US3769026A - Spectrally sensitized silver halide photographic emulsion - Google Patents
Spectrally sensitized silver halide photographic emulsion Download PDFInfo
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- US3769026A US3769026A US00184604A US3769026DA US3769026A US 3769026 A US3769026 A US 3769026A US 00184604 A US00184604 A US 00184604A US 3769026D A US3769026D A US 3769026DA US 3769026 A US3769026 A US 3769026A
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- silver halide
- halide photographic
- photographic emulsion
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- 239000000839 emulsion Substances 0.000 title claims abstract description 64
- -1 silver halide Chemical class 0.000 title claims abstract description 53
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 50
- 239000004332 silver Substances 0.000 title claims abstract description 50
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 41
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 claims abstract description 21
- 239000000298 carbocyanine Substances 0.000 claims abstract description 19
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 9
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000004181 carboxyalkyl group Chemical group 0.000 claims description 3
- 125000004964 sulfoalkyl group Chemical group 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 26
- 206010034960 Photophobia Diseases 0.000 abstract description 9
- 208000013469 light sensitivity Diseases 0.000 abstract description 9
- 150000003536 tetrazoles Chemical class 0.000 abstract description 4
- 239000000975 dye Substances 0.000 description 54
- 206010070834 Sensitisation Diseases 0.000 description 10
- 230000008313 sensitization Effects 0.000 description 10
- 230000003595 spectral effect Effects 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 208000015181 infectious disease Diseases 0.000 description 5
- 230000002458 infectious effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical compound C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000000586 desensitisation Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 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 3
- 239000000126 substance Substances 0.000 description 3
- 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
- 108010010803 Gelatin Proteins 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
- 150000001450 anions Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 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
- 238000005728 strengthening Methods 0.000 description 2
- AGJZCWVTGOVGBS-UHFFFAOYSA-N 1,1'-diethyl-2,2'-cyanine Chemical compound C1=CC2=CC=CC=C2N(CC)\C1=C\C1=CC=C(C=CC=C2)C2=[N+]1CC AGJZCWVTGOVGBS-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- 229920001817 Agar Polymers 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 101100382267 Caenorhabditis elegans cah-1 gene Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- UELITFHSCLAHKR-UHFFFAOYSA-N acibenzolar-S-methyl Chemical compound CSC(=O)C1=CC=CC2=C1SN=N2 UELITFHSCLAHKR-UHFFFAOYSA-N 0.000 description 1
- 229940060198 actron Drugs 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 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
- 229910021538 borax Inorganic materials 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000004195 dipotassium inosinate Substances 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- DKYWVDODHFEZIM-UHFFFAOYSA-N ketoprofen Chemical compound OC(=O)C(C)C1=CC=CC(C(=O)C=2C=CC=CC=2)=C1 DKYWVDODHFEZIM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
Images
Classifications
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- 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
- G03C1/28—Sensitivity-increasing substances together with supersensitising substances
- G03C1/29—Sensitivity-increasing substances together with supersensitising substances the supersensitising mixture being solely composed of dyes ; Combination of dyes, even if the supersensitising effect is not explicitly disclosed
Definitions
- the photographic sensitive materials are required to have high sensitivity at the specific wavelengths different from each other according to the purpose for use.
- sensitizing dyes bring about the lowering of the sensitivity of the emulsion in the intrinsic sensitivity region thereof, i.e., desensitization, while they bring about spectral sensitization. Therefore, it is quite advantageous to use at least two kinds of sensitizing dyes, which are in a supersitizing relation to each other and do not accompany desensitizing actron.
- the object of this invention is to lower the desensitizing action and to raise both the sensitivity intrinsic to silver halide and the panchromatically sensitized spectral sensitivity by using at least two kinds of sensitizing dyes.
- the second object of this invention is to improve the image quality of the spectrally sensitized photographic sensitive material.
- the sensitizing dyes affect the development of the photographic emulsion and, in many cases, lower the quality of the photographic image.
- cationic dyes affect the infectious development, which is employed for photographic plate making, and deteriorate the dot quality obtained. Therefore, it is also the object of this invention to obtain high panchromatic sensitivity by supersensitization using a restricted cyanine dye and another merocyanine dye, which have little effect on infectious development, and to obtain good dot quality, which is difircult to obtain by supersensitization using more than two kinds of cyanine dyes together.
- Merocyanine dyes are generally adsorbed Hat on silver halide to prohibit the formation of the J aggregate of the carbocyanine dye and, as a result thereof, lower the red sensitivity extremely.
- One of the characteristics of this invention is the discovery of a method for strengthening the formation of the J aggregate of the restricted carbocyanine by strictly selecting the chemical structure of the merocyanine dye.
- Theobject of ,this invention is accomplished by'the combined use of at least one sensitizing carbocyanine dye having two heterocyclic nuclei selected from the group consisting of a benzothiazole nucleus,-a benzoselenazolenucleus, a fi-naphthoselenaz ole nucleus, and a B-naphthothiazole nucleus, the m'eso-position of said dye being substituted with a methyl or ethyl group and, preferably, at least one of the N-substituents of said heterocyclic nuclei being a sulfoalkyl group or a carboxy alkyl groupvMore specifically, weare speaking of sensitizing dyes of the following general formula (I), and at least one merocyanine dye, wherein a tetrazole derivative nucleus and a merocyanine nucleus-are connected through a dimethine chain, more specifically, sens
- R and R each represents a lower alkyl group, such as methyl, ehtyl, propyl, gamma-sulfopropyl-, gamma-sulfobutyl, delta-sulfobutyl, beta-hydroxyethyl, beta-carboxyethyl, allyl group, etc.;
- A represents a lower alkyl group, preferably a methyl or an ethyl group;
- Z and Z each represents the 1 non-metallic atoms necessary to complete a benzothiazole; benzoselenazole, beta-naphthoselenazole, or betanaphthothiazole nucleus, which may be substituted with a halogen atom, such as chlorine, bromine, etc., a lower alkyl group, such as methyl, ethyl, etc., an alkoxy group, such as methoxy, ethoxy, etc., an alko x
- the cyanine dyes of this invention having the general formula (I) have their maximum sensitization part between 595 and 690 nm, and many of them have high red sensitivity. Some of the sensitizing dyes having the general formula (11) have their maximum sensitization part between 460 and 560 um, and others do not exhibit remarkable spectral sensitization action, even when used together with a silver iodide emulsion.
- the red sensitivity arising from the sensitizing dye of the general formula (I) is further raised, thewhite light sensitivity is remarkably raised and the silver halide photographic emulsion, which almost does not cause intrinsic desensitization, can be obtained by the combined use of at least one of the sensitizing dyes of the general formula (1) and at least one of the sensitizing dyes of the general formula (11), which have the said characteristics.
- the combination of meso-methyl-carbocyanine being one of the sensitizing dyes represented by the general formula (I), and the sensitizing dye of the general formula (ll) wherein Z is sulfur, remarkably raises the white light sensitivity and red sensitivity, and brings about remarkable maximum sensitization around 630 nm.
- the sensitizing dyes of the general formula (1) do not deteriorate the dot quality obtained by the infectious development employed for the sensitive material for print plate making in proportion to the fact that they strongly and spectrally supersensitize to the relatively long wavelength of 690 nm.
- the application of the known supersensitizing art using cyanine dyes together in order to raise the spectral sensitivity badly deteriorates the dot quality.
- the application of the supersensitizing art described in the specification of US. Pats. Nos. 2,533,426, 2,688,545, and 2,751,298, the specification of German Pat. No. 1,547,641, the specification of German Patent Prepublication No. 1,813,001, Japanese Patent Publication No. 16169/68 and No. 4132/68 are disadvantageous because of the reason described above.
- the merocyanine dye represented by the general formula rather strengthens the infectious development, and is useful to obtain good dot quality. Accordingly, the supersensitizing art of this invention is useful espe cially for the panchromatic sensitization of the sensitive material for printing plates which are to be subjected to the treatment of infectious development.
- the spectral sensitization method of this invention is useful for the spectral sensitization of the gelatinosilver-halide photographic emulsion. It is also useful for the emulsion containing a hydrophilic polymer, other than gelatin, such as agar collodion, water-soluble cellulose derivatives, polyvinyl alcohol, polyvinyl- -pyrrolidone copolymer and other synthesized hydrophilic resin, natural hydrophilic polymer, gelatin derivatives, and the like.
- a hydrophilic polymer other than gelatin, such as agar collodion, water-soluble cellulose derivatives, polyvinyl alcohol, polyvinyl- -pyrrolidone copolymer and other synthesized hydrophilic resin, natural hydrophilic polymer, gelatin derivatives, and the like.
- the photographic emulsion to be used in this invention is suitably a mixed silver halide comprising at least two of silver chloride, silver bromide and silver iodide.
- the sensitizing dye according to this invention is introduced into a photographic emulsion according to a conventional method.
- dyes are dissolved in a solvent, such as methanol, ethanol, water, cellosolve, water-soluble ketones, etc., and added to an emulsion.
- dyes may also be dissolved in an oil, slightly soluble in water, then added to water or a hydrophilic colloid to disperse the same.
- the mol ratio of the sensitizing carbocyanine to the sensitizing merocyanine to be contained in the emulsion can vary widely from 9:1 to 1:9 depending upon the effects desired.
- the amount of each of the dyes is preferably in the range of from 1 X 10" to l X 10 mol per mol of silver according to the character of the emulsion employed.
- the photographic emulsion of this invention can be subjected to further hypersensitization and other supersensitization in the known manner.
- conventional additives such as chemical sensitizers,
- stabilizers may be contained in the photographic emulsion of this invention in a conventional manner.
- the photographic emulsion of this invention may be coated in a common manner on a suitable support, such as a glass plate, film of a cellulose derivative, film of a synthetic resin, Baryta paper, resin-coated paper, etc.
- a suitable support such as a glass plate, film of a cellulose derivative, film of a synthetic resin, Baryta paper, resin-coated paper, etc.
- a silver halide photographic emulsion was prepared 'by adding separately the dye of this invention illustrated before and to be used in this invention independently to a silver bromoiodide emulsion (AglzAgBr 7 molsz93 mols).
- a silver halide photographic emulsion containing both the earbocyanine dye and the merocyanine dye was prepared.
- the white light sensitivity and the red light sensitivity obtained by the combined use of the sensitizing dyes of this invention are far higher than those obtained by the independent use thereof.
- the sensitizing effect obtained by the combination of at least one of the carbocyanine dyes and at least one of the merocyanine dyes is not deteriorated if an orthochromatic sensitizing dye already known, such as that of 11 or 12, is further used together.
- the orthochromatic sensitizing dyes used together with the sensitizing dyes employed in this invention are, for example, 2,2- cyanine and pseudo-type cyanine (e.g., 2'-thiacyanine) having the following chemical structures, but are not solely limited to these.
- a silver halide photographic emulsion comprising a supersensitizing combination of at least one sensitizing carbocyanine dye having two heterocyclic nuclei selected from the group consisting of a benzothiazole nucleus, a benzoselenazole nucleus, a B-naphthoselenazole nucleus and a B-naphthothiazole nucleus, the meso-position of said dye being substituted with a member selected from the group consisting of a methyl and an ethyl group, and at least one merocyanine dye in which a tetrazole derivative nucleus and a merocyanine nucleus are connected through a dimethine chain.
- R, and R each represents a lower alkyl group
- A represents a member selected from the group con sisting of a methyl and an ethyl group
- Z and Z
- ring selected from the group consisting of a benzothiazole nucleus, a benzoselenazole nucleus, a fi-naphthoselenazole nucleus, and a B-naphthothiazole nucleus;
- R and R each represents a lower alkyl group
- B represents a member selected from the group consisting of a lower alkyl and an aryl group
- Z, and Z of formula (I) are nonmetallic atoms necessary to complete a member selected from the group consisting of a benzothiazole and a B-naphthothiazole nucleus.
- A'of formula (I) is a'methyl group and Z of formula (II) is a sulfur atom.
- the orthochromatic sensitizing dye is selected from the group consisting of a 2,2'-cyanine dye and a pseudo-type cyanine dye.
- the silver halide photographic emulsion of claim v1 wherein the carbocyanine dye is selected from the group consisting of and the merocyanine dye is selected from the group 6 consi t ing of H I V ⁇ 102E933 21 22 10.
- the silver halide photographic emulsion of claim and 7, wherein the orthochromatic sensitizing dye is selected from the group consisting of N CHCHS :l S zHa O ⁇ N -S V7 7 C H;CH CHI I 10 13.
- the silver halide photographic material compris- 12.
- the silver halide photographic emulsion comprisin a l r ntai i th ilv r h lid l i f ing a supersensitizing combination of claim 1 V. V.V. mm 7 16.
- the silver halide photographic emulsion of claim 5 s 1, wherein the mol ratio of said carbocyanine dye to said merocyanine dye ranges from 9:1 to l:9.' I 17.
- each of said cyanine and merocyanine dye LL is present in an amount of l X l()' to I X l0 mol pcr nmsommcnma mol of Silven (HDaSOa'
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Spectroscopy & Molecular Physics (AREA)
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- Engineering & Computer Science (AREA)
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- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Silver halide emulsions containing a supersensitizing combination of at least one sensitizing carbocyanine dye and at least one merocyanine dye containing a tetrazole nucleus giving a high white light sensitivity or red sensitivity.
Description
United States Patent 1 Shiba et al.
[ Oct. 30, 1973 SPECTRALLY SENSITIZED SILVER HALIDE PHOTOGRAPHIC EMULSION [30] Foreign Application Priority Data Sept. 28, 1970 Japan 45/84532 [52] US. Cl. 96/126, 96/137, 96/140 [51] Int. Cl G03c 1/14, G03c 1/22 [58] Field of Search 96/124, 140, 126
[56] References Cited UNITED STATES PATENTS 2,430,558 11/1947 Carroll et a1 96/124 FOREIGN PATENTS OR APPLICATIONS 1,019,418 11/1957 Germany 96/140 Primary Examiner-Norman G. Torchin Assistant Examiner-M. F. Kelley AtlomeySughrue, Rothwell, Mion, Zinn and Macpeak [57] ABSTRACT Silver halide emulsions containing a supersensitizing combination of at least one sensitizing carbocyanine dye and at least one merocyanine dye containing a tetrazole nucleus giving a high white light sensitivity or red sensitivity.
17 Claims, 6 Drawing Figures PATENTEDum 30 I915 251G552; E5 Tzbzwdzi ONN 0mm 9% O8 0% own o? 2% 8 8m cw Q8 0% com own own 8v 9 1- c an SPECTRALLY SENSITIZED SILVER HALIDE PHOTOGRAPHIC EMULSION BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a spectrally sensitized silver halide photographic emulsion and more particularly to a silver halide photographic emulsion preparedby the combined use of at least more than two kinds of sensitizing dyes to obtain a high white light sensitivity or red sensitivity.
The photographic sensitive materials are required to have high sensitivity at the specific wavelengths different from each other according to the purpose for use.
2. Description of the Prior Art It has been well known in the art that for making such photographic sensitive materials certain kinds of sensitizing dyes are added to a silver halide photographic emulsion to raise the sensitivity in the region of wavelengths longer thanthe region of wavelengths of sensitivity intrinsic to saidsilver halide; that is, the art of spectral sensitization. Usually more than two kinds of sensitizing dyes are used together, generally, for photographic sensitive materials having panchromatically sensitized spectral sensitivity in order to obtain a desired spectral sensitivity distribution.
Many of the sensitizing dyes, however, bring about the lowering of the sensitivity of the emulsion in the intrinsic sensitivity region thereof, i.e., desensitization, while they bring about spectral sensitization. Therefore, it is quite advantageous to use at least two kinds of sensitizing dyes, which are in a supersitizing relation to each other and do not accompany desensitizing actron.
SUMMARY OF THE INVENTION The object of this invention is to lower the desensitizing action and to raise both the sensitivity intrinsic to silver halide and the panchromatically sensitized spectral sensitivity by using at least two kinds of sensitizing dyes.
The second object of this invention is to improve the image quality of the spectrally sensitized photographic sensitive material. Generally, the sensitizing dyes affect the development of the photographic emulsion and, in many cases, lower the quality of the photographic image. Especially, cationic dyes affect the infectious development, which is employed for photographic plate making, and deteriorate the dot quality obtained. Therefore, it is also the object of this invention to obtain high panchromatic sensitivity by supersensitization using a restricted cyanine dye and another merocyanine dye, which have little effect on infectious development, and to obtain good dot quality, which is difircult to obtain by supersensitization using more than two kinds of cyanine dyes together.
Merocyanine dyes are generally adsorbed Hat on silver halide to prohibit the formation of the J aggregate of the carbocyanine dye and, as a result thereof, lower the red sensitivity extremely. One of the characteristics of this invention is the discovery of a method for strengthening the formation of the J aggregate of the restricted carbocyanine by strictly selecting the chemical structure of the merocyanine dye.
Other objects and advantages will become apparent from the following discussion.
Theobject of ,this invention is accomplished by'the combined use of at least one sensitizing carbocyanine dye having two heterocyclic nuclei selected from the group consisting of a benzothiazole nucleus,-a benzoselenazolenucleus, a fi-naphthoselenaz ole nucleus, and a B-naphthothiazole nucleus, the m'eso-position of said dye being substituted with a methyl or ethyl group and, preferably, at least one of the N-substituents of said heterocyclic nuclei being a sulfoalkyl group or a carboxy alkyl groupvMore specifically, weare speaking of sensitizing dyes of the following general formula (I), and at least one merocyanine dye, wherein a tetrazole derivative nucleus and a merocyanine nucleus-are connected through a dimethine chain, more specifically, sensitizing dyes of the following general formula (II):
wherein R and R each represents a lower alkyl group, such as methyl, ehtyl, propyl, gamma-sulfopropyl-, gamma-sulfobutyl, delta-sulfobutyl, beta-hydroxyethyl, beta-carboxyethyl, allyl group, etc.; A represents a lower alkyl group, preferably a methyl or an ethyl group; Z and Z each represents the 1 non-metallic atoms necessary to complete a benzothiazole; benzoselenazole, beta-naphthoselenazole, or betanaphthothiazole nucleus, which may be substituted with a halogen atom, such as chlorine, bromine, etc., a lower alkyl group, such as methyl, ethyl, etc., an alkoxy group, such as methoxy, ethoxy, etc., an alko xycarbonylgroup, such .as methoxycarbonyl, ethoxycarbonyl, etc., an aryl group, such as phenyl, toluyl, etc.; X, represents an anion, such as chloride, bromide,- iodide,
. methylsulfate, p-toluenesulfonate, etc.; m is 0 or 1, and
m 0 if an intermolecular salt is formed with R1 or R nucleus is defined as a heterocyclic nucleus'containing a O -ii-o= group (refer to C. E. Mees. The Theory of the Photographic Process," Revised Edition. pages 4l5 to 420).
DETAILED DESCRIPTIONOF THE INVENTION The cyanine dyes of this invention having the general formula (I) have their maximum sensitization part between 595 and 690 nm, and many of them have high red sensitivity. Some of the sensitizing dyes having the general formula (11) have their maximum sensitization part between 460 and 560 um, and others do not exhibit remarkable spectral sensitization action, even when used together with a silver iodide emulsion.
The red sensitivity arising from the sensitizing dye of the general formula (I) is further raised, thewhite light sensitivity is remarkably raised and the silver halide photographic emulsion, which almost does not cause intrinsic desensitization, can be obtained by the combined use of at least one of the sensitizing dyes of the general formula (1) and at least one of the sensitizing dyes of the general formula (11), which have the said characteristics. Above all, the combination of meso-methyl-carbocyanine, being one of the sensitizing dyes represented by the general formula (I), and the sensitizing dye of the general formula (ll) wherein Z is sulfur, remarkably raises the white light sensitivity and red sensitivity, and brings about remarkable maximum sensitization around 630 nm. This shows that the dye having the general formula (II) remarkably strengthens the J-band of the J-band type dye of the carbocyanine sensitizing dyes represented by the general formula (I). This is one of the unique characteristics of this invention. The combination of the dye represented by the general formula (I) (e.g., mesoethyl-thiacarbocyanine) and the sensitizing dye represented by the general formula (ll) wherein Z is an oxygen atom rather sensitizes while strengthening the J- band of the J-band type dye without changing the spectral sensitivity distribution thereof. This is effective for the red sensitization for the red-sensitive layer of color photography. The tendency of the .l-band strenghtening, of the supersensitizing action and of the effect of prohibiting the desensitization is not injured by using oghochromatic sensitizing dyes, such as 2,2-cyanine, pseudocyanine, and the like. V
The sensitizing dyes of the general formula (1) do not deteriorate the dot quality obtained by the infectious development employed for the sensitive material for print plate making in proportion to the fact that they strongly and spectrally supersensitize to the relatively long wavelength of 690 nm. The application of the known supersensitizing art using cyanine dyes together in order to raise the spectral sensitivity badly deteriorates the dot quality. For example, the application of the supersensitizing art described in the specification of US. Pats. Nos. 2,533,426, 2,688,545, and 2,751,298, the specification of German Pat. No. 1,547,641, the specification of German Patent Prepublication No. 1,813,001, Japanese Patent Publication No. 16169/68 and No. 4132/68 are disadvantageous because of the reason described above.
The merocyanine dye represented by the general formula rather strengthens the infectious development, and is useful to obtain good dot quality. Accordingly, the supersensitizing art of this invention is useful espe cially for the panchromatic sensitization of the sensitive material for printing plates which are to be subjected to the treatment of infectious development.
The effects brought about by the groups R B and R the region of which is concretely mentioned before, are
HzhOH CaH1 Those skilled in the art can readily synthesize the sensitizing carbocyanine dyes to be used in this invention according to the description in the specification of U.S. Pat. Nos. 2,238,231, 2,503,776 and 3,177,210, German Pat. Nos. 929,080 and 1,072,765, etc., and the sensitizing merocyanine dyes according to the description in the specification of German Pat. No. 1,019,418.
The spectral sensitization method of this invention is useful for the spectral sensitization of the gelatinosilver-halide photographic emulsion. It is also useful for the emulsion containing a hydrophilic polymer, other than gelatin, such as agar collodion, water-soluble cellulose derivatives, polyvinyl alcohol, polyvinyl- -pyrrolidone copolymer and other synthesized hydrophilic resin, natural hydrophilic polymer, gelatin derivatives, and the like.
The photographic emulsion to be used in this invention is suitably a mixed silver halide comprising at least two of silver chloride, silver bromide and silver iodide. To produce the spectrally sensitized photographic emulsion in this invention, the sensitizing dye according to this invention is introduced into a photographic emulsion according to a conventional method. Usually, dyes are dissolved in a solvent, such as methanol, ethanol, water, cellosolve, water-soluble ketones, etc., and added to an emulsion. Alternatively, dyes may also be dissolved in an oil, slightly soluble in water, then added to water or a hydrophilic colloid to disperse the same.
The mol ratio of the sensitizing carbocyanine to the sensitizing merocyanine to be contained in the emulsion can vary widely from 9:1 to 1:9 depending upon the effects desired. The amount of each of the dyes is preferably in the range of from 1 X 10" to l X 10 mol per mol of silver according to the character of the emulsion employed.
The photographic emulsion of this invention can be subjected to further hypersensitization and other supersensitization in the known manner. In the production, conventional additives, such as chemical sensitizers,
7 stabilizers, antibronzing agents, hardeners, surface active agents, antifoggants, plasticizers, development accelerators, color couplers, fluorescent brightening agents, may be contained in the photographic emulsion of this invention in a conventional manner.
The photographic emulsion of this invention may be coated in a common manner on a suitable support, such as a glass plate, film of a cellulose derivative, film of a synthetic resin, Baryta paper, resin-coated paper, etc.
A better understanding of the present invention will be attained from the following examples, which are merely intended to be illustrative and not limitative thereof.
Examples A silver halide photographic emulsion was prepared 'by adding separately the dye of this invention illustrated before and to be used in this invention independently to a silver bromoiodide emulsion (AglzAgBr 7 molsz93 mols). On the other hand, a silver halide photographic emulsion containing both the earbocyanine dye and the merocyanine dye was prepared.
7 pfthese emulsions was coated on a triacetylcel- TABLE 1 The Composition of the Developer Metol 2 g Sodium sulfite 100 g Hydroquinone 5 g Borax 2 g Water to make up 1 I.
In the following Table 2, the resulting white light sensitivity and red sensitivity obtained by the independent addition of the sensitizing dyes illustrated before and/or the combinedaddition thereof and the intrinsic sensitivity relative to that of the starting emulsion are given.
Table 2 Exper- Exsensitizing dye- Emul- I-Iaximum Rel- Rel- In- Specimenam-- Amount of dye s ion sansiative atlvc trintrotal ple added tizawhite red sic gram No. No. ("5mo1/kg of tion light sensisensiemulsion) (mm) sensitivity tivity tivity A (2) AgBr 600 90 94 i /I 1 A (4) 630 100 90 90 Fig.1 A (8) E 632 130 120 Curve 1 (2) 5 0 82 o 100 1 5 0 88 o 116 Curve 51 (8) 5 0 102 120 A (4) 1 (4) 632 A 140 120 120 1 A (8) 1 (4) 632 170 146 120 Curve 2 2 A (4) 1 (4) 630 164 120 116 4 9 (8) 42 86 o 100 4 A (4) X 9 (4) 632 120 100- 100 A (8) I 9 (4) 632 150 120 100 7 (2) 540 o 110 5 7 (8) 540 o 116 5 A (4) '1 (4) 610/630 120 100' A 7 (8) 610 150 100 116 5 8 (4) 530 76 o 88 i 8 (8) 530 76 o 88 L (2) g 600 70 25 94 6 L g 630 90 6o. 88 1, (8) 5 630 90 8o 6 L (4) 8 (4) 628 100 68 88 L (8) g 8 (4) 628 12g 100 80 T3l :?ll'lq,- Expcr- Exsensitizing dye- Emuli-Iaximum Re l- Rel- In- Spec imenam- Amount of dye sion sensia'tive ative trintrocal ple added tizawhite red sic gram No. No. (lO" m0l/kg of tion light sensisensiemulsion) (nm) sensitivi by tivity tivity B g r 95 5 B (4) 6 11 135 88 Fig.6 7 B (8) 665 130 170 78 Curve 6 (4) 535 100 0 110 Curve 9 545 1 1 O 9 J (2) 600 30 Fig.4 J (4) 630 100 88 100 8 J (8) 630 128 98 J (4) 6 630 135 108 110 'f 8 J 6 (8) 612 140 100 110 c (4) 3; 654 100 100 95 Fig.2
0 (6) 658 108 92 Curve 3 c (8) 660 110 90 2 85 O 116 Cfirve 2 9 c (6) 2 H l 660 135 98 c (6) 2 (8) 660 152 1 6 100 Curve 4 3 (4) 1 5 8O 0 94 3 (8) 1 520 88 0 90 lo 10 c (6) 3 (4) 660 118 130 94 c (6) 3 (8) j 660 118 94 0 (1) 634 60 30 94 Fig.5 n G 4 7 43 9 G (4) 5 1 66 5 n 0 (2) 3 (4) 655 82 60 90 G 3 55 82 73 9 Table II Cntinued Expcr- Exsensitizing dye- Emul- Maximum Rel- Rel- In- Specimenam- Amount of dye sion sensiative ative trin- "urotal ple acldad tization white red sic gram No. No. (lO'Smol/kg of (nm) light sensisensiemulsion) sensibivity civity bivity 11 (6) 660 105 150 85 11 (8) 660 112 160 80v 4 00 100 Fig.5
l4 4 (8) 500 83 104 Curve 12 14 F (4) 4 (4) 642 11 88 94 F (4) 4 (8) 642 110 83 104 G (2) 4 (4) 22 80 54 9O Curve 14 15 15 c 2) 4 a) 655 1 9 16 K (4) 6 (4) 630 100 100 Fig- 3 x (8) 6 (4) 630 1 8 110 100 Curve 7 a (1) 2 (8) 684 94 210 104 Curve 8 Table H-Cntinued rtlxper Exsensitizing; dye- Eqmli-laxin aum Re1- TRe-L- In:- Spec- 1menarn- Amount of dye slon sens1- atlve. ative trlnirecal ple added tiza'bion white red sic gram No. No. (lOinol/kg of 1 (nm) light ser'1siscnsiemulsion) sensitivi by tivity tivity 1 (4) u 650 120 86 19 I (6) 650 135 82 I I 5 5 14 75 4 1 1 (4) 5 9 V 5 I (6) 1 (8) 650 110 178 104 E 5 9 71 92 E (4) 650 96 88 88 2O 1: (8) 650 10 85 E (4) 5 (4) 5 1 94 94 20 E (8) 5 (4) 650 110 98 10(4) 540 85 0 106 21 10(8) 5 0 96 0 110 L (4) (4) 628 72 96 21 L (8) 10(4) 628 138 108 9 22 22 L (4) 10(4)) 628 1 6 108 96 A (6 Q) 1 (4) 632' 152 152 108 23 0(0. 3) 24 24 A (6 4) 1 (4i) 630 178 5 152 102 0(0. 3;) 11(21) I H (1)) 670 108 260 86 5 1 Y I (4) H (1%) 680 100 164 84 26 A (4) A (4-). H (1)) 680 118 200 82 27 1s (4) In the aforementioned table, the white light sensitivity and the red sensitivity are given relative to the corresponding sensitivities obtained by exposing to the said daylight source without a filter or through a red filter using a sample containing 4 X moi/kg of emulsion of the sensitizing dye C, being calculated as 100. The intrinsic sensitivity is given relative to the sensitivity obtained by exposing the starting emulsion through a blue filter, being calculated as 100.
As is obvious from the result given in Table 2, the white light sensitivity and the red light sensitivity obtained by the combined use of the sensitizing dyes of this invention are far higher than those obtained by the independent use thereof.
As is shown in Examples Nos. 2, 3 and 22 in Table 2, the sensitizing effect obtained by the combination of at least one of the carbocyanine dyes and at least one of the merocyanine dyes is not deteriorated if an orthochromatic sensitizing dye already known, such as that of 11 or 12, is further used together. The orthochromatic sensitizing dyes used together with the sensitizing dyes employed in this invention are, for example, 2,2- cyanine and pseudo-type cyanine (e.g., 2'-thiacyanine) having the following chemical structures, but are not solely limited to these.
(EzHs Although the present invention has been adequately discussed above in the foregoing specification and examples, it is readily apparent that various changes and modifications can be made without departing from the spirit and scope thereof.
What is claimed is:
l. A silver halide photographic emulsion comprising a supersensitizing combination of at least one sensitizing carbocyanine dye having two heterocyclic nuclei selected from the group consisting of a benzothiazole nucleus, a benzoselenazole nucleus, a B-naphthoselenazole nucleus and a B-naphthothiazole nucleus, the meso-position of said dye being substituted with a member selected from the group consisting of a methyl and an ethyl group, and at least one merocyanine dye in which a tetrazole derivative nucleus and a merocyanine nucleus are connected through a dimethine chain.
2. The silver halide photographic emulsion of claim 1, wherein at least one of the N-substituents of the heterocyclic nuclei of the carbocyanine dye is a member selected from the group consisting of a sulfoalkyl and a carboxyalkyl group.
3. The silver halide photographic emulsion of claim 1, wherein the carbocyanine dye is represented by the following formula (I) and the merocyanine dye by the following generalforrnula (II):
wherein R, and R, each represents a lower alkyl group; A represents a member selected from the group con sisting of a methyl and an ethyl group; Z and Z,
represent nonmetallic atoms necessary to complete a.
ring selected from the group consisting of a benzothiazole nucleus, a benzoselenazole nucleus, a fi-naphthoselenazole nucleus, and a B-naphthothiazole nucleus; X
represents an anion; and m represents 0 or 1, provided that m 0 when an intermolecular salt is-formed:
wherein R and R each represents a lower alkyl group; B represents a member selected from the group consisting of a lower alkyl and an aryl group; Z represents a member selected from the group consisting of =NR an oxygen atom, and a sulfur atom; R being a lower alkyl group.
4. The silver halide photographic emulsion of claim 3, wherein Z; of the formula (II) is an oxygen atom.
5. The silver halide photographic emulsion of claim 4, wherein Z, and Z of formula (I) are nonmetallic atoms necessary to complete a member selected from the group consisting of a benzothiazole and a B-naphthothiazole nucleus.
6. The silver halide photographic emulsion of claim 3, wherein A'of formula (I) is a'methyl group and Z of formula (II) is a sulfur atom.
7. The silver halide photographic emulsion of claim 1, wherein the emulsion further contains at least one orthochromatic sensitizing dye.
8. The silver halide photographic. emulsion of claim 7, wherein the orthochromatic sensitizing dye is selected from the group consisting of a 2,2'-cyanine dye and a pseudo-type cyanine dye.
9. The silver halide photographic emulsion of claim v1, wherein the carbocyanine dye is selected from the group consisting of and the merocyanine dye is selected from the group 6 consi t ing of H I V {102E933 21 22 10. The silver halide photographic emulsion of claim and 7, wherein the orthochromatic sensitizing dye is selected from the group consisting of N CHCHS :l S zHa O \N -S V7 7 C H;CH=CHI I 10 13. The silver halide photographic emulsion compris- 2H5 ing a supersensitizing combination of and Se S a 2 s CH-,=CH fi CH N/ co COQCH3 N N rc miisoanm znm Da a and N-NCH:
l 1. A silver halide photographic emulsion comprising N CH 0 a supersen sitizing combination of (iIH1C H=CH1 O S N s s MM WW M (13135 EH3 =CH =CH- 14. The silver halide photographic emulsion comprisg/ ing a supersensitizing combination of S S Z2115 S 02H =CH- :cn- J =CH- =CH C1 C1 me CH N N If oHnasoaHN orrmsoa- (HmSOsH (HmsOr and and NN-CH, 1TNCH; CHI-CH s 40 CHCH o l L if I Hz-CH=CH 0 =5 zHs O Ig -S 2 11/ 2H5 Hz CH--C2 s 15. The silver halide photographic material compris- 12. The silver halide photographic emulsion comprisin a l r ntai i th ilv r h lid l i f ing a supersensitizing combination of claim 1 V. V.V. mm 7 16. The silver halide photographic emulsion of claim 5 s 1, wherein the mol ratio of said carbocyanine dye to said merocyanine dye ranges from 9:1 to l:9.' I 17. The silver halide photographic emulsion of claim 1, wherein each of said cyanine and merocyanine dye LL is present in an amount of l X l()' to I X l0 mol pcr nmsommcnma mol of Silven (HDaSOa'
Claims (16)
- 2. The silver halide photographic emulsion of claim 1, wherein at least one of the N-substituents of the heterocyclic nuclei of the carbocyanine dye is a member selected from the group consisting of a sulfoalkyl and a carboxyalkyl group.
- 3. The silver halide photographic emulsion of claim 1, wherein the carbocyanine dye is represented by the following formula (I) and the merocyanine dye by the following general formula (II):
- 4. The silver halide photographic emulsion of claim 3, wherein Z3 of the formula (II) is an oxygen atom.
- 5. The silver halide photographic emulsion of claim 4, wherein Z1 and Z2 of formula (I) are nonmetallic atoms necessary to complete a member selected from the group consisting of a benzothiazole and a Beta -naphthothiazole nucleus.
- 6. The silver halide photographic emulsion of claim 3, wherein A of formula (I) is a methyl group and Z3 of formula (II) is a sulfur atom.
- 7. The silver halide photographic emulsion of claim 1, wherein the emulsion further contains at least one orthochromatic sensitizing dye.
- 8. The silver halide photographic emulsion of claim 7, wherein the orthochromatic sensitizing dye is selected from the group consisting of a 2,2''-cyanine dye and a pseudo-type cyanine dye.
- 9. The silver halide photographic emulsion of claim 1, wherein the carbocyanine dye is selected from the group consisting of
- 10. The silver halide photographic emulsion of clAim 7, wherein the orthochromatic sensitizing dye is selected from the group consisting of
- 11. A silver halide photographic emulsion comprising a supersensitizing combination of
- 12. The silver halide photographic emulsion comprising a supersensitizing combination of
- 13. The silver halide photographic emulsion comprising a supersensitizing combination of
- 14. The silver halide photographic emulsion comprising a supersensitizing combination of
- 15. The silver halide photographic material comprising a layer containing the silver halide emulsion of claim 1.
- 16. The silver halide photographic emulsion of claim 1, wherein the mol ratio of said carbocyanine dye to said merocyanine dye ranges from 9:1 to 1:9.
- 17. The silver halide photographic emulsion of claim 1, wherein each of said cyanine and merocyanine dye is present in an amount of 1 X 10 6 to 1 X 10 3 mol per mol of silver.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP45084532A JPS4842500B1 (en) | 1970-09-28 | 1970-09-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3769026A true US3769026A (en) | 1973-10-30 |
Family
ID=13833235
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00184604A Expired - Lifetime US3769026A (en) | 1970-09-28 | 1971-09-28 | Spectrally sensitized silver halide photographic emulsion |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3769026A (en) |
| JP (1) | JPS4842500B1 (en) |
| CA (1) | CA988771A (en) |
| DE (1) | DE2148425B2 (en) |
| FR (1) | FR2108036B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030219685A1 (en) * | 2002-03-13 | 2003-11-27 | Agfa-Gevaert | Method for preparation of a photothermographic material with increased photosensitivity |
| EP1750173A1 (en) | 2005-08-04 | 2007-02-07 | Fuji Photo Film Co., Ltd. | Silver halide photosensitive material and packaged body containing the same |
| WO2025058077A1 (en) | 2023-09-15 | 2025-03-20 | 富士フイルム株式会社 | Compound, composition, functional material, photographic photosensitive silver halide material, and diffusion transfer type photographic photosensitive silver halide material |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60119483U (en) * | 1984-01-23 | 1985-08-12 | 高山 彬弘 | play equipment |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2430558A (en) * | 1945-10-26 | 1947-11-11 | Eastman Kodak Co | Photographic emulsion sensitized with combination of merocyanine dye and a monomethinecyanine, a trimethinecyanine, a dimethinehemicyanine, or a styryl dye |
| DE1019418B (en) * | 1954-01-21 | 1957-11-14 | Hoechst Ag | Process for the preparation of sensitizing dyes |
-
1970
- 1970-09-28 JP JP45084532A patent/JPS4842500B1/ja active Pending
-
1971
- 1971-09-28 CA CA123,828A patent/CA988771A/en not_active Expired
- 1971-09-28 FR FR717134850A patent/FR2108036B1/fr not_active Expired
- 1971-09-28 DE DE2148425A patent/DE2148425B2/en active Granted
- 1971-09-28 US US00184604A patent/US3769026A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2430558A (en) * | 1945-10-26 | 1947-11-11 | Eastman Kodak Co | Photographic emulsion sensitized with combination of merocyanine dye and a monomethinecyanine, a trimethinecyanine, a dimethinehemicyanine, or a styryl dye |
| DE1019418B (en) * | 1954-01-21 | 1957-11-14 | Hoechst Ag | Process for the preparation of sensitizing dyes |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030219685A1 (en) * | 2002-03-13 | 2003-11-27 | Agfa-Gevaert | Method for preparation of a photothermographic material with increased photosensitivity |
| US7067243B2 (en) * | 2002-03-13 | 2006-06-27 | Agfa Gevaert | Method for preparation of a photothermographic material with increased photosensitivity |
| EP1750173A1 (en) | 2005-08-04 | 2007-02-07 | Fuji Photo Film Co., Ltd. | Silver halide photosensitive material and packaged body containing the same |
| WO2025058077A1 (en) | 2023-09-15 | 2025-03-20 | 富士フイルム株式会社 | Compound, composition, functional material, photographic photosensitive silver halide material, and diffusion transfer type photographic photosensitive silver halide material |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2108036A1 (en) | 1972-05-12 |
| JPS4842500B1 (en) | 1973-12-13 |
| DE2148425A1 (en) | 1972-07-20 |
| DE2148425B2 (en) | 1973-10-18 |
| DE2148425C3 (en) | 1974-05-16 |
| CA988771A (en) | 1976-05-11 |
| FR2108036B1 (en) | 1973-05-11 |
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