butyl phthalate and ethyl acetate, and then dispersing the solution in a gelatine solution by means of sodium alkylbenzenesulfonate. This emulsion was thoroughly stirred and was then adjusted to pH 6.8 to obtain a color photographic emulsion.
- Emulsions obtained in the above manner were immediately coated uniformly onto cellulose triacetate film bases and were then dried to prepare samples. These samples were exposed inthe same manner as in Example 1 and were then developed at 21 C. for 10 minutes with a color developer of the following composition:
- the speed is a relative value measured by as suming as 100 the white light speed of the non-incorporated sample.
- the silver halide photographic emulsions in accordance with the present invention give light-sensitive photographic materials which, even when stored under severe conditions, are less subject to formation of fog and free from any decrease in speed.
- EXAMPLE 3 which is not bonded through an oxygen atom to B;
- A is a lower alkylene group, or a polyalkylene ether group having the formula (CH CH O) provided that A and A are not both polyalkylene ether groups at the same time, and p is an integer of 2 to 30';
- B and B are -NH- or O', provided that both are not -O- at the same time;
- R is a lower alkyl group, a phenyl group, an aralkyl group or (CH )q COOR', wherein q is an integer of 1 to 3, and R is a lower alkyl group;
- X is a divalent group of the formula -S, -O,
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
LIGHT-SENSITIVE SILVER HALIDE EMULSIONS ARE SENSITIZED BY INCORPORTING INTO THE EMULSION, A SENSITIZING AMOUNT (0.11000 MK./KG.) OF A COMPOUND OF THE FORMULA:
X(-A-B-CO-B''-A''-S-R)2
WHEREIN A IS A LOWER ALKYLENE GROUP, OR A POLYALKYLENE ETHER GROUP, HAVING THE FORMULA:
-(CH2-CH2-O)P-; -(CH2-CH2-O)P-CH2-CH2-; OR
-(CH(-CH3)-CH2-O)P-
AND WHICH IS NOT BONDED THROUGH AN OXYGEN ATOM TO B;A'' IS A LOWER ALKYLENE GROUP, OR A POLYALKYLENE ETHER GROUP HAVING THE FORMULA
-(CH2-CH2-O)P-CH2-CH2- OR -(CH(-CH3)-CH2-O)P-CH(-CH3)2
PROVIDED THAT A AND A'' ARE NOT BOTH POLYALKYLENE ETHER GROUP AT THE SAME TIEM, AND P IS AN INTEGER OF 2 TO 30; B AND B'' ARE-NH-OR-O-, PROVIDED THAT BOTH ARE NOT -O-AT THE SAME TIME; R IS A LOWER ALKYL GROUP, A PHENYL GROUP, AN ARALKYL GROUP OR -(CH2)Q-COOR'', WHEREIN Q IS AN INTEGER OF 1 TO 3, AND R'' IS A LOWER ALKYL GROUP; AND X IS A DIVALENT GROUP OF THE FORMULA:
-S-; -O-; -CH2-; -CH(-CH3)2-; -CH2-CH2-; PHENYLENE; OR
-N(-R)- WHEREIN R"
IS A LOWERY ALKYL GROUP.
X(-A-B-CO-B''-A''-S-R)2
WHEREIN A IS A LOWER ALKYLENE GROUP, OR A POLYALKYLENE ETHER GROUP, HAVING THE FORMULA:
-(CH2-CH2-O)P-; -(CH2-CH2-O)P-CH2-CH2-; OR
-(CH(-CH3)-CH2-O)P-
AND WHICH IS NOT BONDED THROUGH AN OXYGEN ATOM TO B;A'' IS A LOWER ALKYLENE GROUP, OR A POLYALKYLENE ETHER GROUP HAVING THE FORMULA
-(CH2-CH2-O)P-CH2-CH2- OR -(CH(-CH3)-CH2-O)P-CH(-CH3)2
PROVIDED THAT A AND A'' ARE NOT BOTH POLYALKYLENE ETHER GROUP AT THE SAME TIEM, AND P IS AN INTEGER OF 2 TO 30; B AND B'' ARE-NH-OR-O-, PROVIDED THAT BOTH ARE NOT -O-AT THE SAME TIME; R IS A LOWER ALKYL GROUP, A PHENYL GROUP, AN ARALKYL GROUP OR -(CH2)Q-COOR'', WHEREIN Q IS AN INTEGER OF 1 TO 3, AND R'' IS A LOWER ALKYL GROUP; AND X IS A DIVALENT GROUP OF THE FORMULA:
-S-; -O-; -CH2-; -CH(-CH3)2-; -CH2-CH2-; PHENYLENE; OR
-N(-R)- WHEREIN R"
IS A LOWERY ALKYL GROUP.
Description
United States Patent SENSITIZATION 0F LIGHT-SENSITIV E SILVER HALIDE PHOTOGRAPHIC EMULSKONS Shui Sato and Rintaro Ushiyama, Tokyo, Eiichi Salramoto, Hanno-shi, and Sadatugu Terada and Hiroshi Yarnada, Tokyo, Japan, assiguors to Konishiroku Photo Industry Co., Ltd., Tokyo, Japan No Drawing. Filed Dec. 10, 1969, Ser. No. 884,022 Claims priority, application Japan, Dec. 13, 1968, 43/ 90,990 Int. Cl. G03c 1/28, 1/34 US. Cl. 96-107 5 Claims ABSTRACT OF THE DISCLOSURE Light-sensitive silver halide emulsions are sensitized by incorporating into the emulsion, a sensitizing amount (0.1- 1000 mg./ kg.) of a compound of the formula:
EABC OBAS R -ABCO-BA'SR wherein A is a lower alkylene group, or a polyalkylene ether group, having the formula:
W (OH2CH20) (CH2OHgO) CHg C/H2 or (OHCH2O)D- and which is not bonded through an oxygen atom to B; A is a lower alkylene group, or a polyalkylene ether group having the formula E E (CHgCH20)p CH2CH3 or -(CHCH O) -CHCH2 provided that A and A are not both polyalkylene ether groups at the same time, and p is an integer of 2 to 30; B and B are NH or O, provided that both are not O at the same time; R is a lower alkyl group, a phenyl group, an aralkyl group or -(CH COOR', wherein q is an integer of 1 to 3, and R is a lower alkyl group; and X is a divalent group of the formula:
I Q or N, wherein R is a lower alkyl group.
This invention relates to a light-sensitive silver halide photographic emulsion sensitized by incorporating therein a sulfur-containing compound which will be described below.
Numerous methods are known for the sensitization of light-sensitive silver halide photographic emulsions. Typical of these is chemical sensitization using either a sulfur compound capable of yielding a silver sulfide or a suitable reducing compound; or a noble metal salt. Further, it is well known that the joint use of said compounds can further increase the sensitivity of the emulsion (refer, for example, to The Theory of the Photographic Process, third edition (1967), pages 113-117).
However, the known chemical sensitization process of this kind is severely restricted as far as the amount of the compound to be added, and has such disadvantages that if the amount exceeds a definite limit, the emulsion is greatly increased in fog and becomes low in stability during storage of the resulting film at an elevated temperature. Further, if a photographic emulsion is subjected to high temperature ripening in the presence of such a sensitizer as mentioned above, usually, only fogging of the emulsion is increased while the desired increase in sensitivity can not be attained after a definite sensitivity has been reached.
The object of the present invention is to provide silver halide photographic emulsions improved in photographic properties, which are less in fog formation and which are increased in sensitivity.
As the result of various studies, we have found that the above object can be effectively achieved by applying the novel sensitizing compounds mentioned below to silver halide photographic emulsions.
The compounds employed in the present invention have many characteristics different from those of the conventional chemical sensitizers. For example, they are usable as additives prior to coating and, when used in combination with chemical sensitizers, they can further increase the sensitivity of silver halide photographic emulsions without any accompanying fog formation.
The sensitizing compounds useful in the present invention are represented by the formula ABCO--BA"SR '-ABCOBASR wherein A is a lower alkylene group, or a polyalkylene ether group of the formula (CH CH O) (CH2OHzO) CHz-CHz 0r OHCHzO),,- and which is not bonded through an oxygen atom to B;
A is a lower alkylene group, or a polyalkylene ether group of the formula -(CH CH O) ,-CH CH or CH CH CHCHzO )HoH2 provided that A and A are not both polyalkylene ether groups at the same time, and p is an integer of 2 to 30; B and B are NH or O, provided that both are not O- at the same time; R is a lower alkyl group, a phenyl group, an aralkyl group or (CH ),,'COOR, wherein q is an integer of 1 to 3 and R is a lower alkyl group; and X is a divalent group of the formula S, O,
wherein R is a lower alkyl group.
Typical examples of the above-mentioned compounds are as follows:
1 CHgC/HgNHCOOCHZCH SCH CH OOOC HE (|JH2CH,N'HC o oornomsomorno o 0 C2H5 2 omonmnoooomomsom c'rmonmuoooomcrnsorn (a) omonzoooNnon on soms c'momooorrnomornsmm (4) CH NHCONHCH CH SC H NnooNrronzornsonno n 5 ongonzonmnooNnomonzsozns CHE-N dmon onmno ONHCHZCHZSCZHE.
(s) (0013 0119600oNrron on sozrn omonmnoooomcmsom-Q i omonmnoooomomsomQ Synthesis examples of several compounds among three mentioned above are set forth immediately below.
SYNTHESIS EXAMPLE 1 SYNTHESIS EXAMPLE 2 Synthesis of the compound A solution of 7.3 g. of CH N(CH CH CH NH in dry benzene was added with 13.1 g. of
The mixture was refluxed for 2 hours in a water bath and was then cooled to deposit a crystalline mass. This mass was recrystallized from benzene to obtain the compound (5), MP. 8283 C.
SYNTHESIS EXAMPLE 3 Synthesis of the compound (6):
A solution of g. of HO(CH CH )1 H in 50 cc. of dry benzene was added with 6.1 g. of
The mixture was refluxed for 8 hours and then the benzene was removed by distillation under reduced pressure 4 to obtain the compound (6) in the form of a slightly yellow transparent solution, 11 1.4873.
SYNTHESIS EXAMPLE 4 Synthesis of the compound (12):
A solution of 13.6 g. of
mrkom-Q-om-Nm in dry. benzene was gradually added with 26.2 g. of C H SCH CH NCO. The mixture was refluxed for 3 hours and was then cooled to deposit a crystalline mass. This mass was recovered by filtration and was recrystallized from methanol to obtain the compound (12), MP. 207-208 C.
Other compounds than those mentioned above can also be synthesized according to the above-mentioned synthesis examples.
The thus obtained compounds employed in the present invention may be added to emulsions at any stage during the second ripening. Most desirably, however, they are preferably added at the beginning of the second ripening. Silver halide emulsions containing these compounds are increased in gamma, photographic speed and maximum density and make is possible to obtain light-sensitive photographic materials having improved storability.
The above-mentioned compound useful in the present invention may be added to a silver halide emulsion after dissolving the compound in water or in a water-miscible organic solvent such as methanol or ethanol. The amount of the compound to be added varies depending on the kind of the compound or of the silver halide emulsion employed, but is ordinarily in the range of 0.1 mg.-1'000 mg. per kg. of silver halide emulsion.
The compounds employed in the present invention are applicable to all types of silver halide emulsions such as silver chlorobromide emulsion, silver iodobromide emulsion, etc. Further the emulsions may have been subjected to gold sensitization or sulfur sensitization, and may have been incorporated with spectral sensitizers, polyalkylene oxide type sensitizers, various stabilizers, hardeners and coating aids.
The compounds employed in the present invention can be applied not only to monochhromatic photographic emulsions but also to color photographic emulsions containing oil-soluble or water-soluble color couplers. The silver halide photographic emulsions of the present invention which are obtained in the above-mentioned manner are coated onto common supports such as, for example, glass, cellulose triacetate film bases, polyester film bases or baryta papers.
The present invention is illustrated in further detail below with reference to examples, but the invention is not limited to these examples.
EXAMPLE 1 A silver halide emulsion comprising 2 mole percent of silver iodide and 98 mole percent of silver bromide Was subjected to second ripening by the use of a sulfur sensitizer and a gold sensitizer to prepare a silver iodobromide emulsion for high speed photographic negatives. This emulsion was divided into portions of 100 g. each, and the divided emulsions were individually incorporated with the present compounds set forth in Table 1 below. The thus treated emulsions were coated onto cellulose triacetate film bases and were then dried to prepare samples.
For comparison, the compound disclosed in U.S. Pat. No. 3,021,215 was treated in the same manner as above to prepare a control sample.
These samples were exposed to light by means of a sensitometer KS-I (manufactured and sold by Konishiroku Photo Industry Co., Ltd.) at Lux-5400 K., and
were then developed at 20 C. for minutes with a developer having the following composition:
G. Metol 3 Anhydrous sodium sulfite 50 Hydroquinone 6 Sodium carbonate (monohydrate) 29.5 Potassium bromide 1 Water to make 1 liter.
(The developer was used after dilution with water to 1:1.)
Thereafter, the samples were subjected to sensitometry 20 to obtain the results shown in Table 1.
NOTE .In the table, the speed is a relative value measured by assuming as 100 the speed of the nonineorporated sample. As is clear from Table 1, light-sensitive photographic materials improved in speed, gamma and maximum density can! be obtained by the use of the silver halide photographic emulsions in accordance with the present invention.
EXAMPLE 2 A neutral photographic emulsion for photographic negatives, which comprised 5 mole percent of silver iodide and 95 mole percent of silver bromide, was added with given amounts of a sulfur sensitizer and a gold sensitizer, and was then divided into portions of 100 g. each. The divided emulsions were individually incorporated with the present compounds set forth in Table 2 below. Each emulsion was maintained at 56 C. and was subjected to second ripening so as to attain the maximum density. Subsequently, 20 mg. per 100 g. of the emulsion of 4-hydroxy- 6-methyl-1,3,3a,7-tetrazaindene were added, and then suitable amounts of a film hardener and a coating aid were added. The thus treated emulsions were uniformly coated onto cellulose triacetate film bases and were then dried to prepare samples. These samples were subjected to storage test, and were then subjected to sensitometry in the same manner as in Example 1 to obtain the results as set forth in Table 2.
then added as a magenta coupler a given amount of a dispersion prepared by dissolving at an elevated temperature l (2,4,6 trichlorophenyl)-3-[3-(2,4-di-tertamylphenoxyacetamide) benzarnide] 5 pyrazolone in a mixture comprising di-n-butyl phthalate and ethyl acetate, and then dispersing the solution in a gelatine solution by means of sodium alkylbenzenesulfonate. This emulsion was thoroughly stirred and was then adjusted to pH 6.8 to obtain a color photographic emulsion.
Emulsions obtained in the above manner were immediately coated uniformly onto cellulose triacetate film bases and were then dried to prepare samples. These samples were exposed inthe same manner as in Example 1 and were then developed at 21 C. for 10 minutes with a color developer of the following composition:
N-Ethyl-N-p-methanesulfonamidoethyl 3 me'thyl- G. aminoaniline sulfate 2.5 Anhydrous sodium sulfite 2.0 Benzyl alcohol 3.8 Sodium hexametaphosphate 2.0
Sodium carbonate (monohydrate) 50.0 Potassium bromide 1.0 Caustic soda 0.6 Water to make 1 liter.
Thereafter, the samples were subjected to ordinary bleaching, fixing and water-washing treatments and then to sensitometry to obtain the results as shown in Table 3.
TABLE 3 Amount (mg/100 g. Incorporated compound emulsion) Speed Gamma Fog Compound (1) 1. 5 125 0.85 0.03 Compound (3) 1. 5 130 0. 07 0.03 Non-incorporated sample 100 0. 65 0. 03
No'rE.In the table, the speed is a relative value measured by as suming as 100 the white light speed of the non-incorporated sample.
TABLE 2 Incubated at room temperature for 3 days Incubated at C. relative Amount (mg/100 g. Maximum Maximum Maximum Incorporated compound emulsion) Speed density Fog Speed density Fog Speed density Fog Compound (4) 1. 0 125 2. 35 0. 05 125 2. 32 0. 07 130 2. 30 0. 07 Compound 1. 0 140 2. 40 0. 07 135 2. 42 0.08 135 2. 41 O. 06 Compound (l1) 1. 0 115 2. 30 0. 04 120 2. 32 0. 05 115 2. 30 0. 05 Non-incorporated sample 100 2. 02 0. 08 105 2. 0S 0. 08 100 2. 05 0. 07
(In the table, the speed is a relative value measured by assuming as 100 the speed of the non-incorporated sample.)
From the above table, it is clear that the silver halide photographic emulsions in accordance with the present invention give light-sensitive photographic materials which, even when stored under severe conditions, are less subject to formation of fog and free from any decrease in speed.
EXAMPLE 3 and which is not bonded through an oxygen atom to B; A is a lower alkylene group, or a polyalkylene ether group having the formula (CH CH O) provided that A and A are not both polyalkylene ether groups at the same time, and p is an integer of 2 to 30';
B and B are -NH- or O', provided that both are not -O- at the same time;
R is a lower alkyl group, a phenyl group, an aralkyl group or (CH )q COOR', wherein q is an integer of 1 to 3, and R is a lower alkyl group; and
X is a divalent group of the formula -S, -O,
CH3 u wherein R" is a lower alkyl group.
2. A light-sensitive silver halide photographic emulsion as claimed in claim 1, further comprising a color former.
3. A light-sensitive silver halide photographic emulsion as claimed in claim 1, further comprising at least one other known chemical and/or spectral sensitizer.
4. A light-sensitive silver halide photographic emulsion as claimed in claim 1, further comprising at least one photographic additive selected from the group consisting of stabilizers and hardeners.
5. A light-sensitive silver halide photographic emulsion as claimed in claim 1, wherein the sensitizer is present in an amount of 0.1 to 1000 mg. per kg. of silver halide emulsion.
References Cited UNITED STATES PATENTS 2,739,060 3/1956 Lowe et a1. 96l07 3,021,215 2/1962 Williams et a1. 96l07 3,046,129 7/1962 Graham et al 96l07 NORMAN G. TORCHIN, Primary Examiner R. FIGHTER, Assistant Examiner US. Cl. X.R. 96--109
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9099068 | 1968-12-13 |
Publications (1)
Publication Number | Publication Date |
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US3625697A true US3625697A (en) | 1971-12-07 |
Family
ID=14013934
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US884022A Expired - Lifetime US3625697A (en) | 1968-12-13 | 1969-12-10 | Sensitization of light-sensitive silver halide photographic emulsions |
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US (1) | US3625697A (en) |
GB (1) | GB1249248A (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4251617A (en) * | 1979-10-01 | 1981-02-17 | Polaroid Corporation | Novel silver complexing agents |
US4272632A (en) * | 1979-10-01 | 1981-06-09 | Polaroid Corporation | Novel silver complexing agents |
US4276374A (en) * | 1978-05-30 | 1981-06-30 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion with thioether sensitizer |
US4294920A (en) * | 1978-04-27 | 1981-10-13 | Agfa-Gevaert Aktiengesellschaft | Photographic silver halide emulsion |
EP0124795A2 (en) | 1983-04-11 | 1984-11-14 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion |
US5015567A (en) * | 1983-10-07 | 1991-05-14 | Fuji Photo Film Co., Ltd. | Method for producing silver halide photographic emulsion and silver halide photographic material |
USH1091H (en) | 1988-08-09 | 1992-08-04 | Konica Corporation | Light-sensitive silver halide photographic material |
-
1969
- 1969-12-09 GB GB60128/69A patent/GB1249248A/en not_active Expired
- 1969-12-10 US US884022A patent/US3625697A/en not_active Expired - Lifetime
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4294920A (en) * | 1978-04-27 | 1981-10-13 | Agfa-Gevaert Aktiengesellschaft | Photographic silver halide emulsion |
US4276374A (en) * | 1978-05-30 | 1981-06-30 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion with thioether sensitizer |
US4251617A (en) * | 1979-10-01 | 1981-02-17 | Polaroid Corporation | Novel silver complexing agents |
US4272632A (en) * | 1979-10-01 | 1981-06-09 | Polaroid Corporation | Novel silver complexing agents |
EP0124795A2 (en) | 1983-04-11 | 1984-11-14 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion |
US5015567A (en) * | 1983-10-07 | 1991-05-14 | Fuji Photo Film Co., Ltd. | Method for producing silver halide photographic emulsion and silver halide photographic material |
USH1091H (en) | 1988-08-09 | 1992-08-04 | Konica Corporation | Light-sensitive silver halide photographic material |
Also Published As
Publication number | Publication date |
---|---|
DE1961842B2 (en) | 1976-09-23 |
GB1249248A (en) | 1971-10-13 |
DE1961842A1 (en) | 1970-07-30 |
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