US3617295A - Photographic silver halide emulsion - Google Patents
Photographic silver halide emulsion Download PDFInfo
- Publication number
- US3617295A US3617295A US707478A US3617295DA US3617295A US 3617295 A US3617295 A US 3617295A US 707478 A US707478 A US 707478A US 3617295D A US3617295D A US 3617295DA US 3617295 A US3617295 A US 3617295A
- Authority
- US
- United States
- Prior art keywords
- group
- silver halide
- halide emulsion
- member selected
- sensitizing dye
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- -1 silver halide Chemical class 0.000 title claims abstract description 49
- 239000000839 emulsion Substances 0.000 title claims abstract description 48
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 45
- 239000004332 silver Substances 0.000 title claims abstract description 45
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 claims description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 claims description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 2
- 125000005110 aryl thio group Chemical group 0.000 abstract description 10
- 125000004104 aryloxy group Chemical group 0.000 abstract description 10
- 125000003118 aryl group Chemical group 0.000 abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 abstract description 5
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- 125000005843 halogen group Chemical group 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 125000002947 alkylene group Chemical group 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 125000004070 6 membered heterocyclic group Chemical group 0.000 abstract description 3
- 125000000129 anionic group Chemical group 0.000 abstract description 3
- 125000000547 substituted alkyl group Chemical group 0.000 abstract description 3
- 125000002373 5 membered heterocyclic group Chemical group 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 230000003595 spectral effect Effects 0.000 description 18
- 230000035945 sensitivity Effects 0.000 description 17
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 206010070834 Sensitisation Diseases 0.000 description 5
- 230000008313 sensitization Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000298 carbocyanine Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 2
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical group O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 101150065749 Churc1 gene Proteins 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
- 102100038239 Protein Churchill Human genes 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001556 benzimidazoles Chemical class 0.000 description 2
- KXNQKOAQSGJCQU-UHFFFAOYSA-N benzo[e][1,3]benzothiazole Chemical class C1=CC=C2C(N=CS3)=C3C=CC2=C1 KXNQKOAQSGJCQU-UHFFFAOYSA-N 0.000 description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 2
- 125000004181 carboxyalkyl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000002916 oxazoles Chemical class 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000004964 sulfoalkyl group Chemical group 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical class C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical group CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- 102100021555 RNA cytosine C(5)-methyltransferase NSUN2 Human genes 0.000 description 1
- 101710173722 RNA cytosine C(5)-methyltransferase NSUN2 Proteins 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 241000933336 Ziziphus rignonii Species 0.000 description 1
- 241000981595 Zoysia japonica Species 0.000 description 1
- 125000005526 alkyl sulfate group Chemical group 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- QWYZFXLSWMXLDM-UHFFFAOYSA-M pinacyanol iodide Chemical compound [I-].C1=CC2=CC=CC=C2N(CC)C1=CC=CC1=CC=C(C=CC=C2)C2=[N+]1CC QWYZFXLSWMXLDM-UHFFFAOYSA-M 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 235000010263 potassium metabisulphite Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052718 tin Inorganic materials 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
- G03C1/28—Sensitivity-increasing substances together with supersensitising substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
- C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/10—The polymethine chain containing an even number of >CH- groups
- C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- 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
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/10—Organic substances
- G03C1/12—Methine and polymethine dyes
-
- 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
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
- G03C1/8155—Organic compounds therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/392—Additives
- G03C7/39208—Organic compounds
- G03C7/39292—Dyes
Definitions
- R each represents a member selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atom, an alkoxyl group, an aryloxyl group, and arylthio group
- R represents a member selected from the group consisting of an aryloxyl group and an arylthio group
- W represents a member selected from the group consisting ofCH and N.
- the present invention relates to a spectral sensitized photographic silver halide emulsion and in particular to a photographic silver halide emulsion in which the formation of photographic fogs caused by the addition of a sensitizing dye is inhibited and the reduction of the color sensitivity during the preservation is prevented.
- the silver halide emulsion is spectrally sensitized, it usually has a bad influence on the photographic properties of the photographic silver halide emulsion.
- a sensitizing dye hereinafter, such a fog is called dye fog
- the instability of the dye sensitivity greatly hinders the preparation of a photographic light-sensitive element having high strength spectral sensitivity, reduced fog and good preservability.
- the spectral sensitivity is remarkably reduced in some cases. Further, the spectral sensitivity is degraded extremely in other cases when the material is stored.
- the aforesaid additives must be selected strictly in accordance with the sensitizing dye to be employed.
- An object of the present invention is to provide a photographic silver halide emulsion sensitized by a spectral sensitizing method, in which the formation of dye fogs is inhibited and the degradation of spectral sensitivity with the lapse of time is reduced without lowering the spectral sensitivity.
- Another object of the present invention is to provide an excellent red-sensitive silver halide emulsion for color photographic light sensitive materials.
- D represents a divalent aromatic residual group
- R and R each represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkoxyl group, an aryloxyl group, or an arylthio group
- R and R each represent an aryloxyl group or an arylthio group
- W represents CH or N.
- the 4-quinoline nucleus shown by Z may have a substituent such as a halogen atom, an alkyl group, or an alkoxyl group.
- the examples of the heterocyclic rings to be completed by the nonmetallic atomic group represented by Z are a 4-quinoline nucleus, a 2-quinoline nucleus, a naphthothiazole nucleus, an oxazole nucleus, and a benzimidazole nucleus.
- R or R may be a lower alkyl group such as a methyl group, an ethyl group or a propyl group or a substituted group thereof such as a B-hydroxyethyl group, ,B-acetoxyethyl group, or ethylsulfate group; a carboxyalkyl group or a derivative thereof such as a carboxymethyl group or a 2-(2-carboxy-ethoxy) ethyl group; a sulfoalkyl group or a derivative thereof such as a B-sulfoethyl group, a B- sulfopropyl group, or a 3-methoxy-2-(3-sulfopropoxy) propyl group.
- the main feature of the sensitizing dye having the chemical structure shown by general formula I is that it contains at least one quinoline heterocyclic nucleus.
- the examples of the divalent aromatic residual group represented by D are a biphenylene group, a naphthalene group, a stilbene group and a bibenzyl group.
- each of the pyrimidinylamino nuclei or triazinylamino nuclei bonded by the divalent aromatic residual group has at least one arylthio group or aryl oxyl group.
- the sensitizing dye represented by general formula I (hereinafter the sensitizing dye is called Sensitizing Dye I) can spectrally sensitize a photographic silver halide emulsion in a wavelength region of from a green region to a red region by properly selecting the heterocyclic nucleus shown by However, there is a fault that in the case of incorporating in a silver halide emulsion the sensitizing dye alone, dye fogs tend to be formed and also the color sensitivity by the sensitizing dye is lowered in course of time.
- the compound shown by general formula II does not substantially have spectral absorption at visible ranges but has a strong absorption at a near ultraviolet region.
- sensitizing dye I is incorporated in a silver halide emulsion together with compound II for sensitizing the silver halide emulsion, the formation of dye fogs can be effectively inhibited and markedly prevented without substantially reducing the spectral sensitivity.
- Compound ll of this invention provides the aforesaid merits or effects selectively to only the carbocyanine sensitizing dye represented by general formula I, that is, a sensitizing dye showing a M-band type spectral sensitization among various carbocyanine dyes and when compound II is incorporated in a photographic silver halide emulsion together with other carbocyanine dyes showing a J-band type or H-band type spectral sensitization, the spectral sensitivity is markedly reduced on the contrary.
- the carbocyanine sensitizing dye represented by general formula I that is, a sensitizing dye showing a M-band type spectral sensitization among various carbocyanine dyes and when compound II is incorporated in a photographic silver halide emulsion together with other carbocyanine dyes showing a J-band type or H-band type spectral sensitization, the spectral sensitivity is markedly reduced on the contrary.
- the one of which the pyrimidinylamino nuclei each having at least one aryl oxyl group or arylthio group has such merits when used together with sensitizing dye I in a photographic silver halide emulsion for color photographic light-sensitive 1 materials that the contamination by color development is prevented, the formation of stains by the sensitizing dye is reduced and the reduction of spectral sensitization by the presence of a coupler is prevented besides the aforesaid spectral sensitivity, and the prevention of the reduction in color sensitivity in course of time.
- sensitizing dyes represented by general formula I are shown below although the sensitizing dye is not limited to them only:
- the compound in which Z is -N- that is, the compound having 60 a S-triazine nucleus
- the compound in which Z is -CH-, that is, having a pyrimidine nucleus may be prepared as follows:
- Sensitizing dye l or compound II in this invention may be incorporated in a silver halide emulsion as an aqueous solution t rsqtlq a o i mlhsrwfia5232969 Olvem
- a silver halide emulsion as an aqueous solution
- t rsqtlq a o i mlhsrwfia5232969 Olvem Such as methanol, ethanol, alkaline methanol, and the l ike separately, or as a mixture thereof.
- the amounts thereof and the ratio thereof are suitably selected in accordance with the kinds of each compound, the emulsion to be employed and additives.
- a suitable concentration of sensitizing dye I is 0.002-0.2 g. per 1 g. molecule of the silver halide in a silver halide emulsion and a suitable concentration of compound 11 is 0.01- g. per 1 g. molecule of the silver halide in a silver halide emulsion, and a preferable concentration ratio of Senby a conventional manner and may be applied to a suitable support such as a cellulose derivative film or a baryta coated paper.
- EXAMPLE 1 A definite amount of a 4X10" mol methanol solution of Sensitizing dye l in this invention was added to 100 g. (AgX: 33x10 mol) of silver chloro-bromide emulsion prepared by a conventional method and a definite amount of a 0.1 percent methanol solution of compound II was immediately added to the resulting emulsion. The mixture was stirred for 1 hour at 40 C. and applied to a support in a thickness of 7 ml. per cabinet size followed by drying.
- the light sensitive element thus prepared was exposed by using an optical wedge through a blue filter transmitting only light having shorter wavelengths than 500 m. p. and a yellow filter transmitting only light having longer wavelengths than 500 m. p. and then developed for 10 minutes at 20 C. in a developer having the composition shown below, followed by fixing.
- EXAMPLE 2 A definite amount of a 4X10 mol methanol solution of Sensitizing dye l and a definite amount of a 0.1 percent methanol solution of compound 11 were added to 100 g. (AgX: 3O 10 mol) of a silver bromide emulsion prepared by a conventional method. The resulting emulsion was stirred for 30 minutes at 40 C., mixed with a hardening agent and a wetting agent, and applied to a film base followed by drying.
- the light sensitive film was stored at a temperature of 24-30 C. and a relative humidity of 65 -70 percent and the spectral sensitivity (S using a yellow filter was measured as in example 1 the results ofwhich are shown in table 2.
- Z represents a nonmetallic atomic group forming a nucleus of the 4-quinoline series
- Z represents a nonmetallic atomic group necessary to complete a member selected from the group consisting of a 4-quinoline nucleus, a 2-quinoline nucleus, a naphthothiazole nucleus, an oxazole nucleus, and a benzimidazole nucleus
- R, and R each represents a member selected from the group consisting of an alkyl group, a hydroxyalkyl group, an acetoxyalkyl group, an alkylsulfate group, a carboxyalkyl group, a carboalkoxyalkyl group, a sulfoalkyl group, an alkoxysulfoalkoxyalkyl group
- R represents a member selected from the group consisting of a hydrogen atom and an alkylene group having 2-5 carbon atoms capable of condensing with R X represents an acid anionic group,
- D represents a divalent aromatic residual group selected from the group consisting of a biphenylene group a phenylene group a naphthylene group (-C l-l ),a stilbene group and a bibenzyl group R.
- R each represents a member selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atom, an alkoxyl group, an aryloxyl group and arylthio group,
- R and R each represents a member selected from the group consisting of an aryloxyl group and an arylthio group
- W represents a member selected from the group consisting of CH and N.
- sensitizing dye is a compound selected from the group consisting of:
- said silver halide is selected from the group consisting of silver iodobromide, silver bromide, silver chlorobromide and silver chloride.
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Plural Heterocyclic Compounds (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1166967 | 1967-02-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3617295A true US3617295A (en) | 1971-11-02 |
Family
ID=11784376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US707478A Expired - Lifetime US3617295A (en) | 1967-02-23 | 1968-02-23 | Photographic silver halide emulsion |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3617295A (enrdf_load_html_response) |
| BE (1) | BE711224A (enrdf_load_html_response) |
| DE (1) | DE1622283C3 (enrdf_load_html_response) |
| FR (1) | FR1582816A (enrdf_load_html_response) |
| GB (1) | GB1210943A (enrdf_load_html_response) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3887380A (en) * | 1970-06-02 | 1975-06-03 | Fuji Photo Film Co Ltd | Direct positive silver halide photographic emulsion |
| US4002480A (en) * | 1974-03-07 | 1977-01-11 | Fuji Photo Film Co., Ltd. | Photographic silver halide emulsion |
| EP0124795A2 (en) | 1983-04-11 | 1984-11-14 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion |
| EP0143424A2 (en) | 1983-11-25 | 1985-06-05 | Fuji Photo Film Co., Ltd. | Heat-developable light-sensitive materials |
| EP0210660A2 (en) | 1985-07-31 | 1987-02-04 | Fuji Photo Film Co., Ltd. | Image forming process |
| EP0239363A2 (en) | 1986-03-25 | 1987-09-30 | Konica Corporation | Light-sensitive silver halide photographic material feasible for high speed processing |
| US4710631A (en) * | 1984-08-28 | 1987-12-01 | Fuji Photo Film Co., Ltd. | Temperature compensation for a semiconductor light source used for exposure of light sensitive material |
| EP0253390A2 (en) | 1986-07-17 | 1988-01-20 | Fuji Photo Film Co., Ltd. | Photographic support and color photosensitive material |
| WO1996013755A1 (en) | 1994-10-26 | 1996-05-09 | Eastman Kodak Company | Photographic emulsions of enhanced sensitivity |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2945762A (en) * | 1955-10-12 | 1960-07-19 | Eastman Kodak Co | Supersensitization of photographic emulsions using triazines |
| US3416927A (en) * | 1964-12-08 | 1968-12-17 | Eastman Kodak Co | Silver halide emulsions containing supersensitizing combinations of merocyanine dyes |
-
1968
- 1968-02-20 DE DE1622283A patent/DE1622283C3/de not_active Expired
- 1968-02-21 FR FR1582816D patent/FR1582816A/fr not_active Expired
- 1968-02-23 BE BE711224D patent/BE711224A/xx unknown
- 1968-02-23 US US707478A patent/US3617295A/en not_active Expired - Lifetime
- 1968-02-23 GB GB8982/68A patent/GB1210943A/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2945762A (en) * | 1955-10-12 | 1960-07-19 | Eastman Kodak Co | Supersensitization of photographic emulsions using triazines |
| US3416927A (en) * | 1964-12-08 | 1968-12-17 | Eastman Kodak Co | Silver halide emulsions containing supersensitizing combinations of merocyanine dyes |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3887380A (en) * | 1970-06-02 | 1975-06-03 | Fuji Photo Film Co Ltd | Direct positive silver halide photographic emulsion |
| US4002480A (en) * | 1974-03-07 | 1977-01-11 | Fuji Photo Film Co., Ltd. | Photographic silver halide emulsion |
| EP0124795A2 (en) | 1983-04-11 | 1984-11-14 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion |
| EP0143424A2 (en) | 1983-11-25 | 1985-06-05 | Fuji Photo Film Co., Ltd. | Heat-developable light-sensitive materials |
| US4710631A (en) * | 1984-08-28 | 1987-12-01 | Fuji Photo Film Co., Ltd. | Temperature compensation for a semiconductor light source used for exposure of light sensitive material |
| EP0210660A2 (en) | 1985-07-31 | 1987-02-04 | Fuji Photo Film Co., Ltd. | Image forming process |
| EP0239363A2 (en) | 1986-03-25 | 1987-09-30 | Konica Corporation | Light-sensitive silver halide photographic material feasible for high speed processing |
| EP0253390A2 (en) | 1986-07-17 | 1988-01-20 | Fuji Photo Film Co., Ltd. | Photographic support and color photosensitive material |
| WO1996013755A1 (en) | 1994-10-26 | 1996-05-09 | Eastman Kodak Company | Photographic emulsions of enhanced sensitivity |
Also Published As
| Publication number | Publication date |
|---|---|
| DE1622283C3 (de) | 1974-06-06 |
| DE1622283B2 (de) | 1973-10-31 |
| GB1210943A (en) | 1970-11-04 |
| DE1622283A1 (de) | 1970-12-03 |
| FR1582816A (enrdf_load_html_response) | 1969-10-10 |
| BE711224A (enrdf_load_html_response) | 1968-07-01 |
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